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aminoethylethanolamine mixtures: Experimental measurements and thermodynamic modeling
Accepted Manuscript Thermodynamic properties and CO2 solubility of monoethanolamine + diethylenetriamine/aminoethylethanolamine mixtures: Experimental measurements and thermodynamic modeling Mehrdad Moosavi, Caleb J. Sisco, Abbas Ali Rostami, Francisco M. Vargas PII:
S0378-3812(17)30250-9
DOI:
10.1016/j.fluid.2017.06.018
Reference:
FLUID 11513
To appear in:
Fluid Phase Equilibria
Received Date: 27 February 2017 Revised Date:
18 June 2017
Accepted Date: 19 June 2017
Please cite this article as: M. Moosavi, C.J. Sisco, A.A. Rostami, F.M. Vargas, Thermodynamic properties and CO2 solubility of monoethanolamine + diethylenetriamine/aminoethylethanolamine mixtures: Experimental measurements and thermodynamic modeling, Fluid Phase Equilibria (2017), doi: 10.1016/j.fluid.2017.06.018. This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.
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Table of Contents Graphic
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“For Table of Contents Only”
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Thermodynamic Properties and CO2 Solubility of Monoethanolamine +
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Diethylenetriamine/Aminoethylethanolamine Mixtures: Experimental Measurements and
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Thermodynamic Modeling
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Mehrdad Moosavi1,2, Caleb J. Sisco2, Abbas Ali Rostami1, Francisco M. Vargas2*
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Faculty of Chemistry, University of Mazandaran, P.O. Box 453, Babolsar, Mazandaran, Iran
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2
Department of Chemical and Biomolecular Engineering, Rice University, Houston, Texas
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77005, United States
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Abstract
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The densities, viscosities, and refractive indices of monoethanolamine + diethylenetriamine /
10
aminoethylethanolamine binary liquid mixtures were measured at atmospheric pressure and
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temperatures of 298.15, 303.15 and 308.15 K across the complete composition range. From the
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experimental data, several thermodynamic properties – including the excess volume, partial
13
molar volume, partial molar volume at infinite dilution, excess Gibbs free energy of flow
14
activation and excess refractive index – were calculated. Excess molar volume and excess
15
refractive index data were correlated to the Redlich-Kister equation, and these properties were
16
used to analyze molecular interactions in the binary mixtures. These volumetric properties were
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then predicted using the associating version of the PC-SAFT equation of state to test its
18
applicability for amine systems, for which PC-SAFT showed promising results. Finally,
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viscosities were correlated using various models, including Arrhenius-like and McAllister.
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Keywords: Ethanolamine, Thermodynamic and Transport properties, PC-SAFT, CO2 solubility, Thermal expansion, Refractive index, Viscosity
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*
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E-mail: [email protected]
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Corresponding author: Tel: +1 (713) 348-2384
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1. Introduction
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Concerns over the role of greenhouse gases in climate change have motivated the development
26
of technologies to reduce and capture these gases. Particular attention has turned to carbon
27
dioxide (CO2), a greenhouse gas whose concentration in earth’s atmosphere has steadily
28
increased since the Industrial Revolution, largely due to its production in industrial combustion
29
reactions [1]. Among the various processes for CO2 removal from effluent process streams,
30
embedding of amine scrubbing units has gained considerable popularity [2,3]. The most
31
commonly used amine for CO2 capture is monoethanolamine because of its low price and fast
32
reaction rate. However, low absorption capacity, high energy requirement for regeneration, and
33
corrosion problems of monoethanolamine are among the main reasons for investigating other
34
amines and amine mixtures [4-7].
35
Both primary and secondary amines have been reported to have high reaction rates, absorption
36
capacities and heats of reaction [8-10], whereas tertiary amines have lower heats of reaction and
37
their absorption rates are somewhat limited [9-12]. Furthermore, primary and secondary amines
38
capture significantly less CO2 per mole of amine than tertiary amines due to the formation of
39
carbamate species that require two moles of amine per mole of CO2 captured [9,10]. The
40
reactivity for CO2 in amines is in the order of primary > secondary > tertiary [13].
41
To properly design the processes and equipment for CO2 absorption, a thorough understanding of
42
the physicochemical properties of candidate solvent blends that determine reaction kinetics and
43
transport properties is crucial. These solvents are often multi-component and strongly non-ideal,
44
which makes the prediction of their properties challenging without extensive experimental data.
45
Studies on phase behavior and viscosity are necessary for the determination of heat and mass
46
transfer properties along with the calculation of the power and process requirements for unit
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operations. Many researchers have reported on the thermodynamic and transport properties of
48
amine and amine-containing mixtures [14-31], but studies on amine mixtures like
49
monoethanolamine + diethylenetriamine / aminoethylethanolamine are rare.
50
In this work, densities, viscosities, and refractive indices of monoethanolamine (MEA) +
51
diethylenetriamine (DETA) / aminoethylethanolamine (AEEA) binary mixtures were measured
52
at atmospheric pressure and temperatures of 298.15, 303.15 and 308.15 K over the complete
53
composition range. Various volumetric properties – including excess molar volume, partial
54
molar volume and partial molar volume at infinite dilution – were obtained from density
55
measurements. Excess molar volumes and excess refractive indices were correlated by the
56
Redlich-Kister model, viscometric properties were correlated by several models, including the
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Arrhenius-like [32], Litovitz [33], Andrade [34] and McAllister [35] models, and refractive
58
indices were predicted with different mixing rules [36,37] such as the Arago-Biot, Gladstone-
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Dale, Newton, Eyring–John, Edwards, Lorentz–Lorenz, Weiners, Eykman, Hellers, and Oster.
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Excess refractive indices were then used to analyze optical properties of the mixtures. Finally,
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the PC-SAFT equation of state was applied to predict densities, excess volumes, thermal
62
expansion coefficients and CO2 solubility of the binary amine mixtures at various temperatures
63
and compositions.
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2. Methodology
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2.1. Experimental
66
2.1.1. Chemicals
67
MEA and AEEA were purchased from Sigma-Aldrich. DETA was prepared from Merck. The
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purity of these chemicals was higher than 98% and their water content was around 0.2%. All
69
chemicals were used without further purification. The water content of the chemicals was
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measured with a Kyoto Karl Fischer Moisture Titrator MKS-210 instrument. Table 1 shows the
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detailed specifications of the chemicals used.
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Table 1. Specifications of the chemicals used. Compound
CAS number
Supplier
Purity (supplier) (Mass fraction)
141-43-5
Sigma-Aldrich
≥98%
Diethylenetriamine
111-40-0
Merck
≥98% (GC)
Aminoethylethanolamine
111-41-1
Sigma-Aldrich
99%
Water content (supplier)
Water content (K.F.)a
(Mass fraction)
(Mass fraction)
<0.002%
0.06%
-
0.07%
-
0.08%
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Monoethanolamine
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a
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2.1.2. Experimental Procedures
75
All binary solutions were prepared by mass using a single pan Mettler Toledo AG204 balance
76
with a standard uncertainty of ± 0.1 mg. Liquid density measurements were performed using an
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Anton Paar oscillation U-tube densitometer (model: DMA 500) with a standard uncertainty of ±
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g.cm-3 and temperature standard uncertainty of 0.1 K calibrated at 293.15 K with ambient
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Water content determined by Karl Fischer method.
air and pure water.
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Dynamic viscosities were obtained using an Anton Paar Viscometer Lovis 2000 M rolling-ball
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automated viscometer with standard uncertainty in temperature of 0.02 K. Different capillaries
82
with different diameters (1.59, 1.8, and 2.5 mm) with a percentage relative uncertainty 1 % were
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selected to allow measurement of viscosities from 0.7 to 1700 mPa.s. The calibration was
84
completed using pure water and standard references prepared from CANNON including the S3,
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N7.5, N26, N100 and N415 standard oils with viscosities of 4, 12, 46, 230 and 990 mPa.s,
86
respectively, at T = 298.15 K.
87
Refractive index measurements were performed using an Abbe-2WAJ Refractometer coupled
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with a transparent thermostat water bath (Julabo F34 - Germany), which allows temperature
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stabilization with an uncertainty of 0.01 K. The standard uncertainty of the refractive index
90
measurements was estimated to be less than ± 0.001 units.
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2.2 Theory
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2.2.1 Volumetric Properties
93
To quantify the effect of temperature and composition on the interactions between amine
94
mixtures using volumetric properties, the excess molar volumes of the mixtures
95
determined from density measurements:
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where
98
results can then be fit by a Redlich–Kister-type polynomial [38]:
are the pure component density and molecular weight, respectively. These
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are
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96 and
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where
is a temperature-dependent adjustable parameter. The number of
parameters
101
necessary for acceptable fitting depends on the molecular complexity of the solution, the number
102
of data points available, and the quality of the measured data. Mixtures in which at least four
103
parameters are required for an adequate fitting are categorized as highly complex systems. Partial
104
molar volumes
105
is known. Partial molar volumes for components in a binary are given as:
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can then be calculated once the dependence of excess volume on composition
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108
where
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respectively. In the limit of infinite dilution, solute-solute interactions disappear, so partial molar
110
volumes at infinite dilution can provide information about solute-solvent interactions,
111
independent of composition effects. By the Redlich-Kister equation, partial molar volumes at
112
infinite dilution for components in a binary mixture are calculated by:
,
and
are partial molar volumes and molar volumes of components 1 and 2,
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,
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114 where
are again the Redlich-Kister coefficients.
116
Alternatively, volumetric properties of mixtures can be predicted by equations of state, which
117
become especially useful when experimental data are unavailable. The most commonly used
118
equations of state for fluid-phase modeling are the cubic-type first developed by van der Waals
119
[39]. Unfortunately, the cubics are capable of predicting density to an acceptable degree of
120
accuracy only for nonpolar fluids with low molecular weights. Thus, for this work, the PC-SAFT
121
equation of state was chosen to capture the strong intermolecular forces that dominate in liquid
122
mixtures containing alcohols and amines.
123
PC-SAFT has gained wide industrial acceptance due to its robust performance in predicting the
124
phase behavior of strongly associating fluid mixtures. Various thermodynamic properties – such
125
as density, isothermal compressibility, and saturation properties – can be calculated as
126
derivatives of the residual Helmholtz function, which is expressed in PC-SAFT as a hard chain
127
reference fluid (hc) with contributions from relatively weak London dispersion forces (disp) and
128
strong associating forces due to permanent dipoles (assoc):
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129 The hard chain and dispersion contributions to the Helmholtz energy are described by Gross and
131
Sadowski [40,41] and the association contribution by Chapman [42]. Five parameters, including
132
the number of segments
133
segments , the association energy between associating sites
134
association
135
for non-associating components in PC-SAFT. These parameters are fit so as to minimize the
136
deviation between experimental values of saturation pressure and saturated liquid densities.
137
2.2.2 Viscometric Properties
138
For liquid mixtures, viscosity is largely dependent on temperature and composition while
139
pressure dependence is usually negligible. Based on these dependencies, several equations have
140
been proposed to estimate the viscosity of mixtures. Here, the Arrhenius-like [32], Litovitz [33],
141
Andrade [34] and McAllister equations [35] were used. The Arrhenius-like equation can be
142
expressed as:
, segment diameter , the energy of dispersion interactions between and the volume of ,
and
are required
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, are required for each associating component while only
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143 144
where
145
of flow, and
is equal to viscosity in the high-temperature limit (T→ ∞), is the gas constant. The Litovitz equation is given as:
146 147
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and Andrade’s equation is: 7
is the activation energy
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148 ,
and
150
equation is expressed as:
are adjustable parameters. The two-parameter McAlister
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where
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149
151 152
where ,
153
and 2, and adjustable parameters, respectively.
154
Another flow property of interest can be calculated based on Eyring’s absolute rate theory [43].
155
According to this model, fluid motion is assumed to take place by an individual molecule in a
156
plane (or layer) occasionally acquiring the activation energy necessary to slip over the potential
157
barrier (arising from squeezing against its neighbors) to the next equilibrium position in the same
158
plane. This requires energy which can either be assumed to activate the flow unit or to produce a
159
hole of requisite size for particle translation to occur. The formation of the hole, or of this
160
intermediate activated state, then becomes the rate determining process which can be treated by
161
the theory of rate processes. From the Gibbs free energy of activation, the related excess
162
parameters can be calculated as:
and
are kinematic viscosities of the binary mixture, pure components 1
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The magnitude of
165
molecule must achieve for it to be activated for flow. It is indirectly a measure of the strength of
166
interactions between the molecules in solution.
167
2.2.3 Optical Properties
168
The refractive index is defined as the ratio of the speed of light through a vacuum to the speed of
169
light through a material of interest. These values convey information on the molecular
170
arrangement in a material, as light is bent due to interactions with molecules comprising the
171
material. It is then expected that refractive index results agree with measured densities. The
172
refractive indices measured in this paper were correlated using different mixing rules [36,37]
173
including Arago-Biot, Gladstone–Dale, Newton, Eyring–John, Edwards, Lorentz–Lorenz,
174
Weiners, Eykman, Hellers, and Oster semi-empirical models. These models can only be applied
175
if there are no chemical reactions in the mixture and if there are no changes in volume during
176
mixing. The excess refractive index
177
al. [44]:
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can also be calculated based on the definition of Reis et
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178 where
and
180
respectively, and
are volume fraction and refractive index of components 1 and 2,
is the refractive index of the mixture. Volume fraction is calculated by:
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can be viewed as an energy barrier over the ground state energy that a
182
3. Results and Discussion
183
The densities , dynamic viscosities , and refractive indices
184
experiment are compared with literature values reported in the NIST data archive [45] and shown 9
of pure amines measured from
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in Table 2. The relative standard uncertainties for measured densities, refractive indices and
186
viscosities are 0.002 g.cm-3, 0.001 and 0.1 mPa.s, respectively, indicating good agreement
187
between the experimental values reported in this paper and those found in the literature.
188
The densities, viscosities, and refractive indices for MEA + DETA/AEEA binary mixtures at all
189
studied temperatures are summarized in Tables 3 and 4. Partial molar volumes were calculated
190
by fitting a polynomial to density as a function of composition and differentiating. Thermal
191
expansion coefficients at 303.15 K were calculated by applying the central difference method to
192
densities at 298.15 K and 308.15 K to obtain the derivative of density with respect to temperature
193
at 303.15 K.
194
Table 2. Densities , viscosities , and refractive indices
195
literature values for T = (298.15, 303.15 and 308.15) K and P = 0.1 MPa.
1.0124 303.15 1.0084 1.0045
298.15 303.15
0.9458 0.9421
1.0120 1.0119 1.0121 1.0081 1.0080 1.0084 1.0040 1.0040
[20] [21] [15] [20] [21] [15] [20] [21]
0.9455 0.9317 0.9423 0.9370
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308.15
Ref
308.15
0.9378
of pure liquids with corresponding
Exp Lit Ref Monoethanolamine (MEA) 18.89 [15] 18.72 18.88 [15] 18.74 [15] 14.88 [15] 15.15 15.10 [22] 14.71 [24] 11.96 11.82 [24]
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298.15
Lit
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Exp
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[26] [26] [27] [26]
Diethylenetriamine (DETA) 5.63 5.627 [28] 4.50 4.512 [26] 4.804 [18] 3.85 3.830 [28]
Exp
Lit
Ref
1.4535
1.4540 1.4543
[22] [23]
1.4524 1.4527 1.4488
[22] [23] [25]
1.4519 1.4505
1.4822 1.4808 1.4793
Aminoethylethanolamine (AEEA) 1.0258 1.0252 [31] 98.62 98.60 [26] 1.4843 1.4845 [26] 298.15 1.0213 1.0215 [31] 70.57 70.50 [26] 1.4527 1.4826 [26] 303.15 1.0163 53.11 1.4811 308.15 Standard uncertainties are = 0.01 K, = 10 kPa, = 0.001 g.cm-3 and = 0.001; percentage relative standard uncertainty is = 10%.
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Table 3. Densities , viscosities , refractive indices
198
expansion coefficient
199
MPa.
,
partial molar volumes
, and thermal
of MEA (1) + DETA (2) for T = (298.15 to 308.15) K and P = 0.1
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5.63 8.28 10.37 12.15 13.87 15.47 16.82 18.22 19.23 19.31 18.72
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0.9458 0.9565 0.9646 0.9726 0.9794 0.9863 0.9927 0.9987 1.0051 1.0089 1.0124
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T = 298.15 K 55.642 109.082 0.0000 58.554 108.886 0.0989 59.173 108.711 0.2021 59.501 108.523 0.3013 59.722 108.328 0.4007 59.869 108.120 0.4984 59.958 107.916 0.6007 60.063 107.632 0.7027 60.176 106.958 0.8002 60.270 106.064 0.8987 60.331 104.075 1.0000 T = 303.15 K 0.0000 0.9421 4.50 55.0211 109.510 8.4917 0.0000 0.1619 0.9531 6.59 58.812 109.265 7.7641 0.0989 0.2973 0.9611 8.33 59.421 109.093 7.8036 0.2021 0.4258 0.9690 9.76 59.711 108.934 7.5335 0.3013 0.5307 0.9759 11.18 59.915 108.740 7.2753 0.4007 0.6308 0.9828 12.48 60.059 108.545 7.2243 0.4984 0.7174 0.9892 13.60 60.144 108.365 7.1775 0.6007 0.7980 0.9955 14.73 60.235 108.064 6.7303 0.7027 0.8790 1.0017 15.49 60.384 107.295 6.5888 0.8002 0.9336 1.0056 15.49 60.486 106.156 6.4638 0.8987 1.0000 1.0084 15.15 60.571 103.563 7.8342 1.0000 T = 308.15 K 0.0000 0.9378 3.85 54.085 110.012 0.0000 0.1619 0.9491 5.38 59.130 109.712 0.0989 0.2973 0.9571 6.68 59.548 109.600 0.2021 0.4258 0.9653 7.80 59.816 109.443 0.3013 0.5307 0.9723 8.89 60.104 109.180 0.4007 0.6308 0.9792 9.99 60.283 108.939 0.4984 0.7174 0.9856 10.89 60.341 108.817 0.6007 0.7980 0.9920 11.84 60.399 108.637 0.7027 0.8790 0.9985 12.42 60.549 107.848 0.8002 0.9336 1.0024 12.34 60.686 106.394 0.8987 1.0000 1.0045 11.90 60.806 102.665 1.0000 -3 Standard uncertainties are = 0.01 K, = 10 kPa, = 0.0002, = 0.001 g.cm and percentage relative standard uncertainties are = 10%, = 0.1% and = 5×10-4%. 0.0000 0.1619 0.2973 0.4258 0.5307 0.6308 0.7174 0.7980 0.8790 0.9336 1.0000
11
1.4822 1.4815 1.4806 1.4794 1.4778 1.4758 1.4731 1.4696 1.4657 1.4608 1.4535 1.4808 1.4802 1.4791 1.4778 1.4764 1.4743 1.4717 1.4683 1.4643 1.4591 1.4519
1.4793 1.4791 1.4778 1.4765 1.4752 1.4729 1.4703 1.4670 1.4631 1.4577 1.4505 = 0.001;
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201
Table 4. Densities , viscosities , refractive indices
202
expansion coefficient
203
MPa.
,
partial molar volumes
59.399 59.757 59.833 59.912 60.023 60.101 60.149 60.239 60.269 60.315 60.331
0.0000 0.1005 0.1993 0.2990 0.4047 0.5033 0.5985 0.6981 0.7985 0.8996 1.0000
1.4843 1.4824 1.4799 1.4774 1.4742 1.4714 1.4683 1.4647 1.4611 1.4573 1.4535
0.0000 0.1005 0.1993 0.2990 0.4047 0.5033 0.5985 0.6981 0.7985 0.8996 1.0000
1.4827 1.4810 1.4785 1.4760 1.4728 1.4700 1.4668 1.4633 1.4598 1.4559 1.4519
0.0000 0.1005 0.1993 0.2990 0.4047 0.5033 0.5985 0.6981 0.7985 0.8996 1.0000 = 0.001 g.cm-3 and = 5×10-4%.
1.4811 1.4796 1.4771 1.4745 1.4715 1.4685 1.4652 1.4620 1.4585 1.4545 1.4505 = 0.001;
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98.62 95.09 90.58 78.29 64.72 53.12 44.75 27.93 22.36 17.18 18.72
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1.0258 1.0257 1.0252 1.0244 1.0234 1.0225 1.0217 1.0194 1.0182 1.0152 1.0124
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of MEA (1) + AEEA (2) for T = (298.15 to 308.15) K and P = 0.1
T = 298.15 K 101.530 101.515 101.498 101.458 101.347 101.233 101.139 100.889 100.744 100.328 99.8699 T = 303.15 K 0.0000 1.0213 70.57 59.264 101.977 0.1072 1.0214 69.25 59.972 101.947 0.2634 1.0209 67.59 60.064 101.933 0.4233 1.0202 59.50 60.124 101.894 0.5481 1.0193 48.92 60.255 101.775 0.6305 1.0184 39.84 60.334 101.658 0.6851 1.0176 32.81 60.375 101.571 0.7988 1.0155 20.04 60.452 101.351 0.8459 1.0143 15.94 60.487 101.207 0.9377 1.0114 12.82 60.546 100.645 1.0000 1.0084 15.15 60.571 99.863 T = 308.15 K 0.0000 1.0163 53.11 59.327 102.479 0.1072 1.0166 52.77 60.145 102.441 0.2634 1.0162 52.68 60.306 102.418 0.4233 1.0157 46.92 60.348 102.384 0.5481 1.0149 38.49 60.466 102.270 0.6305 1.0141 31.01 60.549 102.157 0.6851 1.0134 25.15 60.600 102.060 0.7988 1.0114 14.71 60.689 101.791 0.8459 1.0103 11.31 60.723 101.627 0.9377 1.0075 9.55 60.777 101.084 1.0000 1.0045 11.96 60.806 100.416 Standard uncertainties are = 0.01 K, = 10 kPa, = 0.0002, percentage relative standard uncertainties is = 10%, = 0.1% and 0.0000 0.1072 0.2634 0.4233 0.5481 0.6305 0.6851 0.7988 0.8459 0.9377 1.0000
, and thermal
9.3019 8.9093 8.8158 8.5273 8.3881 8.2482 8.1560 7.8779 7.7886 7.6132 7.8342
204
3.1. Volumetric Properties
205
The variation of
206
Kister correlations, are shown in Figure 1, and the corresponding fitting parameters
207
Redlich-Kister equation, along with their standard deviations, are given in Table 5.
against MEA composition for various isotherms, along with the Redlich-
12
of the
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208 Fig. 1. Excess molar volume (
) as a function of MEA mole fraction ( ) for
210
MEA (1) + AEEA/DETA (2) for T = (298.15 to 308.15) K. Dashed lines represent the
211
corresponding Redlich–Kister correlations.
212
Table 5. Coefficients
213
(
M AN U
209
) of the Redlich-Kister equation for excess molar volume
298.15 K 303.15 K 308.15 K
-1.354 -1.963 -3.649 -0.296 -0.708 -0.924
298.15 K 303.15 K 308.15 K 298.15 K 303.15 K 308.15 K
-0.206 -0.185 -0.274
MEA+DETA
-0.762 -0.938 -0.338 -0.028 0.032 0.051
0.011 0.007 0.004
0.003 0.004 0.007
0.001 0.002 0.003
0.002 0.003 0.002
-0.003 -0.002 -0.002
0.001 -0.001 0.001
AC C
0.048 -0.009 -0.047
-2.730 -2.846 -3.046
0.0045 0.0040 0.0049
-0.970 -1.034 -1.087
0.0017 0.0021 0.0016
0.032 0.031 0.031
0.00006 0.00006 0.00007
0.011 0.010 0.010
0.00004 0.00008 0.00003
MEA+AEEA
0.080 0.038 0.093
EP
298.15 K 303.15 K 308.15 K
along with their standard deviations .
TE D
) and excess refractive index
-0.445 -0.442 -0.458
MEA+DETA 0.011 0.011 0.010
MEA+AEEA -0.001 -0.001 -0.001
214
Negative values of
for binary mixtures are often attributed to strong chemical or specific
215
interactions between the components present in the mixtures. These effects can also be attributed
216
in part to structural contributions arising from the geometrical fitting of one component into the 13
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other due to differences in the molar volumes and free volume between unlike molecules
218
(packing effect). The presence and position of NH, amine and hydroxyl groups in both amine
219
mixtures – and the strong association forces from hydrogen-bonding that accompany – produce
220
the highly negative excess molar volumes. Excess molar volumes for MEA + DETA are more
221
negative than those of MEA + AEEA, indicating relatively stronger interactions in MEA +
222
DETA.
223
The variation of partial molar volumes
224
DETA/AEEA are tabulated in Tables 3 and 4 and plotted in Figure 2. Partial molar volumes of
225
MEA in both mixtures increase nonlinearly with increasing MEA composition, while the inverse
226
behavior is seen for the partial molar volumes of DETA and AEEA.
227
The calculated values of
228
298.15, 303.15 and 308.15 K are listed in Table 6. The partial molar volumes of species at
229
infinite dilution were smaller than the corresponding molar volumes of pure components. These
230
values show the strong intermolecular interactions between unlike molecules and the contraction
231
in volume upon mixing. The excess partial molar volumes at infinite dilution are negative and
232
have
SC
M AN U
from Redlich-Kister for all studied binary mixtures at
TE D sign
EP
same
with MEA mole fraction for binary mixtures of MEA +
as
AC C
the
and
RI PT
217
14
the
excess
molar
volumes.
SC
RI PT
ACCEPTED MANUSCRIPT
TE D
M AN U
233
234
Fig. 2. Partial molar volume (
) as a function of MEA mole fraction ( ) for T =
236
(298.15 to 308.15) K. A: MEA and B: DETA in a binary mixture of MEA (1) + DETA (2). C:
237
MEA and D: AEEA in a binary mixture of MEA (1) + AEEA (2).
238
Table 6. Partial molar volumes at infinite dilution (
239
components (
AC C
EP
235
T/K 298.15 303.15 308.15
) and molar volume of pure
) for T = (298.15 to 308.15) K.
MEA (Pure)
MEA+DETA
MEA+AEEA
DETA (Pure)
MEA+DETA
AEEA (Pure)
MEA+AEEA
60.331 60.571 60.806
55.325 54.628 53.450
58.670 58.457 58.481
109.082 109.510 110.024
104.392 103.956 103.312
101.530 101.977 102.479
100.598 100.671 100.883
Standard uncertainties are
= 0.01 K,
= 10 kPa,
15
= 0.0002 and
= 0.005.
ACCEPTED MANUSCRIPT
In cases where experimental data have not been collected, as is required to do fitting for the
241
Redlich-Kister equation, the most reliable method for generating volumetric property predictions
242
is by an equation of state. The PC-SAFT equation of state is used in this work, and the
243
parameters for the studied components are listed in Table 7. These values were fit to density and
244
vapor pressure correlations reported in the DIPPR database [46]. CO2 was treated as non-
245
associating in this work and its PC-SAFT parameters were reported by Gross and Sadowski [40].
246
PC-SAFT predictions for density and excess molar volume for both binary mixtures are shown in
247
Figures 3 and 4, respectively, and compared to experimental measurements. Values of
248
fit to minimize deviations between the excess molar volumes predicted and those measured.
249
Table 7. PC-SAFT parameters of studied pure components.
250
M AN U
SC
RI PT
240
.
and
Associating
(-)
3.5892
104.15
5.0467
45.01
2.0729
169.00
0.178696
TE D
103.16
2.6870
1982.5
4C
2.52
0.75
273-500
3.4692
237.15
0.535593
1952.9
2B
1.19
0.86
273-500
3.0673
225.94
0.051951
2277.2
4C
0.61
0.50
273-500
2.7852
169.21
0
0
-
2.78
2.73
216-304
EP
251
4.1833
range
Scheme
(-)
AC C
CO2
61.08
were
16
SC
RI PT
ACCEPTED MANUSCRIPT
M AN U
252 253
Fig. 3. Density (
254
DETA/AEEA (2) compared with calculated results from PC-SAFT for T = 298.15 K.
AC C
255
EP
TE D
) as a function of MEA mole fraction ( ) for MEA (1) +
256
Fig. 4. Excess molar volume (
) as a function of MEA mole fraction ( ) for T =
257
(298.15 to 308.15) K. A: MEA + DETA, B: MEA + AEEA compared with calculated results
258
from PC-SAFT.
259
Thermal expansion coefficients, given as:
260 17
ACCEPTED MANUSCRIPT
were calculated for pure MEA, DETA and AEEA using the PC-SAFT model and compared with
262
correlated values from the literature [47,30,31]. These results are shown in Figure S1 in
263
Supporting Information. Thermal expansion coefficients for MEA + DETA/AEEA binaries as a
264
function of MEA mole fraction are shown in Figure 5.
265
The maximum AAD for density predictions with PC-SAFT were 0.36% and 0.25% for MEA +
266
DETA and MEA + AEEA, respectively. Good liquid density predictions should be expected, as
267
the PC-SAFT parameters were fit to match experimental saturation pressures and saturated liquid
268
densities. Excess volume showed maximum AAD of 15.61% and 6.73% for MEA + DETA and
269
MEA + AEEA, respectively. For the thermal expansion coefficients calculated at 303.15 K and
270
0.1 MPa, AAD values were 13.62% for MEA + DETA and 9.05% for MEA + AEEA. Pure
271
component thermal expansion coefficients showed AAD values of 10.71%, 5.50% and 9.87% for
272
MEA, DETA and AEEA, respectively.
273
Finally, predictions for CO2 solubility in MEA + DETA/AEEA at 298.15 K and 0.1 MPa are
274
reported in Figure 6. Solubility data for CO2 in MEA + DETA/AEEA have not been found in the
275
literature and there is only sparse data on CO2 solubility in amine mixtures. Various studies with
276
SAFT modeling of CO2 solubility in alkanes [48], polymers [49], ionic liquids [50], and aqueous
277
amines [51] have shown promising results. PC-SAFT predicts that CO2 solubility decreases with
278
increasing MEA composition in both binary mixtures, and CO2 is more soluble in MEA + DETA
279
than in MEA + AEEA.
AC C
EP
TE D
M AN U
SC
RI PT
261
18
SC
RI PT
ACCEPTED MANUSCRIPT
280 Fig. 5. Thermal expansion coefficient (
) as a function of MEA mole fraction ( ) for
282
MEA + DETA (red) and MEA + AEEA (blue) at T = 303.15 K compared with calculated results
283
from PC-SAFT.
TE D
M AN U
281
AC C
284
MEA + DETA
EP
MEA + AEEA
285
Fig. 6. PC-SAFT predicted CO2 solubility as a function of MEA mole fraction ( ) for MEA (1)
286
+ DETA/AEEA (2) for T = 298.15 K and P = 0.1 MPa.
287
3.2. Viscometric Properties
288
Dynamic viscosities for the studied amine mixtures are reported in Tables 3 and 4 and shown
289
graphically in Figure 7. Viscosities were shown to decrease with increasing temperature for both
290
mixtures. The composition dependence of viscosity was more complicated; the viscosities of 19
ACCEPTED MANUSCRIPT
MEA + DETA mixtures increased up to a mole fraction of about 0.9 MEA and then shifted
292
down, whereas, for MEA + AEEA solutions, viscosities decreased up to a mole fraction of about
293
0.9 MEA and then shifted up.
294
In fluid systems at constant temperature, molecular weight and intermolecular forces are the two
295
main factors affecting viscosity. These two factors can often complement each other in their
296
effect on viscosity but may also compete in some scenarios. For example, both DETA and
297
AEEA have nearly identical molecular weights, but the viscosity of pure AEEA is twenty times
298
more than the viscosity of DETA. The discrepancy in viscosity can be attributed to stronger
299
interactions between AEEA molecules than between DETA molecules. Comparison between the
300
viscosity and density results of pure MEA and AEEA shows that interactions between molecules
301
in AEEA are stronger than in MEA.
302
AC C
EP
TE D
M AN U
SC
RI PT
291
303
Fig. 7. Dynamic viscosity (
) as a function of MEA mole fraction ( ) for T = 298.15 K
304
compared with various viscosity models. A: MEA + DETA, B: MEA + AEEA.
305
All calculated adjustable parameter values along with the corresponding standard deviations in
306
the viscosity models are listed in Table 8. Among the three-examined temperature-dependent
307
viscosity models, the Arrhenius-like model produced the lowest AAD%. The McAlister model
20
ACCEPTED MANUSCRIPT
predicted the viscosities of MEA + DETA/AEEA binary mixtures with absolute average
309
deviations less than 0.21% and 14.40%, respectively.
310
Table 8. Adjustable parameters of investigated viscosity models along with their AAD% for
311
MEA (1) + DETA/AEEA (2) binary mixtures.
Andrade
Arrhenius
Litovitz
0.107 -13.6 44.99 0.79 -1.70 1.38 0.57 1.56 245.8 -238 0.31
0.263 -12.2 41.40 0.78 -1.25 1.27 0.56 2.38 207.7 -241 0.15
MEA + DETA 0.425 0.530 -11.1 -11.0 33.85 33.96 0.27 0.50 -2.20 -2.08 1.04 1.04 0.43 0.65 0.002 0.001 2274 33.51 -36.2 62.3 4.89 7.71 MEA + AEEA 0.423 0.548 -11.4 -11.8 39.11 39.70 0.64 0.69 -1.07 -1.35 1.20 1.22 0.44 0.51 1.76 1.73 242.7 215.7 -234 -238 0.07 0.10 McAllister
0.630 -10.7 33.39 0.33 -1.90 1.02 0.50 0.003 23.20 -21.9 5.27
0.717 -10.5 33.19 0.34 -1.78 1.02 0.52 0.004 23.25 -14.3 5.23
0.798 -10.3 32.87 0.27 -1.66 1.01 0.42 0.001 3132 11.63 3.96
0.879 -10.4 33.30 0.23 -1.67 1.02 0.40 0.003 2274 -39.1 3.93
0.933 -10.8 34.19 0.31 -1.78 1.05 0.48 0.005 2092 -40.2 5.03
1.000 -10.8 34.17 0.72 -1.81 1.05 0.86 0.002 3738 122.9 8.66
0.630 -12.6 41.11 0.61 -1.74 1.26 0.42 0.79 285.3 -230 0.18
0.685 -13.9 44.03 0.78 -2.32 1.35 0.56 0.81 238.3 -238 0.30
0.798 -16.4 48.95 0.28 -3.47 1.50 0.04 0.41 246.8 -239 0.89
0.845 -17.8 52.07 0.34 -4.12 1.59 0.60 0.01 888.9 -180 3.18
0.937 -15.2 44.84 0.25 -3.38 1.37 0.51 0.002 1623 -115 4.61
1.000 -10.8 34.17 0.72 -1.81 1.05 0.86 0.002 3738 122.9 8.66
SC
0.000 -14.4 47.29 0.88 -1.98 1.45 0.66 1.61 232.3 -241 0.11
EP
Andrade
0.297 -11.2 33.63 0.19 -2.33 1.03 0.33 0.003 1645 -94.6 2.24
M AN U
Litovitz
0.161 -11.1 32.95 0.37 -2.47 1.01 0.20 0.12 360.8 -211 0.24
TE D
Arrhenius
0.000 -10.0 29.06 1.32 -2.32 8.90 1.17 1.54 31.02 -274 0.22
RI PT
308
AC C
MEA + DETA
298.15 K 303.15 K 308.15 K
19.60 15.88 13.25
12.59 10.12 7.61
MEA + AEEA 2.08 1.88 1.98
36.38 22.43 14.94
152.3 134.5 122
9.62 11.93 14.40
312
The Gibbs free energy of flow activation, calculated from equation 10, is indirectly a measure of
313
the strength of interactions between the molecules in solution. Figure 8 shows the excess Gibbs
314
free energy of flow activation at 298.15, 303.15 and 308.15 K for binary mixtures of MEA +
315
DETA/AEEA. Excess Gibbs free energy of flow activation for MEA + DETA is positive for all
21
ACCEPTED MANUSCRIPT
temperatures and compositions with extrema around 0.5 mole fraction of MEA.
is negative
317
in the MEA rich region for MEA + AEEA binary mixture. Positive values of
show that
318
specific interactions between unlike molecules are dominant in the studied binary mixtures.
M AN U
SC
RI PT
316
319
Fig. 8. Excess Gibbs free energy of flow activation (
) as a function of MEA mole
321
fraction ( ) for T = (298.15 to 308.15) K. A: MEA + DETA, B: MEA + AEEA.
322
3.3. Optical Properties
323
The refractive indices of MEA + DETA/AEEA binary mixtures at temperatures of 298.15,
324
303.15 and 308.15 K are reported in Tables 3 and 4 and shown graphically in Figure S2 in
325
Supporting Information. At all temperatures, the refractive indices for both amine mixtures
326
decrease non-linearly with increasing MEA composition. The refractive index values for the pure
327
chemicals vary in the order of AEEA > DETA > MEA and decrease as temperature increases.
328
The refractive indices were correlated using various models, including Arago-Biot, Gladstone–
329
Dale, Newton, Eyring–John, Edwards, Lorentz–Lorenz, Weiners, Eykman, Hellers, and Oster
330
semi-empirical models. The absolute average deviations of these models are shown graphically
AC C
EP
TE D
320
22
ACCEPTED MANUSCRIPT
in Figure 9. All studied models can predict the refractive index values of MEA + DETA/AEEA
332
binary mixtures with maximum AAD of less than 0.8% and 0.3%, respectively. The deviations
333
of these models for MEA + DETA decrease with increasing temperature, while for MEA +
334
AEEA the opposite trend is seen.
M AN U
SC
RI PT
331
335
Fig. 9. Comparison between AAD% from experimental and calculated refractive indices for T =
337
298.15 K. (red) MEA + DETA, (blue) MEA + AEEA.
338
The excess refractive index
339
function of MEA mole fraction are shown in Figure 10. Excess refractive index values are
340
positive for both amine mixtures with a maximum at MEA mole fractions of 0.6 and 0.5 for
341
MEA + DETA and MEA + AEEA, respectively. Positive values of
342
values and vice versa, and both
343
Therefore, a more positive
344
light velocity in the medium, and a lower refractive index than the ideal solution.
TE D
336
AC C
EP
, calculated based on the definition of Reis et al. [44], as a
and
correspond to negative
shift to zero values with increasing temperature.
value is indicative of more free volume in the solution, higher
23
345
SC
RI PT
ACCEPTED MANUSCRIPT
Fig. 10. Excess refractive index (
) as a function of MEA mole fraction ( ) for MEA (1) +
347
DETA /AEEA (2) for T = (298.15 to 308.15) K.
348
4. Conclusions
349
Thermophysical properties of the monoethanolamine (MEA) + diethylenetriamine (DETA) /
350
aminoethylethanolamine (AEEA) binary mixtures – including densities, viscosities, and
351
refractive indices – were measured at atmospheric pressure for 298.15, 303.15 and 308.15 K.
352
Negative excess molar volumes and positive excess refractive indices were obtained that
353
indicated stronger interactions between unlike components in the mixtures than like components.
354
Excess parameter values of all studied systems shift toward zero when temperature increases,
355
showing that solutions approach ideality in the high-temperature limit.
356
The Redlich-Kister model satisfactorily correlated the values of
357
standard deviations of 0.0049 and 6 x 10-5, respectively, for MEA + DETA and 0.0021 and 8 x
358
10-5, respectively for MEA + AEEA.
359
Experimental viscosities were well correlated with Arrhenius-like, Litovitz, Andrade and
360
McAlister models, with maximum AAD% of 1.32, 1.17, 7.71 and 2.08, respectively, for MEA +
361
DETA and 0.88, 0.86, 8.66 and 14.40, respectively, for MEA + AEEA.
AC C
EP
TE D
M AN U
346
24
and
, yielding maximum
ACCEPTED MANUSCRIPT
Refractive indices were correlated satisfactorily using Lorentz-Lorenz, Eykman and Edwards
363
semi-empirical models with maximum AAD% equal to 0.2.
364
PC-SAFT predictions for density, excess molar volume, thermal expansion coefficient and CO2
365
solubility were presented. Density predictions for both binaries were excellent, while excess
366
molar volumes and thermal expansion coefficients showed more deviation. Excess volume
367
predictions showed maximum AAD% of 15.61 and 6.73 for MEA + DETA and MEA + AEEA,
368
respectively, and thermal expansion coefficients calculated at 303.15 K and 0.1 MPa showed
369
AAD% of 13.62 and 9.05 for MEA + DETA and MEA + AEEA, respectively.
370
Acknowledgment
371
The experimental support from University of Mazandaran is gratefully acknowledged.
AC C
EP
TE D
M AN U
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362
25
ACCEPTED MANUSCRIPT
372
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373
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Highlights
Density, viscosity and refractive index of amines mixtures were measured
•
Different excess properties were calculated from the experimental measurements
•
PC-SAFT models were used to calculation of volumetric properties and CO2 solubility
•
Different models were used to reproduce the viscosities and refractive indices data
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S0378-3812(17)30250-9
DOI:
10.1016/j.fluid.2017.06.018
Reference:
FLUID 11513
To appear in:
Fluid Phase Equilibria
Received Date: 27 February 2017 Revised Date:
18 June 2017
Accepted Date: 19 June 2017
Please cite this article as: M. Moosavi, C.J. Sisco, A.A. Rostami, F.M. Vargas, Thermodynamic properties and CO2 solubility of monoethanolamine + diethylenetriamine/aminoethylethanolamine mixtures: Experimental measurements and thermodynamic modeling, Fluid Phase Equilibria (2017), doi: 10.1016/j.fluid.2017.06.018. This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.
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Table of Contents Graphic
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“For Table of Contents Only”
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Thermodynamic Properties and CO2 Solubility of Monoethanolamine +
2
Diethylenetriamine/Aminoethylethanolamine Mixtures: Experimental Measurements and
3
Thermodynamic Modeling
4
Mehrdad Moosavi1,2, Caleb J. Sisco2, Abbas Ali Rostami1, Francisco M. Vargas2*
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1
Faculty of Chemistry, University of Mazandaran, P.O. Box 453, Babolsar, Mazandaran, Iran
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2
Department of Chemical and Biomolecular Engineering, Rice University, Houston, Texas
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77005, United States
8
Abstract
9
The densities, viscosities, and refractive indices of monoethanolamine + diethylenetriamine /
10
aminoethylethanolamine binary liquid mixtures were measured at atmospheric pressure and
11
temperatures of 298.15, 303.15 and 308.15 K across the complete composition range. From the
12
experimental data, several thermodynamic properties – including the excess volume, partial
13
molar volume, partial molar volume at infinite dilution, excess Gibbs free energy of flow
14
activation and excess refractive index – were calculated. Excess molar volume and excess
15
refractive index data were correlated to the Redlich-Kister equation, and these properties were
16
used to analyze molecular interactions in the binary mixtures. These volumetric properties were
17
then predicted using the associating version of the PC-SAFT equation of state to test its
18
applicability for amine systems, for which PC-SAFT showed promising results. Finally,
19
viscosities were correlated using various models, including Arrhenius-like and McAllister.
20 21
Keywords: Ethanolamine, Thermodynamic and Transport properties, PC-SAFT, CO2 solubility, Thermal expansion, Refractive index, Viscosity
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*
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E-mail: [email protected]
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Corresponding author: Tel: +1 (713) 348-2384
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1. Introduction
25
Concerns over the role of greenhouse gases in climate change have motivated the development
26
of technologies to reduce and capture these gases. Particular attention has turned to carbon
27
dioxide (CO2), a greenhouse gas whose concentration in earth’s atmosphere has steadily
28
increased since the Industrial Revolution, largely due to its production in industrial combustion
29
reactions [1]. Among the various processes for CO2 removal from effluent process streams,
30
embedding of amine scrubbing units has gained considerable popularity [2,3]. The most
31
commonly used amine for CO2 capture is monoethanolamine because of its low price and fast
32
reaction rate. However, low absorption capacity, high energy requirement for regeneration, and
33
corrosion problems of monoethanolamine are among the main reasons for investigating other
34
amines and amine mixtures [4-7].
35
Both primary and secondary amines have been reported to have high reaction rates, absorption
36
capacities and heats of reaction [8-10], whereas tertiary amines have lower heats of reaction and
37
their absorption rates are somewhat limited [9-12]. Furthermore, primary and secondary amines
38
capture significantly less CO2 per mole of amine than tertiary amines due to the formation of
39
carbamate species that require two moles of amine per mole of CO2 captured [9,10]. The
40
reactivity for CO2 in amines is in the order of primary > secondary > tertiary [13].
41
To properly design the processes and equipment for CO2 absorption, a thorough understanding of
42
the physicochemical properties of candidate solvent blends that determine reaction kinetics and
43
transport properties is crucial. These solvents are often multi-component and strongly non-ideal,
44
which makes the prediction of their properties challenging without extensive experimental data.
45
Studies on phase behavior and viscosity are necessary for the determination of heat and mass
46
transfer properties along with the calculation of the power and process requirements for unit
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operations. Many researchers have reported on the thermodynamic and transport properties of
48
amine and amine-containing mixtures [14-31], but studies on amine mixtures like
49
monoethanolamine + diethylenetriamine / aminoethylethanolamine are rare.
50
In this work, densities, viscosities, and refractive indices of monoethanolamine (MEA) +
51
diethylenetriamine (DETA) / aminoethylethanolamine (AEEA) binary mixtures were measured
52
at atmospheric pressure and temperatures of 298.15, 303.15 and 308.15 K over the complete
53
composition range. Various volumetric properties – including excess molar volume, partial
54
molar volume and partial molar volume at infinite dilution – were obtained from density
55
measurements. Excess molar volumes and excess refractive indices were correlated by the
56
Redlich-Kister model, viscometric properties were correlated by several models, including the
57
Arrhenius-like [32], Litovitz [33], Andrade [34] and McAllister [35] models, and refractive
58
indices were predicted with different mixing rules [36,37] such as the Arago-Biot, Gladstone-
59
Dale, Newton, Eyring–John, Edwards, Lorentz–Lorenz, Weiners, Eykman, Hellers, and Oster.
60
Excess refractive indices were then used to analyze optical properties of the mixtures. Finally,
61
the PC-SAFT equation of state was applied to predict densities, excess volumes, thermal
62
expansion coefficients and CO2 solubility of the binary amine mixtures at various temperatures
63
and compositions.
64
2. Methodology
65
2.1. Experimental
66
2.1.1. Chemicals
67
MEA and AEEA were purchased from Sigma-Aldrich. DETA was prepared from Merck. The
68
purity of these chemicals was higher than 98% and their water content was around 0.2%. All
69
chemicals were used without further purification. The water content of the chemicals was
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measured with a Kyoto Karl Fischer Moisture Titrator MKS-210 instrument. Table 1 shows the
71
detailed specifications of the chemicals used.
72
Table 1. Specifications of the chemicals used. Compound
CAS number
Supplier
Purity (supplier) (Mass fraction)
141-43-5
Sigma-Aldrich
≥98%
Diethylenetriamine
111-40-0
Merck
≥98% (GC)
Aminoethylethanolamine
111-41-1
Sigma-Aldrich
99%
Water content (supplier)
Water content (K.F.)a
(Mass fraction)
(Mass fraction)
<0.002%
0.06%
-
0.07%
-
0.08%
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Monoethanolamine
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73
a
74
2.1.2. Experimental Procedures
75
All binary solutions were prepared by mass using a single pan Mettler Toledo AG204 balance
76
with a standard uncertainty of ± 0.1 mg. Liquid density measurements were performed using an
77
Anton Paar oscillation U-tube densitometer (model: DMA 500) with a standard uncertainty of ±
78
g.cm-3 and temperature standard uncertainty of 0.1 K calibrated at 293.15 K with ambient
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Water content determined by Karl Fischer method.
air and pure water.
80
Dynamic viscosities were obtained using an Anton Paar Viscometer Lovis 2000 M rolling-ball
81
automated viscometer with standard uncertainty in temperature of 0.02 K. Different capillaries
82
with different diameters (1.59, 1.8, and 2.5 mm) with a percentage relative uncertainty 1 % were
83
selected to allow measurement of viscosities from 0.7 to 1700 mPa.s. The calibration was
84
completed using pure water and standard references prepared from CANNON including the S3,
85
N7.5, N26, N100 and N415 standard oils with viscosities of 4, 12, 46, 230 and 990 mPa.s,
86
respectively, at T = 298.15 K.
87
Refractive index measurements were performed using an Abbe-2WAJ Refractometer coupled
88
with a transparent thermostat water bath (Julabo F34 - Germany), which allows temperature
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stabilization with an uncertainty of 0.01 K. The standard uncertainty of the refractive index
90
measurements was estimated to be less than ± 0.001 units.
91
2.2 Theory
92
2.2.1 Volumetric Properties
93
To quantify the effect of temperature and composition on the interactions between amine
94
mixtures using volumetric properties, the excess molar volumes of the mixtures
95
determined from density measurements:
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where
98
results can then be fit by a Redlich–Kister-type polynomial [38]:
are the pure component density and molecular weight, respectively. These
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are
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where
is a temperature-dependent adjustable parameter. The number of
parameters
101
necessary for acceptable fitting depends on the molecular complexity of the solution, the number
102
of data points available, and the quality of the measured data. Mixtures in which at least four
103
parameters are required for an adequate fitting are categorized as highly complex systems. Partial
104
molar volumes
105
is known. Partial molar volumes for components in a binary are given as:
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can then be calculated once the dependence of excess volume on composition
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108
where
109
respectively. In the limit of infinite dilution, solute-solute interactions disappear, so partial molar
110
volumes at infinite dilution can provide information about solute-solvent interactions,
111
independent of composition effects. By the Redlich-Kister equation, partial molar volumes at
112
infinite dilution for components in a binary mixture are calculated by:
,
and
are partial molar volumes and molar volumes of components 1 and 2,
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are again the Redlich-Kister coefficients.
116
Alternatively, volumetric properties of mixtures can be predicted by equations of state, which
117
become especially useful when experimental data are unavailable. The most commonly used
118
equations of state for fluid-phase modeling are the cubic-type first developed by van der Waals
119
[39]. Unfortunately, the cubics are capable of predicting density to an acceptable degree of
120
accuracy only for nonpolar fluids with low molecular weights. Thus, for this work, the PC-SAFT
121
equation of state was chosen to capture the strong intermolecular forces that dominate in liquid
122
mixtures containing alcohols and amines.
123
PC-SAFT has gained wide industrial acceptance due to its robust performance in predicting the
124
phase behavior of strongly associating fluid mixtures. Various thermodynamic properties – such
125
as density, isothermal compressibility, and saturation properties – can be calculated as
126
derivatives of the residual Helmholtz function, which is expressed in PC-SAFT as a hard chain
127
reference fluid (hc) with contributions from relatively weak London dispersion forces (disp) and
128
strong associating forces due to permanent dipoles (assoc):
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129 The hard chain and dispersion contributions to the Helmholtz energy are described by Gross and
131
Sadowski [40,41] and the association contribution by Chapman [42]. Five parameters, including
132
the number of segments
133
segments , the association energy between associating sites
134
association
135
for non-associating components in PC-SAFT. These parameters are fit so as to minimize the
136
deviation between experimental values of saturation pressure and saturated liquid densities.
137
2.2.2 Viscometric Properties
138
For liquid mixtures, viscosity is largely dependent on temperature and composition while
139
pressure dependence is usually negligible. Based on these dependencies, several equations have
140
been proposed to estimate the viscosity of mixtures. Here, the Arrhenius-like [32], Litovitz [33],
141
Andrade [34] and McAllister equations [35] were used. The Arrhenius-like equation can be
142
expressed as:
, segment diameter , the energy of dispersion interactions between and the volume of ,
and
are required
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, are required for each associating component while only
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where
145
of flow, and
is equal to viscosity in the high-temperature limit (T→ ∞), is the gas constant. The Litovitz equation is given as:
146 147
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and Andrade’s equation is: 7
is the activation energy
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148 ,
and
150
equation is expressed as:
are adjustable parameters. The two-parameter McAlister
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where
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149
151 152
where ,
153
and 2, and adjustable parameters, respectively.
154
Another flow property of interest can be calculated based on Eyring’s absolute rate theory [43].
155
According to this model, fluid motion is assumed to take place by an individual molecule in a
156
plane (or layer) occasionally acquiring the activation energy necessary to slip over the potential
157
barrier (arising from squeezing against its neighbors) to the next equilibrium position in the same
158
plane. This requires energy which can either be assumed to activate the flow unit or to produce a
159
hole of requisite size for particle translation to occur. The formation of the hole, or of this
160
intermediate activated state, then becomes the rate determining process which can be treated by
161
the theory of rate processes. From the Gibbs free energy of activation, the related excess
162
parameters can be calculated as:
and
are kinematic viscosities of the binary mixture, pure components 1
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164
The magnitude of
165
molecule must achieve for it to be activated for flow. It is indirectly a measure of the strength of
166
interactions between the molecules in solution.
167
2.2.3 Optical Properties
168
The refractive index is defined as the ratio of the speed of light through a vacuum to the speed of
169
light through a material of interest. These values convey information on the molecular
170
arrangement in a material, as light is bent due to interactions with molecules comprising the
171
material. It is then expected that refractive index results agree with measured densities. The
172
refractive indices measured in this paper were correlated using different mixing rules [36,37]
173
including Arago-Biot, Gladstone–Dale, Newton, Eyring–John, Edwards, Lorentz–Lorenz,
174
Weiners, Eykman, Hellers, and Oster semi-empirical models. These models can only be applied
175
if there are no chemical reactions in the mixture and if there are no changes in volume during
176
mixing. The excess refractive index
177
al. [44]:
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can also be calculated based on the definition of Reis et
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178 where
and
180
respectively, and
are volume fraction and refractive index of components 1 and 2,
is the refractive index of the mixture. Volume fraction is calculated by:
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179
181
can be viewed as an energy barrier over the ground state energy that a
182
3. Results and Discussion
183
The densities , dynamic viscosities , and refractive indices
184
experiment are compared with literature values reported in the NIST data archive [45] and shown 9
of pure amines measured from
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in Table 2. The relative standard uncertainties for measured densities, refractive indices and
186
viscosities are 0.002 g.cm-3, 0.001 and 0.1 mPa.s, respectively, indicating good agreement
187
between the experimental values reported in this paper and those found in the literature.
188
The densities, viscosities, and refractive indices for MEA + DETA/AEEA binary mixtures at all
189
studied temperatures are summarized in Tables 3 and 4. Partial molar volumes were calculated
190
by fitting a polynomial to density as a function of composition and differentiating. Thermal
191
expansion coefficients at 303.15 K were calculated by applying the central difference method to
192
densities at 298.15 K and 308.15 K to obtain the derivative of density with respect to temperature
193
at 303.15 K.
194
Table 2. Densities , viscosities , and refractive indices
195
literature values for T = (298.15, 303.15 and 308.15) K and P = 0.1 MPa.
1.0124 303.15 1.0084 1.0045
298.15 303.15
0.9458 0.9421
1.0120 1.0119 1.0121 1.0081 1.0080 1.0084 1.0040 1.0040
[20] [21] [15] [20] [21] [15] [20] [21]
0.9455 0.9317 0.9423 0.9370
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308.15
Ref
308.15
0.9378
of pure liquids with corresponding
Exp Lit Ref Monoethanolamine (MEA) 18.89 [15] 18.72 18.88 [15] 18.74 [15] 14.88 [15] 15.15 15.10 [22] 14.71 [24] 11.96 11.82 [24]
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298.15
Lit
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Exp
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[26] [26] [27] [26]
Diethylenetriamine (DETA) 5.63 5.627 [28] 4.50 4.512 [26] 4.804 [18] 3.85 3.830 [28]
Exp
Lit
Ref
1.4535
1.4540 1.4543
[22] [23]
1.4524 1.4527 1.4488
[22] [23] [25]
1.4519 1.4505
1.4822 1.4808 1.4793
Aminoethylethanolamine (AEEA) 1.0258 1.0252 [31] 98.62 98.60 [26] 1.4843 1.4845 [26] 298.15 1.0213 1.0215 [31] 70.57 70.50 [26] 1.4527 1.4826 [26] 303.15 1.0163 53.11 1.4811 308.15 Standard uncertainties are = 0.01 K, = 10 kPa, = 0.001 g.cm-3 and = 0.001; percentage relative standard uncertainty is = 10%.
196
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197
Table 3. Densities , viscosities , refractive indices
198
expansion coefficient
199
MPa.
,
partial molar volumes
, and thermal
of MEA (1) + DETA (2) for T = (298.15 to 308.15) K and P = 0.1
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5.63 8.28 10.37 12.15 13.87 15.47 16.82 18.22 19.23 19.31 18.72
200
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0.9458 0.9565 0.9646 0.9726 0.9794 0.9863 0.9927 0.9987 1.0051 1.0089 1.0124
RI PT
T = 298.15 K 55.642 109.082 0.0000 58.554 108.886 0.0989 59.173 108.711 0.2021 59.501 108.523 0.3013 59.722 108.328 0.4007 59.869 108.120 0.4984 59.958 107.916 0.6007 60.063 107.632 0.7027 60.176 106.958 0.8002 60.270 106.064 0.8987 60.331 104.075 1.0000 T = 303.15 K 0.0000 0.9421 4.50 55.0211 109.510 8.4917 0.0000 0.1619 0.9531 6.59 58.812 109.265 7.7641 0.0989 0.2973 0.9611 8.33 59.421 109.093 7.8036 0.2021 0.4258 0.9690 9.76 59.711 108.934 7.5335 0.3013 0.5307 0.9759 11.18 59.915 108.740 7.2753 0.4007 0.6308 0.9828 12.48 60.059 108.545 7.2243 0.4984 0.7174 0.9892 13.60 60.144 108.365 7.1775 0.6007 0.7980 0.9955 14.73 60.235 108.064 6.7303 0.7027 0.8790 1.0017 15.49 60.384 107.295 6.5888 0.8002 0.9336 1.0056 15.49 60.486 106.156 6.4638 0.8987 1.0000 1.0084 15.15 60.571 103.563 7.8342 1.0000 T = 308.15 K 0.0000 0.9378 3.85 54.085 110.012 0.0000 0.1619 0.9491 5.38 59.130 109.712 0.0989 0.2973 0.9571 6.68 59.548 109.600 0.2021 0.4258 0.9653 7.80 59.816 109.443 0.3013 0.5307 0.9723 8.89 60.104 109.180 0.4007 0.6308 0.9792 9.99 60.283 108.939 0.4984 0.7174 0.9856 10.89 60.341 108.817 0.6007 0.7980 0.9920 11.84 60.399 108.637 0.7027 0.8790 0.9985 12.42 60.549 107.848 0.8002 0.9336 1.0024 12.34 60.686 106.394 0.8987 1.0000 1.0045 11.90 60.806 102.665 1.0000 -3 Standard uncertainties are = 0.01 K, = 10 kPa, = 0.0002, = 0.001 g.cm and percentage relative standard uncertainties are = 10%, = 0.1% and = 5×10-4%. 0.0000 0.1619 0.2973 0.4258 0.5307 0.6308 0.7174 0.7980 0.8790 0.9336 1.0000
11
1.4822 1.4815 1.4806 1.4794 1.4778 1.4758 1.4731 1.4696 1.4657 1.4608 1.4535 1.4808 1.4802 1.4791 1.4778 1.4764 1.4743 1.4717 1.4683 1.4643 1.4591 1.4519
1.4793 1.4791 1.4778 1.4765 1.4752 1.4729 1.4703 1.4670 1.4631 1.4577 1.4505 = 0.001;
ACCEPTED MANUSCRIPT
201
Table 4. Densities , viscosities , refractive indices
202
expansion coefficient
203
MPa.
,
partial molar volumes
59.399 59.757 59.833 59.912 60.023 60.101 60.149 60.239 60.269 60.315 60.331
0.0000 0.1005 0.1993 0.2990 0.4047 0.5033 0.5985 0.6981 0.7985 0.8996 1.0000
1.4843 1.4824 1.4799 1.4774 1.4742 1.4714 1.4683 1.4647 1.4611 1.4573 1.4535
0.0000 0.1005 0.1993 0.2990 0.4047 0.5033 0.5985 0.6981 0.7985 0.8996 1.0000
1.4827 1.4810 1.4785 1.4760 1.4728 1.4700 1.4668 1.4633 1.4598 1.4559 1.4519
0.0000 0.1005 0.1993 0.2990 0.4047 0.5033 0.5985 0.6981 0.7985 0.8996 1.0000 = 0.001 g.cm-3 and = 5×10-4%.
1.4811 1.4796 1.4771 1.4745 1.4715 1.4685 1.4652 1.4620 1.4585 1.4545 1.4505 = 0.001;
SC
98.62 95.09 90.58 78.29 64.72 53.12 44.75 27.93 22.36 17.18 18.72
AC C
EP
TE D
M AN U
1.0258 1.0257 1.0252 1.0244 1.0234 1.0225 1.0217 1.0194 1.0182 1.0152 1.0124
RI PT
of MEA (1) + AEEA (2) for T = (298.15 to 308.15) K and P = 0.1
T = 298.15 K 101.530 101.515 101.498 101.458 101.347 101.233 101.139 100.889 100.744 100.328 99.8699 T = 303.15 K 0.0000 1.0213 70.57 59.264 101.977 0.1072 1.0214 69.25 59.972 101.947 0.2634 1.0209 67.59 60.064 101.933 0.4233 1.0202 59.50 60.124 101.894 0.5481 1.0193 48.92 60.255 101.775 0.6305 1.0184 39.84 60.334 101.658 0.6851 1.0176 32.81 60.375 101.571 0.7988 1.0155 20.04 60.452 101.351 0.8459 1.0143 15.94 60.487 101.207 0.9377 1.0114 12.82 60.546 100.645 1.0000 1.0084 15.15 60.571 99.863 T = 308.15 K 0.0000 1.0163 53.11 59.327 102.479 0.1072 1.0166 52.77 60.145 102.441 0.2634 1.0162 52.68 60.306 102.418 0.4233 1.0157 46.92 60.348 102.384 0.5481 1.0149 38.49 60.466 102.270 0.6305 1.0141 31.01 60.549 102.157 0.6851 1.0134 25.15 60.600 102.060 0.7988 1.0114 14.71 60.689 101.791 0.8459 1.0103 11.31 60.723 101.627 0.9377 1.0075 9.55 60.777 101.084 1.0000 1.0045 11.96 60.806 100.416 Standard uncertainties are = 0.01 K, = 10 kPa, = 0.0002, percentage relative standard uncertainties is = 10%, = 0.1% and 0.0000 0.1072 0.2634 0.4233 0.5481 0.6305 0.6851 0.7988 0.8459 0.9377 1.0000
, and thermal
9.3019 8.9093 8.8158 8.5273 8.3881 8.2482 8.1560 7.8779 7.7886 7.6132 7.8342
204
3.1. Volumetric Properties
205
The variation of
206
Kister correlations, are shown in Figure 1, and the corresponding fitting parameters
207
Redlich-Kister equation, along with their standard deviations, are given in Table 5.
against MEA composition for various isotherms, along with the Redlich-
12
of the
SC
RI PT
ACCEPTED MANUSCRIPT
208 Fig. 1. Excess molar volume (
) as a function of MEA mole fraction ( ) for
210
MEA (1) + AEEA/DETA (2) for T = (298.15 to 308.15) K. Dashed lines represent the
211
corresponding Redlich–Kister correlations.
212
Table 5. Coefficients
213
(
M AN U
209
) of the Redlich-Kister equation for excess molar volume
298.15 K 303.15 K 308.15 K
-1.354 -1.963 -3.649 -0.296 -0.708 -0.924
298.15 K 303.15 K 308.15 K 298.15 K 303.15 K 308.15 K
-0.206 -0.185 -0.274
MEA+DETA
-0.762 -0.938 -0.338 -0.028 0.032 0.051
0.011 0.007 0.004
0.003 0.004 0.007
0.001 0.002 0.003
0.002 0.003 0.002
-0.003 -0.002 -0.002
0.001 -0.001 0.001
AC C
0.048 -0.009 -0.047
-2.730 -2.846 -3.046
0.0045 0.0040 0.0049
-0.970 -1.034 -1.087
0.0017 0.0021 0.0016
0.032 0.031 0.031
0.00006 0.00006 0.00007
0.011 0.010 0.010
0.00004 0.00008 0.00003
MEA+AEEA
0.080 0.038 0.093
EP
298.15 K 303.15 K 308.15 K
along with their standard deviations .
TE D
) and excess refractive index
-0.445 -0.442 -0.458
MEA+DETA 0.011 0.011 0.010
MEA+AEEA -0.001 -0.001 -0.001
214
Negative values of
for binary mixtures are often attributed to strong chemical or specific
215
interactions between the components present in the mixtures. These effects can also be attributed
216
in part to structural contributions arising from the geometrical fitting of one component into the 13
ACCEPTED MANUSCRIPT
other due to differences in the molar volumes and free volume between unlike molecules
218
(packing effect). The presence and position of NH, amine and hydroxyl groups in both amine
219
mixtures – and the strong association forces from hydrogen-bonding that accompany – produce
220
the highly negative excess molar volumes. Excess molar volumes for MEA + DETA are more
221
negative than those of MEA + AEEA, indicating relatively stronger interactions in MEA +
222
DETA.
223
The variation of partial molar volumes
224
DETA/AEEA are tabulated in Tables 3 and 4 and plotted in Figure 2. Partial molar volumes of
225
MEA in both mixtures increase nonlinearly with increasing MEA composition, while the inverse
226
behavior is seen for the partial molar volumes of DETA and AEEA.
227
The calculated values of
228
298.15, 303.15 and 308.15 K are listed in Table 6. The partial molar volumes of species at
229
infinite dilution were smaller than the corresponding molar volumes of pure components. These
230
values show the strong intermolecular interactions between unlike molecules and the contraction
231
in volume upon mixing. The excess partial molar volumes at infinite dilution are negative and
232
have
SC
M AN U
from Redlich-Kister for all studied binary mixtures at
TE D sign
EP
same
with MEA mole fraction for binary mixtures of MEA +
as
AC C
the
and
RI PT
217
14
the
excess
molar
volumes.
SC
RI PT
ACCEPTED MANUSCRIPT
TE D
M AN U
233
234
Fig. 2. Partial molar volume (
) as a function of MEA mole fraction ( ) for T =
236
(298.15 to 308.15) K. A: MEA and B: DETA in a binary mixture of MEA (1) + DETA (2). C:
237
MEA and D: AEEA in a binary mixture of MEA (1) + AEEA (2).
238
Table 6. Partial molar volumes at infinite dilution (
239
components (
AC C
EP
235
T/K 298.15 303.15 308.15
) and molar volume of pure
) for T = (298.15 to 308.15) K.
MEA (Pure)
MEA+DETA
MEA+AEEA
DETA (Pure)
MEA+DETA
AEEA (Pure)
MEA+AEEA
60.331 60.571 60.806
55.325 54.628 53.450
58.670 58.457 58.481
109.082 109.510 110.024
104.392 103.956 103.312
101.530 101.977 102.479
100.598 100.671 100.883
Standard uncertainties are
= 0.01 K,
= 10 kPa,
15
= 0.0002 and
= 0.005.
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In cases where experimental data have not been collected, as is required to do fitting for the
241
Redlich-Kister equation, the most reliable method for generating volumetric property predictions
242
is by an equation of state. The PC-SAFT equation of state is used in this work, and the
243
parameters for the studied components are listed in Table 7. These values were fit to density and
244
vapor pressure correlations reported in the DIPPR database [46]. CO2 was treated as non-
245
associating in this work and its PC-SAFT parameters were reported by Gross and Sadowski [40].
246
PC-SAFT predictions for density and excess molar volume for both binary mixtures are shown in
247
Figures 3 and 4, respectively, and compared to experimental measurements. Values of
248
fit to minimize deviations between the excess molar volumes predicted and those measured.
249
Table 7. PC-SAFT parameters of studied pure components.
250
M AN U
SC
RI PT
240
.
and
Associating
(-)
3.5892
104.15
5.0467
45.01
2.0729
169.00
0.178696
TE D
103.16
2.6870
1982.5
4C
2.52
0.75
273-500
3.4692
237.15
0.535593
1952.9
2B
1.19
0.86
273-500
3.0673
225.94
0.051951
2277.2
4C
0.61
0.50
273-500
2.7852
169.21
0
0
-
2.78
2.73
216-304
EP
251
4.1833
range
Scheme
(-)
AC C
CO2
61.08
were
16
SC
RI PT
ACCEPTED MANUSCRIPT
M AN U
252 253
Fig. 3. Density (
254
DETA/AEEA (2) compared with calculated results from PC-SAFT for T = 298.15 K.
AC C
255
EP
TE D
) as a function of MEA mole fraction ( ) for MEA (1) +
256
Fig. 4. Excess molar volume (
) as a function of MEA mole fraction ( ) for T =
257
(298.15 to 308.15) K. A: MEA + DETA, B: MEA + AEEA compared with calculated results
258
from PC-SAFT.
259
Thermal expansion coefficients, given as:
260 17
ACCEPTED MANUSCRIPT
were calculated for pure MEA, DETA and AEEA using the PC-SAFT model and compared with
262
correlated values from the literature [47,30,31]. These results are shown in Figure S1 in
263
Supporting Information. Thermal expansion coefficients for MEA + DETA/AEEA binaries as a
264
function of MEA mole fraction are shown in Figure 5.
265
The maximum AAD for density predictions with PC-SAFT were 0.36% and 0.25% for MEA +
266
DETA and MEA + AEEA, respectively. Good liquid density predictions should be expected, as
267
the PC-SAFT parameters were fit to match experimental saturation pressures and saturated liquid
268
densities. Excess volume showed maximum AAD of 15.61% and 6.73% for MEA + DETA and
269
MEA + AEEA, respectively. For the thermal expansion coefficients calculated at 303.15 K and
270
0.1 MPa, AAD values were 13.62% for MEA + DETA and 9.05% for MEA + AEEA. Pure
271
component thermal expansion coefficients showed AAD values of 10.71%, 5.50% and 9.87% for
272
MEA, DETA and AEEA, respectively.
273
Finally, predictions for CO2 solubility in MEA + DETA/AEEA at 298.15 K and 0.1 MPa are
274
reported in Figure 6. Solubility data for CO2 in MEA + DETA/AEEA have not been found in the
275
literature and there is only sparse data on CO2 solubility in amine mixtures. Various studies with
276
SAFT modeling of CO2 solubility in alkanes [48], polymers [49], ionic liquids [50], and aqueous
277
amines [51] have shown promising results. PC-SAFT predicts that CO2 solubility decreases with
278
increasing MEA composition in both binary mixtures, and CO2 is more soluble in MEA + DETA
279
than in MEA + AEEA.
AC C
EP
TE D
M AN U
SC
RI PT
261
18
SC
RI PT
ACCEPTED MANUSCRIPT
280 Fig. 5. Thermal expansion coefficient (
) as a function of MEA mole fraction ( ) for
282
MEA + DETA (red) and MEA + AEEA (blue) at T = 303.15 K compared with calculated results
283
from PC-SAFT.
TE D
M AN U
281
AC C
284
MEA + DETA
EP
MEA + AEEA
285
Fig. 6. PC-SAFT predicted CO2 solubility as a function of MEA mole fraction ( ) for MEA (1)
286
+ DETA/AEEA (2) for T = 298.15 K and P = 0.1 MPa.
287
3.2. Viscometric Properties
288
Dynamic viscosities for the studied amine mixtures are reported in Tables 3 and 4 and shown
289
graphically in Figure 7. Viscosities were shown to decrease with increasing temperature for both
290
mixtures. The composition dependence of viscosity was more complicated; the viscosities of 19
ACCEPTED MANUSCRIPT
MEA + DETA mixtures increased up to a mole fraction of about 0.9 MEA and then shifted
292
down, whereas, for MEA + AEEA solutions, viscosities decreased up to a mole fraction of about
293
0.9 MEA and then shifted up.
294
In fluid systems at constant temperature, molecular weight and intermolecular forces are the two
295
main factors affecting viscosity. These two factors can often complement each other in their
296
effect on viscosity but may also compete in some scenarios. For example, both DETA and
297
AEEA have nearly identical molecular weights, but the viscosity of pure AEEA is twenty times
298
more than the viscosity of DETA. The discrepancy in viscosity can be attributed to stronger
299
interactions between AEEA molecules than between DETA molecules. Comparison between the
300
viscosity and density results of pure MEA and AEEA shows that interactions between molecules
301
in AEEA are stronger than in MEA.
302
AC C
EP
TE D
M AN U
SC
RI PT
291
303
Fig. 7. Dynamic viscosity (
) as a function of MEA mole fraction ( ) for T = 298.15 K
304
compared with various viscosity models. A: MEA + DETA, B: MEA + AEEA.
305
All calculated adjustable parameter values along with the corresponding standard deviations in
306
the viscosity models are listed in Table 8. Among the three-examined temperature-dependent
307
viscosity models, the Arrhenius-like model produced the lowest AAD%. The McAlister model
20
ACCEPTED MANUSCRIPT
predicted the viscosities of MEA + DETA/AEEA binary mixtures with absolute average
309
deviations less than 0.21% and 14.40%, respectively.
310
Table 8. Adjustable parameters of investigated viscosity models along with their AAD% for
311
MEA (1) + DETA/AEEA (2) binary mixtures.
Andrade
Arrhenius
Litovitz
0.107 -13.6 44.99 0.79 -1.70 1.38 0.57 1.56 245.8 -238 0.31
0.263 -12.2 41.40 0.78 -1.25 1.27 0.56 2.38 207.7 -241 0.15
MEA + DETA 0.425 0.530 -11.1 -11.0 33.85 33.96 0.27 0.50 -2.20 -2.08 1.04 1.04 0.43 0.65 0.002 0.001 2274 33.51 -36.2 62.3 4.89 7.71 MEA + AEEA 0.423 0.548 -11.4 -11.8 39.11 39.70 0.64 0.69 -1.07 -1.35 1.20 1.22 0.44 0.51 1.76 1.73 242.7 215.7 -234 -238 0.07 0.10 McAllister
0.630 -10.7 33.39 0.33 -1.90 1.02 0.50 0.003 23.20 -21.9 5.27
0.717 -10.5 33.19 0.34 -1.78 1.02 0.52 0.004 23.25 -14.3 5.23
0.798 -10.3 32.87 0.27 -1.66 1.01 0.42 0.001 3132 11.63 3.96
0.879 -10.4 33.30 0.23 -1.67 1.02 0.40 0.003 2274 -39.1 3.93
0.933 -10.8 34.19 0.31 -1.78 1.05 0.48 0.005 2092 -40.2 5.03
1.000 -10.8 34.17 0.72 -1.81 1.05 0.86 0.002 3738 122.9 8.66
0.630 -12.6 41.11 0.61 -1.74 1.26 0.42 0.79 285.3 -230 0.18
0.685 -13.9 44.03 0.78 -2.32 1.35 0.56 0.81 238.3 -238 0.30
0.798 -16.4 48.95 0.28 -3.47 1.50 0.04 0.41 246.8 -239 0.89
0.845 -17.8 52.07 0.34 -4.12 1.59 0.60 0.01 888.9 -180 3.18
0.937 -15.2 44.84 0.25 -3.38 1.37 0.51 0.002 1623 -115 4.61
1.000 -10.8 34.17 0.72 -1.81 1.05 0.86 0.002 3738 122.9 8.66
SC
0.000 -14.4 47.29 0.88 -1.98 1.45 0.66 1.61 232.3 -241 0.11
EP
Andrade
0.297 -11.2 33.63 0.19 -2.33 1.03 0.33 0.003 1645 -94.6 2.24
M AN U
Litovitz
0.161 -11.1 32.95 0.37 -2.47 1.01 0.20 0.12 360.8 -211 0.24
TE D
Arrhenius
0.000 -10.0 29.06 1.32 -2.32 8.90 1.17 1.54 31.02 -274 0.22
RI PT
308
AC C
MEA + DETA
298.15 K 303.15 K 308.15 K
19.60 15.88 13.25
12.59 10.12 7.61
MEA + AEEA 2.08 1.88 1.98
36.38 22.43 14.94
152.3 134.5 122
9.62 11.93 14.40
312
The Gibbs free energy of flow activation, calculated from equation 10, is indirectly a measure of
313
the strength of interactions between the molecules in solution. Figure 8 shows the excess Gibbs
314
free energy of flow activation at 298.15, 303.15 and 308.15 K for binary mixtures of MEA +
315
DETA/AEEA. Excess Gibbs free energy of flow activation for MEA + DETA is positive for all
21
ACCEPTED MANUSCRIPT
temperatures and compositions with extrema around 0.5 mole fraction of MEA.
is negative
317
in the MEA rich region for MEA + AEEA binary mixture. Positive values of
show that
318
specific interactions between unlike molecules are dominant in the studied binary mixtures.
M AN U
SC
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316
319
Fig. 8. Excess Gibbs free energy of flow activation (
) as a function of MEA mole
321
fraction ( ) for T = (298.15 to 308.15) K. A: MEA + DETA, B: MEA + AEEA.
322
3.3. Optical Properties
323
The refractive indices of MEA + DETA/AEEA binary mixtures at temperatures of 298.15,
324
303.15 and 308.15 K are reported in Tables 3 and 4 and shown graphically in Figure S2 in
325
Supporting Information. At all temperatures, the refractive indices for both amine mixtures
326
decrease non-linearly with increasing MEA composition. The refractive index values for the pure
327
chemicals vary in the order of AEEA > DETA > MEA and decrease as temperature increases.
328
The refractive indices were correlated using various models, including Arago-Biot, Gladstone–
329
Dale, Newton, Eyring–John, Edwards, Lorentz–Lorenz, Weiners, Eykman, Hellers, and Oster
330
semi-empirical models. The absolute average deviations of these models are shown graphically
AC C
EP
TE D
320
22
ACCEPTED MANUSCRIPT
in Figure 9. All studied models can predict the refractive index values of MEA + DETA/AEEA
332
binary mixtures with maximum AAD of less than 0.8% and 0.3%, respectively. The deviations
333
of these models for MEA + DETA decrease with increasing temperature, while for MEA +
334
AEEA the opposite trend is seen.
M AN U
SC
RI PT
331
335
Fig. 9. Comparison between AAD% from experimental and calculated refractive indices for T =
337
298.15 K. (red) MEA + DETA, (blue) MEA + AEEA.
338
The excess refractive index
339
function of MEA mole fraction are shown in Figure 10. Excess refractive index values are
340
positive for both amine mixtures with a maximum at MEA mole fractions of 0.6 and 0.5 for
341
MEA + DETA and MEA + AEEA, respectively. Positive values of
342
values and vice versa, and both
343
Therefore, a more positive
344
light velocity in the medium, and a lower refractive index than the ideal solution.
TE D
336
AC C
EP
, calculated based on the definition of Reis et al. [44], as a
and
correspond to negative
shift to zero values with increasing temperature.
value is indicative of more free volume in the solution, higher
23
345
SC
RI PT
ACCEPTED MANUSCRIPT
Fig. 10. Excess refractive index (
) as a function of MEA mole fraction ( ) for MEA (1) +
347
DETA /AEEA (2) for T = (298.15 to 308.15) K.
348
4. Conclusions
349
Thermophysical properties of the monoethanolamine (MEA) + diethylenetriamine (DETA) /
350
aminoethylethanolamine (AEEA) binary mixtures – including densities, viscosities, and
351
refractive indices – were measured at atmospheric pressure for 298.15, 303.15 and 308.15 K.
352
Negative excess molar volumes and positive excess refractive indices were obtained that
353
indicated stronger interactions between unlike components in the mixtures than like components.
354
Excess parameter values of all studied systems shift toward zero when temperature increases,
355
showing that solutions approach ideality in the high-temperature limit.
356
The Redlich-Kister model satisfactorily correlated the values of
357
standard deviations of 0.0049 and 6 x 10-5, respectively, for MEA + DETA and 0.0021 and 8 x
358
10-5, respectively for MEA + AEEA.
359
Experimental viscosities were well correlated with Arrhenius-like, Litovitz, Andrade and
360
McAlister models, with maximum AAD% of 1.32, 1.17, 7.71 and 2.08, respectively, for MEA +
361
DETA and 0.88, 0.86, 8.66 and 14.40, respectively, for MEA + AEEA.
AC C
EP
TE D
M AN U
346
24
and
, yielding maximum
ACCEPTED MANUSCRIPT
Refractive indices were correlated satisfactorily using Lorentz-Lorenz, Eykman and Edwards
363
semi-empirical models with maximum AAD% equal to 0.2.
364
PC-SAFT predictions for density, excess molar volume, thermal expansion coefficient and CO2
365
solubility were presented. Density predictions for both binaries were excellent, while excess
366
molar volumes and thermal expansion coefficients showed more deviation. Excess volume
367
predictions showed maximum AAD% of 15.61 and 6.73 for MEA + DETA and MEA + AEEA,
368
respectively, and thermal expansion coefficients calculated at 303.15 K and 0.1 MPa showed
369
AAD% of 13.62 and 9.05 for MEA + DETA and MEA + AEEA, respectively.
370
Acknowledgment
371
The experimental support from University of Mazandaran is gratefully acknowledged.
AC C
EP
TE D
M AN U
SC
RI PT
362
25
ACCEPTED MANUSCRIPT
372
References
373
[1]
IPCC, Intergovernmental Panel on Climate Change 2007: The Physical Science Basis, Cambridge University Press 32 Avenue of the Americas, New York, NY 10013-2473,
375
USA, New York, 2007. http://www.cambridge.org/9780521880091.
376
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374
B. Dutcher, M. Fan, A.G. Russell, Amine-Based CO 2 Capture Technology Development
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P. V. Kortunov, L.S. Baugh, M. Siskin, Pathways of the Chemical Reaction of Carbon
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Highlights
Density, viscosity and refractive index of amines mixtures were measured
•
Different excess properties were calculated from the experimental measurements
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PC-SAFT models were used to calculation of volumetric properties and CO2 solubility
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Different models were used to reproduce the viscosities and refractive indices data
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