Available online at www.sciencedirect.com Energy Procedia 00 (2016) 000 000 www.elsevier.com/locate/procedia The 8 th International Conference on Applied Energy ICAE2016 Viscosity data of aqueous MDEA [Bmim][BF 4 ] solutions within carbon capture operating conditions Worrada Nookuea a,*, Fu Wang b, Jie Yang c, Yuting Tan d, Hailong Li a, Eva Thorin a, Xinhai Yu e, Jinyue Yan a,c, * a School of Business, Society and Engineering, Mälardalen University, SE 721 23 Västerås, Sweden b Key Laboratory of Efficient Utilization of Low and Medium Grade Energy (Tianjin University), Ministry of Education of China, Tianjin, 300072, China c School of Energy and Power Engineering, University of Shanghai for Science and Technology, Shanghai, 200093, China d School of Chemical Science and Engineering, Royal Institute of Technology, SE 100 44 Stockholm, Sweden e Key Laboratory of Pressure Systems and Safety, Ministry of Education, School of Mechanical and Power Engineering, East China University of Science and Technology, Shanghai, 200237, China Abstract Post combustion capture with chemical absorption shows higher potential for commercial scale application compared with other technologies. To capture CO2 from the industrial and power plant s flue gases, aqueous alkanolamine solutions are widely used. However, several drawbacks from utilizing the aqueous alkanolamines such as MEA still need to be solved. For example, alkanolamine solutions require intensive energy for regeneration and cause severe corrosion to the equipment though they have high reactivity in capturing CO2. Ionic liquids have been of interest in the recent development of chemical absorption according to their unique characteristics including wide liquid range, negligible volatility and thermal stability. However, due to their high price, high viscosity and low absorption capacity compared to alkanolamines, ionic liquids are still non desirable for industrial applications. One possible solution to improve the performance of ionic liquids is to use mixtures of ionic liquids and alkanolamines. For a better understanding of the absorption using the mixture of aqueous alkanolamines and ionic liquids, the knowledge of thermo physical properties of the solutions, especially the viscosity and density are of importance. This paper reports the measured viscosity of MDEA [Bmim][BF4] aqueous mixtures at various temperatures and concentrations. It was found that the viscosity increase with an increase in [Bmim][BF4] concentration, but decrease with an increase in temperature. Moreover, the impact of temperature on the viscosity is more significant at low temperature range. 2016 The Authors. Published by Elsevier Ltd. Selection and/or peer review under responsibility of ICAE Keywords: MDEA, [Bmim][BF 4], viscosity, chemical absorption, CO 2 capture, ionic liquids
2 W. Nookuea et al./ Energy Procedia 00 (2016) 000 000 1. Introduction As reported by the IEA Energy Technology Perspectives 2015, in order to achieve the 2 degree target by 2050, Carbon Capture and Storage (CCS) accounts for 13% of the total GHG mitigation potential. Post combustion capture, pre combustion capture and oxy fuel combustion are the main available capture technologies. In comparison with other technologies, post combustion capture with chemical absorption shows higher potential for commercial scale application, since it does not require a radical changes in the plant structure [1 2]. To remove the acid gases such as CO 2 and H 2S from the industrial and flue gases, aqueous alkanolamine solutions are widely used. Several studies have investigated the absorption performances of different alkanolamine solutions including primary, secondary, tertiary and sterically hindered amines [3 5]. Even though they have high reactivity in capturing CO 2, alkanolamine solutions require intensive energy for regeneration and cause severe corrosion to the equipments, especially for monoethanolamine (MEA) and diglycolamine (DGA). Among the alkanolamine solutions, tertiary amine, such as N methyldiethanolamines (MDEA) has several advantages over the primary and secondary amines which are higher equilibrium loading capacity, higher thermal stability and lower regeneration energy requirement. However, due to its slow absorption rate, MDEA is usually mixed with an activator to increase the absorption rate in the industrial application [6]. In the recent development of chemical absorption, ionic liquids (ILs) have been of interest according to their unique characteristics. Wide liquid range, negligible volatility, thermal stability, good CO 2 solubility, tunable physicochemical characteristics and nonflammability make ILs to potential solvents for energy efficient CO 2 capture [7 8]. Several ILs are designed and synthesized as absorbent for CO 2 absorption, such as 1 butyl 3 methylimidazolium hexafluorophosphate ([Bmim][PF 6]), 1 butyl 3 methylimidazolium tetrafluoroborate ([Bmim][BF 4]), and hydroxyl ammonium ILs. However, for industry, amine solutions are still preferable due to their higher absorption capacity, lower price and lower solution viscosity [9]. One solution to combine the advantages of both amines and ILs is to incorporating an amine function in the structure of the ionic liquid to produce a task specific ionic liquid (TSIL) for CO 2 capture. However, this solution requires several synthesis and purification steps which make it difficult to get it cost competitive. Another simpler solution is to use the mixture of ionic liquids with alkanolamines to improve the performance of ionic liquids. Yang et al. [10] studied the performance of CO 2 capture by the mixtures of 30 wt % MEA + 40 wt % [Bmim][BF 4] + 30 wt %H 2O. Compared to the absorption with 30 wt% aqueous MEA, by adding 40 wt % [Bmim][BF 4], the energy demand of the system was reduced by 37.2%, the loss of MEA per ton of captured CO 2 decreased with 2.39 kg and no [Bmim][BF 4] loss was detected. Moreover, the mixed ionic solution also has low viscosity which benefits in reduction of the mechanical energy requirement for solvent pumping. Among the thermo physical properties of the fluids in chemical absorption, the liquid phase viscosity is one of the key properties which has significant impacts on the design of absorber and also on the energy demand of the system [2, 11 12]. However, the experimental viscosity data of MDEA [Bmim][BF 4] aqueous mixtures at different temperatures and concentrations have rarely been studied. This paper reports the measured viscosity of MDEA [Bmim][BF 4] aqueous mixtures at various temperature and concentration of MDEA and [Bmim][BF 4], which has little been reported. 2. Experiments 2.1 Materials Table 1 shows the MDEA and [Bmim][ BF 4] used in this study. The purity of both chemicals is more than 99%. To prepare the solutions, a digital balance with an accuracy of ±0.0001g was used to measure the mass of distilled water, MDEA and [Bmim][BF 4].
W. Nookuea et al. / Energy Procedia 00 (2016) 000 000 3 Table 1. Chemicals used in this study Name Formula CAS Purity Source Methyldiethanolamines C 5H 13NO 2 105 59 9 99% Tianjin Kermel Chemical (MDEA) Reagent Co., Ltd 1 butyl 3 methylimidazolium tetrafluoroborate ([Bmim][BF 4]) C 8H 15BF 4N 2 174501 65 6 99% Shanghai Chemical Technology Co., Ltd. 2.2 Apparatus The viscosities of MDEA [Bmim][BF 4] aqueous mixtures were measured using a NDJ 5S digital rotary viscometer produced by Shanghai Hengping instrument factory. The measurement ranges for temperature and viscosity are 0 110 C and 0.1 100,000 mpa s, respectively. Around 25 ml of the prepared solutions were poured into a steel cylinder before immersing a stainless steel rod which is connected with the rotator. During the experiment, the rotation speed was kept constant. The experimental temperature was controlled by a circulated water bath with a temperature range of 20 C to 80 C at atmospheric pressure. 3. Results and Discussion The viscosity of aqueous mixtures at 46.5 wt% of MDEA and 4.4 wt% of [Bmim][BF 4] at 30 C, 40 C, 50 C and 60 C were measured and compared to the data reported by Ahmady et al. [8] to confirm the procedure of the obtained viscosity data. As reported in Table 2, the average absolute deviation (AAD) calculated by Eq. (1) of the two data sets is 4.9% which represent good consistency between the generated data and the data from [8]. AAD (%) = N i ( 1 η/η 100) N (1) where N is the number of data, η and η are the measured viscosity and the viscosity from the literature, respectively. Table 2. Viscosity of MDEA [Bmim][BF 4] aqueous mixtures at 46.5 wt% of MDEA and 4.4 wt% of [Bmim][BF 4] from this work and a comparison with [8]. Temperature Viscosity (mpa s) AAD (%) ( C) η*, Ahmady et al. [8] η, This study 30 6.79 7.04 40 4.86 4.88 50 3.64 3.94 4.9 60 2.90 3.11 The measured viscosity of the MDEA [Bmim][BF 4] aqueous mixtures at 20, 30, and 40 wt% of MDEA and 10, 20, and 40 wt% of [Bmim][BF 4] at 20 C 80 C are given in Table 3 and plotted in Fig. 1 (a) 1(c). The viscosity increases significantly by increasing [Bmim][BF 4] concentration, especially at low temperatures. The viscosity decreases with an increase of temperature. The decrease of viscosity is more significant at lower temperature and becomes less affected by the temperature at high temperature range (60 C 80 C).
4 W. Nookuea et al./ Energy Procedia 00 (2016) 000 000 Table 3. Experimental results of viscosity for MDEA [Bmim][BF 4] aqueous mixtures. Mass fraction (wt%) Viscosity (mpa s) MDEA [Bmim][BF 4] H 2O 20 C 30 C 40 C 50 C 60 C 70 C 80 C 20 10 70 2.80 2.29 1.84 1.62 1.43 1.34 1.23 20 60 3.98 3.26 2.78 2.44 2.20 1.90 1.82 40 40 5.74 4.82 3.78 3.24 2.84 2.58 2.36 30 10 60 4.77 3.73 3.01 2.48 1.95 1.78 1.52 20 50 5.72 4.48 3.60 2.98 2.46 2.24 1.92 40 30 9.84 7.70 5.60 4.18 3.60 3.04 2.84 40 10 50 7.58 5.82 5.05 4.03 3.20 2.71 2.51 20 40 9.45 6.88 5.22 4.07 3.34 2.82 2.36 40 20 18.90 12.80 8.99 6.66 5.20 4.14 3.62
W. Nookuea et al. / Energy Procedia 00 (2016) 000 000 5 Fig. 1. Viscosity of MDEA [Bmim][BF 4] aqueous mixtures as a function of temperature at (a) 20 wt% of MDEA, (b) 30 wt% of MDEA and (c) 40 wt% of MDEA. In comparison with the pure [Bmim][BF 4], the MDEA [Bmim][BF 4] aqueous mixtures have significant lower viscosity. The reported viscosity of pure [Bmim][BF 4] at 50 C is 35.70 mpa s [13] which is almost six times higher than the viscosity of the mixture at 40 wt% of MDEA and [Bmim][BF 4] at the same temperature. The difference in viscosity value causes remarkable difference in the mechanical energy requirement to deliver the solvent. Thus, by using the mixed solvent of alkanolamines and ILs, one of the most important drawback of using the ILs in industrial purposes due to their high viscosity can be solved. The reported viscosity data are useful for the design of the chemical absorption process such as the diameter and required packing height of the absorber/desorber, the required power of the solvent pump, and also the required heat transfer area of the heat exchanger [2]. Moreover, they will be further used to generate a correlation to predict the viscosity of the MDEA [Bmim][BF 4] aqueous mixtures as a function of mixture s temperature and each specie s concentration. 4. Conclusions The viscosities for the tertiary mixtures of MDEA, [Bmim][BF 4] and H 2O over the composition ranges of 20, 30, and 40 wt% of MDEA and 10, 20, and 40 wt% of [Bmim][BF 4] have been investigated at atmospheric pressure and temperatures ranging from 20 80 C. The viscosity was found to increase with the increase in [Bmim][BF 4] concentration, but decrease with an increase in temperature. Moreover, the impact of temperature on the viscosity is more significant at lower temperature range. Such results will be used for design of CCS while using the mixtures of aqueous alkanolamines and ILs as capture solvents.
6 W. Nookuea et al./ Energy Procedia 00 (2016) 000 000 Moreover, they will be used to generate the correlation for predicting the viscosity of the mixtures at different temperatures and mass fraction of each specie. Acknowledgements The financial support by Swedish Energy Agency and Swedish Research Council is appreciated. Worrada Nookuea would like to appreciate the foundation of tandläkare Gustav Dahls memory. Wang Fu thanks the funding from the project 51506149 supported by China National Natural Science Foundation. Yuting Tan also thanks the scholarship from China Scholarship Council (CSC). References [1] International Energy Agency. IEA Energy Technology Perspectives 2015. Ed 2015. [2] Tan Y, Nookuea W, Li H, Thorin E, Yan J. Property impacts on Carbon Capture and Storage (CCS) processes: A review. Energy Convers Manag 2016;118:204 22. [3] Notz R, Mangalapally HP, Hasse H. Post combustion CO 2 capture by reactive absorption: Pilot plant description and results of systematic studies with MEA. Int J Greenh Gas Control 2012;6:84 112. [4] Closmann F, Nguyen T, Rochelle GT. MDEA/Piperazine as a solvent for CO 2 capture. Energy Procedia 2009;1:1351 7. [5] Fredriksen SB, Jens K J. Oxidative Degradation of Aqueous Amine Solutions of MEA, AMP, MDEA, Pz: A Review. Energy Procedia 2013;37:1770 7. [6] Foo CK, Leo CY, Aramesh R, Aroua MK, Aghamohammadi N, Shafeeyan MS, et al. Density and viscosity of aqueous mixtures of N methyldiethanolamines (MDEA), piperazine (PZ) and ionic liquids. J Mol Liq 2015;209:596 602. [7] R. Yusoff,* M. K. Aroua, Ahmad Shamiri, Afshin Ahmady, N. S. Jusoh, N. F. Asmuni LCB, Thee and SH. Density and Viscosity of Aqueous Mixtures of N Methyldiethanolamines (MDEA) and Ionic Liquids. J. Chem. Eng. Data 2013;58:240 7. [8] Ahmady A, Hashim MA, Aroua MK. Density, viscosity, physical solubility and diffusivity of CO 2 in aqueous MDEA+[bmim][BF4] solutions from 303 to 333K. Chem Eng J 2011;172:763 70. [9] Zhao Y, Zhang X, Zeng S, Zhou Q, Dong H, Tian X, et al. Density, Viscosity, and Performances of Carbon Dioxide Capture in 16 Absorbents of Amine + Ionic Liquid + H 2O, Ionic Liquid + H 2O, and Amine + H 2O Systems. J Chem Eng Data 2010;55:3513 9. [10] Yang J, Yu X, Yan J, Tu S T. CO 2 Capture Using Amine Solution Mixed with Ionic Liquid. Ind Eng Chem Res 2014;53:2790 9. [11] Nookuea W, Tan Y, Li H, Thorin E, Yan J. Impacts of thermo physical properties of gas and liquid phases on design of absorber for CO 2 capture using monoethanolamine. Int J Greenh Gas Control 2016;52:190 200. [12] Li H, Wilhelmsen Ø, Lv Y, Wang W, Yan J. Viscosities, thermal conductivities and diffusion coefficients of CO 2 mixtures: Review of experimental data and theoretical models. Int J Greenh Gas Control 2011;5:1119 39. [13] Song D, Chen J. Densities and viscosities for ionic liquids mixtures containing [eohmim][bf 4], [bmim][bf 4] and [bpy][bf 4]. J Chem Thermodyn 2014;77:137 43. Biography Worrada Nookuea is currently a Ph.D. student in the School of Business, Society and Engineering, Mälardalen University. Her research interest is in Carbon Capture and Storage (CCS).