Systematic screening procedure and innovative energy-saving design for ionic liquid-based extractive distillation process

doi:10.1007/s11705-022-2234-3

Front. Chem. Sci. Eng.

2023, Vol. 17

Issue (1) : 34-45 https://doi.org/10.1007/s11705-022-2234-3

RESEARCH ARTICLE

Systematic screening procedure and innovative energy-saving design for ionic liquid-based extractive distillation process

Tuanjie Shen¹, Liumei Teng², Yanjie Hu³(

), Weifeng Shen⁴(

)

¹. Anhui XinShiJi Pharmaceutical Co., Ltd., Hefei 230000, China
². School of Materials Science and Engineering, Chongqing University of Arts and Sciences, Chongqing 402160, China
³. School of Materials and Energy, Guangdong University of Technology, Guangzhou 510006, China
⁴. School of Chemistry and Chemical Engineering, Chongqing University, Chongqing 400044, China

Download: PDF(6974 KB) HTML
Export: BibTeX | EndNote | Reference Manager | ProCite | RefWorks

Abstract

In the traditional extractive distillation process, organic solvents are often used as entrainers. However, environmental influence and high energy-consumption are significant problems in industrial application. In this study, a systematic screening strategy and innovative energy-saving design for ionic liquid-based extractive distillation process was proposed. The innovative energy-saving design focused on the binary minimum azeotrope mixtures isopropanol and water. Miscibility, environmental impact and physical properties (e.g., melting point and viscosity) of 30 ionic liquids were investigated. 1-Ethyl-3-methyl-imidazolium dicyanamide and 1-butyl-3-methyl-imidazolium dicyanamide were selected as candidate entrainers. Feasibility analysis of these two ionic liquids was further performed via residue curve maps, isovolatility line and temperature profiles. An innovative ionic liquid-based extractive distillation process combining distillation column and stripping column was designed and optimized with the objective function of minimizing the total annualized cost. The results demonstrate that the total annualized cost was reduced by 19.9% with 1-ethyl-3-methyl-imidazolium dicyanamide as the entrainer and by 24.3% with 1-butyl-3-methyl-imidazolium dicyanamide, compared with that of dimethyl sulfoxide. The method proposed in this study is conducive to the green and sustainable development of extractive distillation process.

Keywords ionic liquid entrainer screening feasibility analysis extractive distillation

Corresponding Author(s): Yanjie Hu,Weifeng Shen

About author:

Changjian Wang and Zhiying Yang contributed equally to this work.

Online First Date: 15 December 2022 Issue Date: 21 February 2023

Cite this article:

Tuanjie Shen,Liumei Teng,Yanjie Hu, et al. Systematic screening procedure and innovative energy-saving design for ionic liquid-based extractive distillation process[J]. Front. Chem. Sci. Eng., 2023, 17(1): 34-45.

URL:

https://academic.hep.com.cn/fcse/EN/10.1007/s11705-022-2234-3
https://academic.hep.com.cn/fcse/EN/Y2023/V17/I1/34

Fig.1 (a) The thermodynamic phase diagram of the azeotrope system using a heavy entrainer and (b) temperature profiles of each tray in the distillation column.

Fig.2 Existing isopropanol dehydration process by the conventional ED process.

Fig.3 The proposed isopropanol?water separation process by the use of ED and stripping columns.

Fig.4 The flowsheet of the sequential iterative linear optimization search.

Fig.5 Thermodynamic analysis on ED of isopropanol?water: (a) isovolatility line and RCM and (b) temperature profiles.

Tab.1 The physical properties of ILs [EMIM]DCA and [BMIM]DCA

Tab.2 NRTL binary interaction parameters for the isopropanol?water-entrainers system

Fig.6 (a) Effect of [EMIM]DCA entrainer solvent flowrate on the bottom temperature of distillation column and (b) effect of [BMIM]DCA entrainer solvent flowrate on the bottom temperature of distillation column.

Fig.7 The influence of key operating variables of DMSO on TAC, including (a) solvent flowrate, (b) the number of stage (N_T1) of EC, (c) TAC vs N_E and N_F for S = 100 kmol?h^–1, (d) number of stage (N_T2) of the recovery column and (e) the feed location of entrainer and water (N_B) of the recovery column.

Fig.8 The optimal isopropanol dehydration processes using DMSO as the entrainers.

Fig.9 The impacts of key operating variables of [EMIM]DCA: (a) solvent flowrate, (b) the number of stage (N_T1) of EC, (c) TAC vs N_E and N_F for S = 60 kmol?h^–1, (d) the number of stage (N_T2) of stripping column, and (e) the optimal isopropanol dehydration processes with [EMIM]DCA as the entrainer.

Fig.10 The impacts of key operating variables of [BMIM]DCA: (a) solvent flowrate, (b) the number of stage (N_T1) of EC, (c) TAC vs N_E and N_F for S = 60 kmol?h^–1 and (d) the number of stage (N_T2) of stripping column, and (e) the optimal isopropanol dehydration processes using [BMIM]DCA as entrainer.

Tab.3 Comparison of TAC for isopropanol dehydration by ED using DMSO, [EMIM]DCA, and [BMIM]DCA at the optimized conditions

1	T Qiu, P Zhang, J B Yang, L Xiao, C S Ye. Novel procedure for production of isopropanol by transesterification of isopropyl acetate with reactive distillation. Industrial & Engineering Chemistry Research, 2014, 53(36): 13881–13891 https://doi.org/10.1021/ie5026584
2	S Arifin, I L Chien. Design and control of an isopropyl alcohol dehydration process via extractive distillation using dimethyl sulfoxide as an entrainer. Industrial & Engineering Chemistry Research, 2008, 47(3): 790–803 https://doi.org/10.1021/ie070996n
3	T Shi, W Chun, A Yang, Y Su, S Jin, J Ren, W Shen. Isobaric vapor-liquid equilibria for the extractive distillation of 2-propanol + water mixtures using 1-ethyl-3-methylimidazolium dicyanamide ionic liquid. Journal of Chemical Thermodynamics, 2017, 110: 16–24 https://doi.org/10.1016/j.jct.2017.02.005
4	V Gerbaud, I Rodriguez-Donis, L Hegely, P Lang, F Denes, X Q You. Optimization and control of energy saving side-stream extractive distillation with heat integration for separating ethyl acetate-ethanol azeotrope. Chemical Engineering Science, 2020, 215: 115373 https://doi.org/10.1016/j.ces.2019.115373
5	A Yang, Y Su, T Shi, J Z Ren, W F Shen, T Zhou. Energy-efficient recovery of tetrahydrofuran and ethyl acetate by triple-column extractive distillation: entrainer design and process optimization. Frontiers of Chemical Science and Engineering, 2022, 16(2): 303–315 https://doi.org/10.1007/s11705-021-2044-z
6	Y Su, A Yang, S Jin, W Shen, P Cui, J Ren. Investigation on ternary system tetrahydrofuran/ethanol/water with three azeotropes separation via the combination of reactive and extractive distillation. Journal of Cleaner Production, 2020, 273(5760): 123145 https://doi.org/10.1016/j.jclepro.2020.123145
7	E Graczová, B Šulgan, S Barabas, P Steltenpohl. Methyl acetate-methanol mixture separation by extractive distillation: economic aspects. Frontiers of Chemical Science and Engineering, 2018, 12(4): 670–682 https://doi.org/10.1007/s11705-018-1769-9
8	H Li, G L Sun, D Y Li, L Xi, P Zhou, X G Li, J Zhang, X Gao. Molecular interaction mechanism in the separation of a binary azeotropic system by extractive distillation with ionic liquid. Green Energy & Environment, 2021, 6(3): 329–338 https://doi.org/10.1016/j.gee.2020.11.025
9	H Li, P Zhou, J Zhang, D Y Li, X G Li, X Gao. A theoretical guide for screening ionic liquid extractants applied in the separation of a binary alcohol-ester azeotrope through a DFT method. Journal of Molecular Liquids, 2018, 251: 51–60 https://doi.org/10.1016/j.molliq.2017.12.049
10	X Gao, X L Geng. Application of the chemical-looping concept for azoetrope separation. Engineering, 2021, 7(1): 84–93 https://doi.org/10.1016/j.eng.2020.06.022
11	T Zhou, Z Song, X Zhang, R Gani, K Sundmacher. Optimal solvent design for extractive distillation processes: a multiobjective optimization-based hierarchical framework. Industrial & Engineering Chemistry Research, 2019, 58(15): 5777–5786 https://doi.org/10.1021/acs.iecr.8b04245
12	L Hegely, P Lang. Influence of entrainer recycle for batch heteroazeotropic distillation. Frontiers of Chemical Science and Engineering, 2018, 12(4): 643–659 https://doi.org/10.1007/s11705-018-1760-5
13	Y C Wu, P H C Hsu, I L Chien. Critical assessment of the energy-saving potential of an extractive dividing-wall column. Industrial & Engineering Chemistry Research, 2013, 52(15): 5384–5399 https://doi.org/10.1021/ie3035898
14	W T Chang, C T Huang, S H Cheng. Design and control of a complete azeotropic distillation system incorporating stripping columns for isopropyl alcohol dehydration. Industrial & Engineering Chemistry Research, 2012, 51(7): 2997–3006 https://doi.org/10.1021/ie202021g
15	K Liang, W S Li, H T Luo, M Xia, C J Xu. Energy-efficient extractive distillation process by combining preconcentration column and entrainer recovery column. Industrial & Engineering Chemistry Research, 2014, 53(17): 7121–7131 https://doi.org/10.1021/ie5002372
16	S J Wang, W Y Chen, W T Chang, C C Hu, S H Cheng. Optimal design of mixed acid esterification and isopropanol dehydration systems via incorporation of dividing-wall columns. Chemical Engineering and Processing, 2014, 85: 108–124 https://doi.org/10.1016/j.cep.2014.08.011
17	P Lek-utaiwan, B Suphanit, P L Douglas, N Mongkolsiri. Design of extractive distillation for the separation of close-boiling mixture: solvent selection and column optimization. Computers & Chemical Engineering, 2011, 35(6): 1088–1100 https://doi.org/10.1016/j.compchemeng.2010.12.005
18	K M Gupta, J W Jiang. Cellulose dissolution and regeneration in ionic liquids: a computational perspective. Chemical Engineering Science, 2015, 121(6): 180–189 https://doi.org/10.1016/j.ces.2014.07.025
19	H Zhao, G A Baker. Oxidative desulfurization of fuels using ionic liquids: a review. Frontiers of Chemical Science and Engineering, 2015, 9(3): 262–279 https://doi.org/10.1007/s11705-015-1528-0
20	Z Song, X X Li, H Chao, F Mo, T Zhou, H Y Cheng, L F Chen, Z W Qi. Computer-aided ionic liquid design for alkane/cycloalkane extractive distillation process. Green Energy & Environment, 2019, 4(2): 154–165 https://doi.org/10.1016/j.gee.2018.12.001
21	Y Q Huang, Y B Zhang, H B Xing. Separation of light hydrocarbons with ionic liquids: a review. Chinese Journal of Chemical Engineering, 2019, 27(6): 1374–1382 https://doi.org/10.1016/j.cjche.2019.01.012
22	M Seiler, C Jork, A Kavarnou, W Arlt, R Hirsch. Separation of azeotropic mixtures using hyperbranched polymers or ionic liquids. AIChE Journal, 2004, 50(10): 2439–2454 https://doi.org/10.1002/aic.10249
23	H H Chen, M K Chen, B C Chen, I L Chien. Critical assessment of using an ionic liquid as entrainer via extractive distillation. Industrial & Engineering Chemistry Research, 2017, 56(27): 7768–7782 https://doi.org/10.1021/acs.iecr.7b01223
24	K Kulajanpeng, U Suriyapraphadilok, R Gani. Systematic screening methodology and energy efficient design of ionic liquid-based separation processes. Journal of Cleaner Production, 2016, 111: 93–107 https://doi.org/10.1016/j.jclepro.2015.07.052
25	J P Gutiérrez, G W Meindersma, Haan A B de. COSMO-RS-based ionic-liquid selection for extractive distillation processes. Industrial & Engineering Chemistry Research, 2012, 51(35): 11518–11529 https://doi.org/10.1021/ie301506n
26	R J Bernot, M A Brueseke, M A Evans-White, G A Lamberti. Acute and chronic toxicity of imidazolium-based ionic liquids on daphnia magna. Environmental Toxicology and Chemistry, 2005, 24(1): 87–92 https://doi.org/10.1897/03-635.1
27	D J Couling, R J Bernot, K M Docherty, J K Dixon, E J Maginn. Toxicological evaluation of ionic liquid in a biological functional tissue construct model based on nano-hydroxyapatite/chitosan/gelatin hybrid scaffolds. International Journal of Biological Macromolecules, 2020, 158(1): 800–810
28	C Pretti, C Chiappe, I Baldetti, S Brunini, G Monni, L Intorre. Acute toxicity of ionic liquids for three freshwater organisms: Pseudokirchneriella subcapitata, Daphnia magna and Danio rerio. Ecotoxicology and Environmental Safety, 2009, 72(4): 1170–1176 https://doi.org/10.1016/j.ecoenv.2008.09.010
29	X Q You, J L Gu, C J Peng, W F Shen, H L Liu. Improved design and optimization for separating azeotropes with heavy component as distillate through energy-saving extractive distillation by varying pressure. Industrial & Engineering Chemistry Research, 2017, 56(32): 9156–9166 https://doi.org/10.1021/acs.iecr.7b00687
30	I Rodriguez-Donis, V Gerbaud, X Joulia. Thermodynamic insights on the feasibility of homogeneous batch extractive distillation. 1. Azeotropic mixtures with a heavy entrainer. Industrial & Engineering Chemistry Research, 2009, 48(7): 3544–3559 https://doi.org/10.1021/ie801060n
31	R Turton, R C Bailie, W B Whiting, J A Shaeiwitz. Analysis, Synthesis and Design of Chemical Processes. 3rd ed. New York: Pearson Education, 2009,
32	L L William, I L Chien. Design and Control of Distillation Systems for Separating Azeotropes. New York: John Wiley & Sons, 2010,
33	P Navarro, M Larriba, J García, F Rodríguez. Design of the recovery section of the extracted aromatics in the separation of BTEX from naphtha feed to ethylene crackers using [4empy][Tf2N] and [emim][DCA] mixed ionic liquids as solvent. Separation and Purification Technology, 2017, 180: 149–156 https://doi.org/10.1016/j.seppur.2017.02.052
34	R P Swatloski, J D Holbrey, R D Rogers. Ionic liquids are not always green: hydrolysis of 1-butyl-3-methylimidazolium hexafluorophosphate. Green Chemistry, 2003, 5(4): 361–363 https://doi.org/10.1039/b304400a
35	S Himmler, S Hörmann, Hal R van, P S Schulz, P Wasserscheid. Transesterification of methylsulfate and ethylsulfate ionic liquids—an environmentally benign way to synthesize long-chain and functionalized alkylsulfate ionic liquids. Green Chemistry, 2006, 8(10): 887–894 https://doi.org/10.1039/B601583B
36	W H Awad, J W Gilman, M Nyden, R H H Jr, T E Sutto, J Callahan, P C Trulove, H C De Long, D M Fox. Thermal degradation studies of alkylimidazolium salts and their application in nanocomposites. Thermochimica Acta, 2004, 409(1): 3–11 https://doi.org/10.1016/S0040-6031(03)00334-4
37	H L Ngo, K LeCompte, L Hargens, A B McEwen. Thermal properties of imidazolium ionic liquids. Thermochimica Acta, 2000, 357-358: 97–102 https://doi.org/10.1016/S0040-6031(00)00373-7
38	J M Lopes, F A Sánchez, S B R Reartes, M D Bermejo, Á Martín, M J Cocero. Melting point depression effect with CO2 in high melting temperature cellulose dissolving ionic liquids. modeling with group contribution equation of state. Journal of Supercritical Fluids, 2016, 107: 590–604 https://doi.org/10.1016/j.supflu.2015.07.021
39	U Domańska, A Pobudkowska, F Ecker. Liquid-liquid equilibria in the binary systems (1,3-dimethylimidazolium, or 1-butyl-3-methylimidazolium methylsulfate + hydrocarbons). Green Chemistry, 2006, 8(3): 268–276 https://doi.org/10.1039/b514521j
40	F Wendler, L N Todi, F Meister. Thermostability of imidazolium ionic liquids as direct solvents for cellulose. Thermochimica Acta, 2012, 528: 76–84 https://doi.org/10.1016/j.tca.2011.11.015
41	J Lazzús, G Pulgar-Villarroel. A group contribution method to estimate the viscosity of ionic liquids at different temperatures. Journal of Molecular Liquids, 2015, 209: 161–168 https://doi.org/10.1016/j.molliq.2015.05.030
42	W M D Wan Normazlan, N A Sairi, Y Alias, A F Udaiyappan, A Jouyban, M Khoubnasabjafari. Composition and temperature dependence of density, durface tension, and viscosity of EMIM DEP/MMIM DMP + water + 1-propanol/2-propanol ternary mixtures and their mathematical representation using the Jouyban−Acree model. Journal of Chemical & Engineering Data, 2014, 59(8): 2337–2348 https://doi.org/10.1021/je400576e
43	D Groff, A George, N Sun, N Sathitsuksanoh, G Bokinsky, B A Simmons, B M Holmes, J D Keasling. Acid enhanced ionic liquid pretreatment of biomass. Green Chemistry, 2013, 15(5): 1264–1267 https://doi.org/10.1039/c3gc37086k
44	J Shi, J M Gladden, N Sathitsuksanoh, P Kambam, L Sandoval, D Mitra, S Zhang, A George, S W Singer, B A Simmons, S Singh. One-pot ionic liquid pretreatment and saccharification of switchgrass. Green Chemistry, 2013, 15(9): 2579–2589 https://doi.org/10.1039/c3gc40545a
45	M G Montalbán, J M Hidalgo, M Collado-González, Baños F G Díaz, G Víllora. Assessing chemical toxicity of ionic liquids on Vibrio fischeri: correlation with structure and composition. Chemosphere, 2016, 155: 405–414 https://doi.org/10.1016/j.chemosphere.2016.04.042
46	J Arning, S Stolte, A Böschen, F Stock, W R Pitner, U Welz-Biermann, B Jastorff, J Ranke. Qualitative and quantitative structure activity relationships for the inhibitory effects of cationic head groups, functionalised side chains and anions of ionic liquids on acetylcholinesterase. Green Chemistry, 2008, 10: 47–58 https://doi.org/10.1039/B712109A
47	M Matzke, S Stolte, K Thiele, T Juffernholz, J Arning, J Ranke, U Welz-Biermannd, B Jastorff. The influence of anion species on the toxicity of ionic liquids observed in an (eco)toxicological test battery. Green Chemistry, 2006, 8: 621–629
48	Y Yoshida, O Baba, G Saito. Ionic liquids based on dicyanamide anion: influence of structural variations in cationic structures on ionic conductivity. Journal of Physical Chemistry B, 2007, 111(18): 4742–4749 https://doi.org/10.1021/jp067055t
49	P Wasserscheid, T Welton. Ionic Liquid in Synthesis. New York: John Wiley & Sons, 2002,
50	P Navarro, M Larriba, E Rojo, J García, F Rodríguez. Thermal properties of cyano-based ionic liquids. Journal of Chemical & Engineering Data, 2013, 58(8): 2187–2193 https://doi.org/10.1021/je400140n
51	J O Valderrama, L A Forero, R E Rojas. Extension of a group contribution method to estimate the critical properties of ionic liquids of high molecular mass. Industrial & Engineering Chemistry Research, 2015, 54(13): 3480–3487 https://doi.org/10.1021/acs.iecr.5b00260
52	R Ge, C Hardacre, J Jacquemin, P Nancarrow, D W Rooney. Heat capacities of ionic liquids as a function of temperature at 0.1 MPa. Measurement and prediction. Journal of Chemical & Engineering Data, 2008, 53(9): 2148–2153 https://doi.org/10.1021/je800335v
53	L Z Zhang, J Z Han, D S Deng, J B Ji. Selection of ionic liquids as entrainers for separation of water and 2-propanol. Fluid Phase Equilibria, 2007, 255(2): 179–185 https://doi.org/10.1016/j.fluid.2007.04.016

[1]	Linlin You, Yandong Guo, Yanjing He, Feng Huo, Shaojuan Zeng, Chunshan Li, Xiangping Zhang, Xiaochun Zhang. Molecular level understanding of CO₂ capture in ionic liquid/polyimide composite membrane[J]. Front. Chem. Sci. Eng., 2022, 16(2): 141-151.
[2]	Ao Yang, Yang Su, Tao Shi, Jingzheng Ren, Weifeng Shen, Teng Zhou. Energy-efficient recovery of tetrahydrofuran and ethyl acetate by triple-column extractive distillation: entrainer design and process optimization[J]. Front. Chem. Sci. Eng., 2022, 16(2): 303-315.
[3]	Guojia Yu, Dongyu Jin, Xinyu Li, Fan Zhang, Shichao Tian, Yixin Qu, Zhiyong Zhou, Zhongqi Ren. Extractive desulfurization of model fuels with a nitrogen-containing heterocyclic ionic liquid[J]. Front. Chem. Sci. Eng., 2022, 16(12): 1735-1742.
[4]	Na Wang, Fujian Li, Bangyu Fan, Suojiang Zhang, Lu Bai, Xiangping Zhang. Rare-earth separation based on the differences of ionic magnetic moment via quasi-liquid strategy[J]. Front. Chem. Sci. Eng., 2022, 16(11): 1584-1594.
[5]	Jie Liu, Jiahao Shen, Jingjing Wang, Yuan Liang, Routeng Wu, Wenwen Zhang, Delin Shi, Saixiang Shi, Yanping Wang, Yimin Wang, Yumin Xia. Polymeric ionic liquid—assisted polymerization for soluble polyaniline nanofibers[J]. Front. Chem. Sci. Eng., 2021, 15(1): 118-126.
[6]	Zhaoyou Zhu, Guoxuan Li, Yao Dai, Peizhe Cui, Dongmei Xu, Yinglong Wang. Determination of a suitable index for a solvent via two-column extractive distillation using a heuristic method[J]. Front. Chem. Sci. Eng., 2020, 14(5): 824-833.
[7]	Huixin Zhang, Jinying Liang, Bangwang Xia, Yang Li, Shangfeng Du. Ionic liquid modified Pt/C electrocatalysts for cathode application in proton exchange membrane fuel cells[J]. Front. Chem. Sci. Eng., 2019, 13(4): 695-701.
[8]	Muhammad Faisal, Azeem Haider, Quret ul Aein, Aamer Saeed, Fayaz Ali Larik. Deep eutectic ionic liquids based on DABCO-derived quaternary ammonium salts: A promising reaction medium in gaining access to terpyridines[J]. Front. Chem. Sci. Eng., 2019, 13(3): 586-598.
[9]	Atanu Biswas, Carlucio R. Alves, Maria T. S. Trevisan, Roseane L. E. da Silva, Roselayne F. Furtado, Zengshe Liu, H. N. Cheng. Synthesis of a cardanol-amine derivative using an ionic liquid catalyst[J]. Front. Chem. Sci. Eng., 2016, 10(3): 425-431.
[10]	Hua Zhao,Gary A. Baker. Oxidative desulfurization of fuels using ionic liquids: A review? ?[J]. Front. Chem. Sci. Eng., 2015, 9(3): 262-279.
[11]	Zimeng HE,Ling YUE,Meng LI,Yazhuo SHANG,Honglai LIU. Rheological behavior of mixed system of ionic liquid [C₈mim]Br and sodium oleate in water[J]. Front. Chem. Sci. Eng., 2015, 9(2): 232-241.
[12]	Rui YAO, Hua WANG, Jinyu HAN. Polyethylene glycol-supported ionic liquid as a highly efficient catalyst for the synthesis of propylene carbonate under mild conditions[J]. Front Chem Sci Eng, 2012, 6(3): 239-245.
[13]	Xiaomeng WANG, Mingjuan HAN, Hui WAN, Cao YANG, Guofeng GUAN. Study on extraction of thiophene from model gasoline with br?nsted acidic ionic liquids[J]. Front Chem Sci Eng, 2011, 5(1): 107-112.
[14]	Beilei ZHOU, Yanxiong FANG, Hao GU, Saidan ZHANG, Baohua HUANG, Kun ZHANG. Ionic liquid mediated esterification of alcohol with acetic acid[J]. Front Chem Eng Chin, 2009, 3(2): 211-214.
[15]	Hiroshi MACHIDA, Ryosuke TAGUCHI, Yoshiyuki SATO, Louw J. FLOURUSSE, Cor J. PETERS, Richard L. SMITH. Measurement and correlation of supercritical CO₂ and ionic liquid systems for design of advanced unit operations[J]. Front Chem Eng Chin, 2009, 3(1): 12-19.

Viewed

Full text

Abstract

Cited

Shared

Discussed