Efficient and reversible separation of NH3 by deep eutectic solvents with multiple active sites and low viscosities

doi:10.1016/j.cjche.2023.10.012

中国化学工程学报 ›› 2024, Vol. 67 ›› Issue (3): 97-105.DOI: 10.1016/j.cjche.2023.10.012

Efficient and reversible separation of NH₃ by deep eutectic solvents with multiple active sites and low viscosities

Jiayin Zhang¹, Lu Zheng¹, Siqi Fang¹, Hongwei Zhang¹, Zhenping Cai¹, Kuan Huang^1,2, Lilong Jiang^1,2

1 National Engineering Research Center of Chemical Fertilizer Catalyst (NERC-CFC), College of Chemical Engineering, Fuzhou University, Fuzhou 350002, China;
2 Qingyuan Innovation Laboratory, Quanzhou 362801, China

收稿日期:2023-07-09 修回日期:2023-10-25 出版日期:2024-03-28 发布日期:2024-06-01
通讯作者: Kuan Huang,E-mail address:huangk@fzu.edu.cn;Lilong Jiang,E-mail address:jll@fzu.edu.cn.
基金资助:
This work was supported by the National Natural Science Foundation of China (22221005 and 22008033).

Efficient and reversible separation of NH₃ by deep eutectic solvents with multiple active sites and low viscosities

Jiayin Zhang¹, Lu Zheng¹, Siqi Fang¹, Hongwei Zhang¹, Zhenping Cai¹, Kuan Huang^1,2, Lilong Jiang^1,2

1 National Engineering Research Center of Chemical Fertilizer Catalyst (NERC-CFC), College of Chemical Engineering, Fuzhou University, Fuzhou 350002, China;
2 Qingyuan Innovation Laboratory, Quanzhou 362801, China

Received:2023-07-09 Revised:2023-10-25 Online:2024-03-28 Published:2024-06-01
Contact: Kuan Huang,E-mail address:huangk@fzu.edu.cn;Lilong Jiang,E-mail address:jll@fzu.edu.cn.
Supported by:
This work was supported by the National Natural Science Foundation of China (22221005 and 22008033).

摘要/Abstract

摘要： The efficient separation and collection of ammonia (NH₃) during NH₃ synthesis process is essential to improve the economic efficiency and protect the environment. In this work, ethanolammonium hydrochloride (EtOHACl) and phenol (PhOH) were used to prepare a novel class of deep eutectic solvents (DESs) with multiple active sites and low viscosities. The NH₃ separation performance of EtOHACl + PhOH DESs was analyzed completely. It is figured out that the NH₃ absorption rates in EtOHACl + PhOH DESs are very fast. The NH₃ absorption capacities are very high and reach up to 5.52 and 10.74 mol·kg^-1 at 11.2 and 100.4 kPa under 298.2 K, respectively. In addition, the EtOHACl + PhOH DESs present highly selective absorption of NH₃ over N₂ and H₂ and good regenerative properties after seven cycles of absorption/desorption. The intrinsic separation mechanism of NH₃ by EtOHACl + PhOH DESs was further revealed by spectroscopic analysis and quantum chemistry calculations.

关键词: Separation, Absorption, Ionic liquid, Deep eutectic solvent, Multiple active site, Low viscosity

Abstract: The efficient separation and collection of ammonia (NH₃) during NH₃ synthesis process is essential to improve the economic efficiency and protect the environment. In this work, ethanolammonium hydrochloride (EtOHACl) and phenol (PhOH) were used to prepare a novel class of deep eutectic solvents (DESs) with multiple active sites and low viscosities. The NH₃ separation performance of EtOHACl + PhOH DESs was analyzed completely. It is figured out that the NH₃ absorption rates in EtOHACl + PhOH DESs are very fast. The NH₃ absorption capacities are very high and reach up to 5.52 and 10.74 mol·kg^-1 at 11.2 and 100.4 kPa under 298.2 K, respectively. In addition, the EtOHACl + PhOH DESs present highly selective absorption of NH₃ over N₂ and H₂ and good regenerative properties after seven cycles of absorption/desorption. The intrinsic separation mechanism of NH₃ by EtOHACl + PhOH DESs was further revealed by spectroscopic analysis and quantum chemistry calculations.

Key words: Separation, Absorption, Ionic liquid, Deep eutectic solvent, Multiple active site, Low viscosity

Jiayin Zhang, Lu Zheng, Siqi Fang, Hongwei Zhang, Zhenping Cai, Kuan Huang, Lilong Jiang. Efficient and reversible separation of NH₃ by deep eutectic solvents with multiple active sites and low viscosities[J]. 中国化学工程学报, 2024, 67(3): 97-105.

参考文献

[1] A.R. Mankar, A. Pandey, A. Modak, K.K. Pant, Pretreatment of lignocellulosic biomass:A review on recent advances, Bioresour. Technol. 334(2021)125235.
[2] A. Pearson, Refrigeration with ammonia, Int. J. Refrig. 31(4)(2008)545-551.
[3] H. Kobayashi, A. Hayakawa, K.D.K.A. Somarathne, E.C. Okafor, Science and technology of ammonia combustion, Proc. Combust. Inst. 37(1)(2019)109-133.
[4] M.S. Huberty, A.L. Wagner, A. McCormick, E. Cussler, Ammonia absorption at Haber process conditions, AIChE J. 58(11)(2012)3526-3532.
[5] M.A. Sutton, J.W. Erisman, F. Dentener, D. Moller, Ammonia in the environ-ment:From ancient times to the present, Environ. Pollut. 156(3)(2008)583-604.
[6] L. Zhang, H.F. Dong, S.J. Zeng, Z.Y. Hu, S. Hussain, X.P. Zhang, An overview of ammonia separation by ionic liquids, Ind. Eng. Chem. Res. 60(19)(2021)6908-6924.
[7] F.J. Liu, K.A. Huang, L.L. Jiang, Promoted adsorption of CO₂ on amineimpregnated adsorbents by functionalized ionic liquids, AIChE J. 64(10)(2018)3671-3680.
[8] Z.P. Cai, Y.D. Ma, J.Y. Zhang, W.Q. Wu, Y.N. Cao, L.L. Jiang, K. Huang, Tunable ionic liquids as oil-soluble precursors of dispersed catalysts for suspendedbed hydrocracking of heavy residues, Fuel 313(2022)122664.
[9] K. Huang, X.M. Zhang, L.S. Zhou, D.J. Tao, J.P. Fan, Highly efficient and selective absorption of H₂S in phenolic ionic liquids:A cooperative result of anionic strong basicity and cationic hydrogen-bond donation, Chem. Eng. Sci. 173(2017)253-263.
[10] F.F. Chen, K.A. Huang, J.P. Fan, D.J. Tao, Chemical solvent in chemical solvent:A class of hybrid materials for effective capture of CO₂, AIChE J. 64(2)(2018)632-639.
[11] W.J. Xiong, X.M. Zhang, X.B. Hu, Y.T. Wu, Self-separation ionic liquid catalyst for the highly effective conversion of H₂S by a, b-unsaturated carboxylate esters under mild conditions, Green Energy Environ.(2023), https://doi.org/10.1016/j.gee.2023.03.001.
[12] S.Y. Wen, T. Wang, X.M. Zhang, W.G. Xu, X.B. Hu, Y.T. Wu, Novel amino acid ionic liquids prepared via one-step lactam hydrolysis for the highly efficient capture of CO₂, AlChE. J. 69(11)(2023) e18206.
[13] Z.J. Li, X.P. Zhang, H.F. Dong, X.C. Zhang, H.S. Gao, S.J. Zhang, J.W. Li, C.M. Wang, Efficient absorption of ammonia with hydroxyl-functionalized ionic liquids, RSC Adv. 5(99)(2015)81362-81370.
[14] D.W. Shang, X.P. Zhang, S.J. Zeng, K. Jiang, H.S. Gao, H.F. Dong, Q.Y. Yang, S.J. Zhang, Protic ionic liquid[Bim][NTf₂] with strong hydrogen bond donating ability for highly efficient ammonia absorption, Green Chem. 19(4)(2017)937-945.
[15] J.L. Wang, S.J. Zeng, F. Huo, D.W. Shang, H.Y. He, L. Bai, X.P. Zhang, J.W. Li, Metal chloride anion-based ionic liquids for efficient separation of NH₃, J. Clean. Prod. 206(2019)661-669.
[16] Z.P. Cai, J.Y. Zhang, Y.D. Ma, W.Q. Wu, Y.N. Cao, K.A. Huang, L.L. Jiang, Chelation-activated multiple-site reversible chemical absorption of ammonia in ionic liquids, AIChE J. 68(5)(2022) e17632.
[17] S.J. Zeng, L. Liu, D.W. Shang, J.P. Feng, H.F. Dong, Q.X. Xu, X.P. Zhang, S.J. Zhang, Efficient and reversible absorption of ammonia by cobalt ionic liquids through Lewis acid-base and cooperative hydrogen bond interactions, Green Chem. 20(9)(2018)2075-2083.
[18] D.W. Shang, S.J. Zeng, X.P. Zhang, X.C. Zhang, L. Bai, H.F. Dong, Highly efficient and reversible absorption of NH₃ by dual functionalised ionic liquids with protic and Lewis acidic sites, J. Mol. Liq. 312(2020)113411.
[19] J.Y. Zhang, L. Zheng, Y.D. Ma, Z.P. Cai, Y.N. Cao, K.A. Huang, L.L. Jiang, A minireview on NH₃ separation technologies:Recent advances and future directions, Energy Fuels 36(24)(2022)14516-14533.
[20] F.J. Liu, W. Chen, J.X. Mi, J.Y. Zhang, X. Kan, F.Y. Zhong, K.A. Huang, A.M. Zheng, L. L. Jiang, Thermodynamic and molecular insights into the absorption of H₂S, CO₂, and CH₄ in choline chloride plus urea mixtures, AIChE J. 65(5)(2019) e16574.
[21] O.V. Kazarina, V.N. Agieienko, A.N. Petukhov, A.V. Vorotyntsev, M.E. Atlaskina, A.A. Atlaskin, S.S. Kryuchkov, A.N. Markov, A.V. Nyuchev, I.V. Vorotyntsev, Deep eutectic solvents composed of urea and new salts of a choline family for efficient ammonia absorption, J. Chem. Eng. Data 67(1)(2022)138-150.
[22] W.J. Jiang, F.Y. Zhong, Y. Liu, K.A. Huang, Effective and reversible capture of NH₃ by ethylamine hydrochloride plus glycerol deep eutectic solvents, ACS Sustain. Chem. Eng. 7(12)(2019)10552-10560.
[23] N.N. Cheng, Z.L. Li, H.C. Lan, W.L. Xu, W.J. Jiang, K. Huang, H.L. Peng, Deep eutectic solvents with multiple weak acid sites for highly efficient, reversible and selective absorption of ammonia, Sep. Purif. Technol. 269(2021)118791.
[24] Y.N. Cao, J.Y. Zhang, Y.D. Ma, W.Q. Wu, K.A. Huang, L.L. Jiang, Designing lowviscosity deep eutectic solvents with multiple weak-acidic groups for ammonia separation, ACS Sustain. Chem. Eng. 9(21)(2021)7352-7360.
[25] N.N. Cheng, Z.L. Li, H.C. Lan, W.L. Xu, K.A. Huang, Remarkable NH₃ absorption in metal-based deep eutectic solvents by multiple coordination and hydrogen-bond interaction, AIChE J. 68(6)(2022) e17660.
[26] X.X. Sun, Q.H. Wang, S.H. Wu, X.Y. Zhao, L.G. Wei, K.L. Li, J.G. Hao, L. Wei, S.R. Zhai, Q.D. An, Metal chlorides-promoted ammonia absorption of deep eutectic solvent, Int. J. Hydrogen Energy 47(36)(2022)16121-16131.
[27] Z.L. Li, F.Y. Zhong, J.Y. Huang, H.L. Peng, K. Huang, Sugar-based natural deep eutectic solvents as potential absorbents for NH₃ capture at elevated temperatures and reduced pressures, J. Mol. Liq. 317(2020)113992.
[28] Y.D. Ma, J.Y. Zhang, K. Huang, L.L. Jiang, Highly efficient and selective separation of ammonia by deep eutectic solvents through cooperative acid-base and strong hydrogen-bond interaction, J. Mol. Liq. 337(2021)116463.
[29] K. Li, K. Zong, Z.Y. Zhou, D.S. Deng, Highly efficient absorption and separation of NH₃ by simple lithium deep eutectic solvents, Sep. Purif. Technol. 279(2021)119763.
[30] J.Y. Zhang, Y.D. Ma, W.Q. Wu, Z.P. Cai, Y.N. Cao, K. Huang, L.L. Jiang, Carboxylic functionalized mesoporous polymers for fast, highly efficient, selective and reversible adsorption of ammonia, Chem. Eng. J. 448(2022)137640.
[31] W.J. Jiang, F.Y. Zhong, L.S. Zhou, H.L. Peng, J.P. Fan, K. Huang, Chemical dualsite capture of NH₃ by unprecedentedly low-viscosity deep eutectic solvents, Chem. Commun. 56(16)(2020)2399-2402.
[32] L. Zheng, X.Y. Zhang, Q.K. Li, Y.D. Ma, Z.P. Cai, Y.N. Cao, K. Huang, L.L. Jiang, Effective ammonia separation by non-chloride deep eutectic solvents composed of dihydroxybenzoic acids and ethylene glycol through multiplesite interaction, Sep. Purif. Technol. 309(2023)123136.
[33] P.J. Stephens, F.J. Devlin, C.S. Ashvar, C.F. Chabalowski, M.J. Frisch, Theoretical calculation of vibrational circular dichroism spectra, Faraday Discuss 99(1994)103-119.
[34] S. Grimme, J. Antony, S. Ehrlich, H. Krieg, A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu, J. Chem. Phys. 132(15)(2010)154104.
[35] M. Cossi, V. Barone, R. Cammi, J. Tomasi, Ab initio study of solvated molecules:A new implementation of the polarizable continuum model, Chem. Phys. Lett. 255(4-6)(1996)327-335.
[36] F.Y. Zhong, L.S. Zhou, J.A. Shen, Y. Liu, J.P. Fan, K.A. Huang, Rational design of azole-based deep eutectic solvents for highly efficient and reversible capture of ammonia, ACS Sustain. Chem. Eng. 7(16)(2019)14170-14179.
[37] M. Frenkel, X. Hong, Q. Dong, X. Yan, R.D. Chirico, 7.2. Unsaturated nitriles, densities, in:M. Frenkel, K.N. Marsh (Eds.), Densities of Phenols, Aldehydes, Ketones, Carboxylic Acids, Amines, Nitriles, and Nitrohydrocarbons, SpringerVerlag, Berlin, 2005, pp. 393-395.
[38] V.P. Wystrach, D.W. Kaiser, F.C. Schaefer, Preparation of ethylenimine and triethylenemelamine, J. Am. Chem. Soc. 77(22)(1955)5915-5918.
[39] R. Seto, K. Matsumoto, T. Endo, Stable heterocumulene monomer in water; Synthesis and polymerization of (meth) acrylates having an isothiocyanate structure, J. Polym. Sci. 51(21)(2013)4522-4529.
[40] X.Z. Duan, B. Gao, C. Zhang, D.S. Deng, Solubility and thermodynamic properties of NH₃ in choline chloride-based deep eutectic solvents, J. Chem. Thermodyn. 133(2019)79-84.
[41] Q. Luo, J.G. Hao, L.G. Wei, S.R. Zhai, Z.Y. Xiao, Q.D. An, Protic ethanolamine hydrochloride-based deep eutectic solvents for highly efficient and reversible absorption of NH₃, Sep. Purif. Technol. 260(2021)118240.
[42] J.Y. Huang, W.J. Jiang, P. Xiao, Z.T. Fan, F.Y. Zhong, H.L. Peng, J. Du, K. Huang, Physical properties and NH₃ solubilities of deep eutectic solvents formed by choline chloride and glycols, Fluid Phase Equil. 529(2021)112871.
[43] J.Y. Zhang, L.Y. Kong, K.A. Huang, NH₃ solubilities and physical properties of ethylamine hydrochloride plus urea deep eutectic solvents, J. Chem. Eng. Data 64(9)(2019)3821-3830.
[44] D.S. Deng, X.X. Deng, X.Z. Duan, L. Gong, Protic guanidine isothiocyanate plus acetamide deep eutectic solvents with low viscosity for efficient NH₃ capture and NH₃/CO₂ separation, J. Mol. Liq. 324(2021)114719.
[45] L. Yuan, H.S. Gao, H.Y. Jiang, S.J. Zeng, T. Li, B.Z. Ren, X.P. Zhang, Experimental and thermodynamic analysis of NH₃ absorption in dual-functionalized pyridinium-based ionic liquids, J. Mol. Liq. 323(2021)114601.
[46] Z.L. Li, F.Y. Zhong, L.S. Zhou, Z.Q. Tian, K.A. Huang, Deep eutectic solvents formed by N-methylacetamide and heterocyclic weak acids for highly efficient and reversible chemical absorption of ammonia, Ind. Eng. Chem. Res. 59(5)(2020)2060-2067.
[47] Z.Y. Zhou, R.J. Li, K. Li, K. Zong, D.S. Deng, Efficient and reversible absorption of low pressure NH₃ by functional type V deep eutectic solvents based on phenol and hydroxypyridine, New J. Chem. 46(45)(2022)21730-21736.
[48] Q. Luo, Q.H. Wang, X.X. Sun, H. Wu, J.G. Hao, L.G. Wei, S.R. Zhai, Z.Y. Xiao, Q.D. An, Dual-active-sites deep eutectic solvents based on imidazole and resorcinol for efficient capture of NH₃, Chem. Eng. J. 416(2021)129114.
[49] W.J. Jiang, J.B. Zhang, Y.T. Zou, H.L. Peng, K.A. Huang, Manufacturing acidities of hydrogen-bond donors in deep eutectic solvents for effective and reversible NH₃ capture, ACS Sustain. Chem. Eng. 8(35)(2020)13408-13417.
[50] O.V. Kazarina, A.N. Petukhov, R.N. Nagrimanov, A.V. Vorotyntsev, M.E. Atlaskina, A.A. Atlaskin, A.S. Kazarin, A.A. Golovacheva, Z.A. Markin, A.N. Markov, A. V. Barysheva, I.V. Vorotyntsev, The role of HBA structure of deep eutectic solvents consisted of ethylene glycol and chlorides of a choline family for improving the ammonia capture performance, J. Mol. Liq. 373(2023)121216.
[51] T. Makino, M. Kanakubo, NH₃ absorption in Brønsted acidic imidazolium-and ammonium-based ionic liquids, New J. Chem. 44(47)(2020)20665-20675.
[52] Y.L. Shi, Z.X. Wang, Z.Y. Li, H.Y. Wang, D.Z. Xiong, J.K. Qiu, X.X. Tian, G. Feng, J.J. Wang, Anchoring LiCl in the nanopores of metaleorganic frameworks for ultra-high uptake and selective separation of ammonia, Angew. Chem. Int. Ed. 61(47)(2022) e202212032.

Efficient and reversible separation of NH₃ by deep eutectic solvents with multiple active sites and low viscosities

Efficient and reversible separation of NH₃ by deep eutectic solvents with multiple active sites and low viscosities

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 15

编辑推荐

Metrics

本文评价

[1]	Shutong Pang, Hualiang An, Xinqiang Zhao, Yanji Wang. Ionic liquid-assisted preparation of hydroxyapatite and its catalytic performance for decarboxylation of itaconic acid[J]. 中国化学工程学报, 2024, 67(3): 9-15.
[2]	Kun Li, Han Tang, Shuangshuang Li, Zixuan Huang, Bei Liu, Chun Deng, Changyu Sun, Guangjin Chen. Highly efficient CO₂ capture using 2-methylimidazole aqueous solution on laboratory and pilot-scale[J]. 中国化学工程学报, 2024, 67(3): 148-156.
[3]	Shangyuan Cheng, Guisheng Qi, Yuliang Li, Yixuan Yang. Visual experimental study of nanofluids application to promote CO₂ absorption in a bubble column[J]. 中国化学工程学报, 2024, 67(3): 228-237.
[4]	Haozhe Yi, Taotao Fu, Chunying Zhu, Youguang Ma. The flow behavior of droplet adsorption on a liquid–liquid interface accompanied by cross-linking reaction and phase separation in a microchannel[J]. 中国化学工程学报, 2024, 66(2): 60-70.
[5]	Hongwei Jin, Yun Teng, Kangkang Li, Zhou Feng, Zhonghao Li, Shiqi Qu, Hongzhi Xia, Huanong Cheng, Yugang Li, Xinshun Tan, Shiqing Zheng. Absorption characteristics, model, and molecular mechanism of hydrogen sulfide in morpholine acetate aqueous solution[J]. 中国化学工程学报, 2024, 66(2): 125-135.
[6]	Xuepu Cao, Shengkun Jia, Xing Qian, Yiqing Luo, Xigang Yuan. Cascade equilibrium stage relaxation method by introducing equilibrium efficiency parameter[J]. 中国化学工程学报, 2024, 66(2): 145-156.
[7]	Zijiang Dou, Weiqiang Tang, Peng Xie, Shuangliang Zhao. Solvent effects on Diels–Alder reaction in ionic liquids: A reaction density functional study[J]. 中国化学工程学报, 2024, 66(2): 180-188.
[8]	Xiaodong Zhang, Lu Jin, Jinsheng Sun. Optimal synthesis of heat-integrated distillation configurations using the two-column superstructure[J]. 中国化学工程学报, 2024, 66(2): 238-249.
[9]	Xiaoxia Ye, Rixin Huang, Zhihong Zheng, Juan Liu, Jie Chen, Yuancai Lv. Anti-abrasion collagen fiber-based membrane functionalized by UiO-66-NH₂ with ultra-high efficiency and stability for oil-in-water emulsions separation[J]. 中国化学工程学报, 2024, 66(2): 285-297.
[10]	Yixuan Ma, Cong Yu, Lifeng Yang, Rimin You, Yawen Bo, Qihan Gong, Huabin Xing, Xili Cui. Boosting kinetic separation of ethylene and ethane on microporous materials via crystal size control[J]. 中国化学工程学报, 2024, 65(1): 85-91.
[11]	Peizhe Cui, Jiafu Xing, Chen Li, Mengjin Zhou, Jifu Zhang, Yasen Dai, Limei Zhong, Yinglong Wang. Environmental, economic and exergy analysis of separation of ternary azeotrope by variable pressure extractive distillation based on multi-objective optimization[J]. 中国化学工程学报, 2024, 65(1): 145-157.
[12]	Xudong Zhang, Yanhua Liu, Jun Shen, Yugao Wang, Gang Liu, Yanxia Niu, Qingtao Sheng. Insight into the experiment and extraction mechanism for separating carbazole from anthracene oil with quaternary ammonium-based deep eutectic solvents[J]. 中国化学工程学报, 2024, 65(1): 188-199.
[13]	Yuanyuan Yin, Xujun Wang, Lei Xu, Binbin He, Yunxiang Nie, Yi Mei. Simultaneous removal of sulfur dioxide and nitrogen oxide from flue gas by phosphorus sludge: The performance and absorption mechanism[J]. 中国化学工程学报, 2024, 65(1): 212-221.
[14]	Hui Yu, Xiaojia Wu, Chuanqi Geng, Xinyu Li, Chencan Du, Zhiyong Zhou, Zhongqi Ren. Highly selective extraction of aromatics from aliphatics by using metal chloride-based ionic liquids[J]. 中国化学工程学报, 2024, 65(1): 222-229.
[15]	Wenjian Yue, Xiaojiang Li, Junhao Jing, Li Tong, Na Wang, Hongsheng Lu, Zhiyu Huang. A CO₂-controllable phase change absorbent solvent used to waste recycling of dining lampblack[J]. 中国化学工程学报, 2023, 61(9): 110-117.