Acs Iecr 9b03512

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Thermodynamics, Transport, and Fluid Mechanics

Modelling hydrate dissociation curves in the presence
of hydrate inhibitors with a modified CPA EoS.
André M. Palma, Antonio J. Queimada, and Joao A.P. Coutinho
Ind. Eng. Chem. Res., Just Accepted Manuscript • DOI: 10.1021/acs.iecr.9b03512 • Publication Date (Web): 20 Sep 2019
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Page 1 of 25 Industrial & Engineering Chemistry Research
1
2
3
4 Modelling hydrate dissociation curves in the
5
6
7 presence of hydrate inhibitors with a modified CPA
8
9
10 EoS.
11
12
13 André M. Palma1, António J. Queimada2,* and João A. P. Coutinho1
14
1CICECO, Chemistry Department, University of Aveiro, Campus de Santiago, 3810-193 Aveiro,
15
16 Portugal.
17
18 2KBCAdvanced Technologies Limited (A Yokogawa Company), 42-50 Hersham Road, Walton-on-
19 Thames, Surrey, United Kingdom, KT12 1RZ.
20
21 *Corresponding author. E-mail address: aqueimada@kbcat.com
22
23 Abstract
24
25 A modified CPA equation of state has been applied for the description of non-inhibited hydrates.
26 In this work, this model is applied to the description of dissociation curves of hydrates inhibited
27 by six thermodynamic inhibitors (methanol, ethanol, MEG, DEG, TEG and glycerol), while also
28
focusing on promoting a correct simultaneous description of SLE and VLE between the inhibitors
29
30 and water. The study concern some of the most well-known hydrate formers (methane, ethane,
31 propane, CO2, Xe and H2S ) and mixtures of these gases. The maximum number of binary
32 interaction parameters applied between water and the hydrate inhibitor is two, one for the
33 physical term and one for association. A comparison between this approach and the hydrates
34
model present on Multiflash is reported, revealing that the present approach, while less
35
36 accurate than Multiflash is still able to correctly describe hydrate inhibition, VLE and LLE, while
37 using a smaller number of parameters.
38
39 Keywords: CPA, Equation of state, Gas hydrates, Hydrate inhibition, van der Waals-Platteeuw
40
41 1. Introduction
42
The formation of hydrates inside pipelines or equipment are one of the major hazards that flow
43
44 assurance engineers need to consider. Even with low water contents, gaseous streams rich in
45 gases like methane or CO2 may form this type of solid structures at low temperatures and/or
46 high pressures. The most common method to deal with this issue is the addition of
47 thermodynamic inhibitors, which interact with water, reducing the temperature, and/or
48
49
increasing the pressure of hydrate formation.
50
A dedicated model is necessary to describe hydrate phases, with the most well-known models
51
52 being based on the van der Waals and Platteeuw theory, 1 such as the modification proposed by
53 Parrish and Prausnitz, 2 which is still one of the most popular. However, these models only
54 describe the thermodynamics of the hydrate phase and a second model is necessary to describe
55 fluid phases. In most industrial software fluid phases are either described by an equation of state
56
or by an activity coefficient model (or both, using excess Gibbs energy mixing rules). For the case
57
58 of hydrate calculations, the first is more commonly applied because of the high dissociation
59 pressures involved. 3
60
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Industrial & Engineering Chemistry Research Page 2 of 25
1
2
3 In the present study a modified CPA equation of state 4 is applied for the fluid phases. This model
4
explicitly accounts for hydrogen bonding interactions between water and hydrate inhibitors,
5
6 while keeping the simplicity of a cubic equation of state for the interactions between the
7 different gases and the non-polar components in study. Other studies to describe hydrate
8 inhibition with equations of state, explicitly accounting for hydrogen bonding to describe
9 hydrate inhibition, include those of Folas et al. 5 and Pedrosa et al. 6 with CPA, Li et al. with SAFT,
10 7 Dufal et al. with SAFT-VR 8 and Kondori et al. with a combination of PC-SAFT with UNIQUAC. 9
11
12 In this study we evaluate the performance of a modified CPA model for representing hydrate
13
14
inhibition. Six hydrate inhibitors are studied (methanol, ethanol, ethylene glycol (MEG),
15 diethylene glycol (DEG), triethylene glycol (TEG) and glycerol) in presence of single hydrate
16 formers. The performance of the modified CPA is also investigated for some natural/sour gas
17 mixtures in presence of inhibitors. The results here obtained are compared with those of a
18 commercial model present in the Multiflash software 10 (6.1 version), one of the industry
19
20
standards for hydrate calculations.
21
2. Models
22
23 The hydrate phase is described using the modified van der Waals and Platteeuw theory, 1
24
proposed by Parrish and Prausnitz. 2 This model is known to accurately predict hydrate
25
26 dissociation temperatures for multicomponent fluids. However, there are still issues/limitations
27 in the description obtained by this theory: The model assumes spherical symmetry; the
28 interactions between the molecules inside each cage are not considered; and the cavities are
29 not distorted by the presence of the guest molecule. Despite these limitations, the model is
30
31
known for its accuracy and has been successfully coupled with diverse equations of state.
32
In this work the fluid phases are described using the modified CPA as detailed in the following
33
34 section.
35
2.1 Modified CPA
36
37 Most of the modified CPA structure is based on the simplified CPA: 11
38
39 1 𝐴(𝑇)𝜌 1
40 (
𝑍 = 𝑍𝑝ℎ𝑦𝑠 + 𝑍𝑎𝑠𝑠𝑜𝑐 = 1 ― 𝐵𝜌 ― 𝑅𝑇(1 + 𝐵𝜌) ― 2 1 + 𝜌
𝛿𝑙𝑛𝑔
𝛿𝜌 )∑𝑖𝑚𝑖(1 ― 𝑋𝑖) (1)
41
42 𝐴 is the energy parameter (𝐴(𝑇) = 𝑛2𝑎(𝑇)), 𝐵 is the co-volume (𝐵 = 𝑛𝑏), 𝜌 represents the
43 density, 𝑔 is a simplified hard-sphere radial distribution function,11 𝑋𝐴𝑖 represents the mole
44 fraction of component i not bonded at site A and 𝑚𝑖 is the mole number of sites of type i.
45
46 Equations 2-3 show the mixing rules for a and b:
47
48
𝑎 = ∑𝑖∑𝑗𝑥𝑖𝑥𝑗𝑎𝑖𝑗 (2)
49
50
51
52
𝑏 = ∑𝑖𝑥𝑖𝑏𝑖 (3)
53
54 with:
55
56 𝑎𝑖𝑗 = 𝑎𝑖𝑎𝑗(1 ― 𝑘𝑖𝑗) (4)
57
kij are binary interaction parameters.
58
59
60

1
2
3 The first of the four differences between the simplified CPA and the present model is in the alpha
4
function used (based on a Mathias-Copeman polynomial). For some specific cases, like water,
5
6 there are relevant changes in the description of pure component properties, when using this
7 alpha function. 12
8 2
9 𝑎(𝑇) = 𝑎𝑐(1 + 𝑇′ × 𝑐1 + 𝑇′2 × 𝑐2 + 𝑇′3 × 𝑐3 + 𝑇′4 × 𝑐4 + 𝑇′5 × 𝑐5) (5)
10
11 with T’=(1 ― 𝑇𝑟), Tr =T/Tc
12
13 𝑋𝑖is calculated as:
14
15
16 1
17 𝑋𝑖 = 1 + 𝑔𝜌∑ 𝑚 𝑋 Δ𝑖𝑗 (6)
𝑗 𝑗
18 𝑗
19
20
21 where the association strength (Δij) given by:
22
23 𝜀𝑖𝑗
24
𝑖𝑗
Δ = 𝑔𝑏 𝛽 𝑒 ― 1 𝑖𝑗 𝑖𝑗
( 𝑅𝑇
) (7)
25
26
27
28 𝜀𝑖𝑗 and 𝛽𝑖𝑗 are the association energy and volume for interactions between sites i and j.
29
30 The simplified radial distribution function is presented in equation 8.11,13
31
32
33 1
34 𝑔(𝜌) = 1 ― 0.475𝑏𝜌 (8)
35
36
37
38 When two or more associative compounds are present in a mixture, CPA needs combining rules
39 for the cross-associative parameters. CR-214 combining rules, as proposed by Kontogeorgis et
40 al.15 were applied:
41
42 𝛽𝑖𝑗 = 𝛽𝑖𝛽𝑗 (9)
43
44 (𝜀 𝑖 + 𝜀 𝑗 )
45 𝜀𝑖𝑗 = 2 (10)
46
47
48
49 The second of the four changes in comparison to the simplified CPA is the correct description of
50 the pure component critical temperatures and pressures, which imply that ac and the co-volume
51 (b) are not regressed simultaneously, but instead obtained by solving the following set of
52 equations:
53
54 𝑃𝐶𝑃𝐴 (𝑇𝑒𝑥𝑝
𝑐 ,𝑣𝑐 ) = 𝑃𝑐
𝑐𝑎𝑙𝑐 𝑒𝑥𝑝
(11)
55
56
57
(∂𝑃∂𝑣)𝑇| 𝑇 = 𝑇𝑐
=0 (12)
𝑣 = 𝑣𝑐, 𝑐𝑎𝑙𝑐
58
59
60

1
2
3
4 ( )|
∂2𝑃
∂𝑣2
𝑇 𝑇 = 𝑇𝑐
=0 (13)
5 𝑣 = 𝑣𝑐, 𝑐𝑎𝑙𝑐
6
7 where T is temperature, P is pressure, v is molar volume and the subscript c means critical. A
8 detailed discussion on this change of parameterization can be found on previous works with this
9 version of CPA. 4,16,17
10
11 The third modification lies in the use of a volume shift at 0.7 Tc to fit density, instead of fitting
12 this property directly.
13
14 𝑣𝑡 = 𝑣0 ― 𝑐𝑣𝑠 (14)
15
16 vt is the volume after translation, v0 is the volume before translation and cvs is the volume shift.
17
18 The fourth difference, is a consequence of the present alpha function showing inversion points
19 on its second derivative. This fourth change introduces an extrapolation between Tc and 1.1 x Tc
20 after which the model considers the API alpha function for the compound. 18
21
22 The following equations were considered to optimize the values of kij.
23
24 𝑐𝑎𝑙𝑐. 2
(
𝑒𝑥𝑝.
25 𝑂𝐹 = ∑𝑖
𝑛𝑝 𝑇𝑏𝑢𝑏 ― 𝑇𝑏𝑢𝑏
𝑇𝑒𝑥𝑝.
𝑏𝑢𝑏
) (15)
26
(
𝑒𝑥𝑝.
28
29
𝑂𝐹 = ∑𝑖
𝑛𝑝 𝑃𝑏𝑢𝑏 ― 𝑃𝑏𝑢𝑏
𝑃𝑒𝑥𝑝.
𝑏𝑢𝑏
) (16)
31
32
𝑛𝑝𝑜 𝑛𝑐
𝑂𝐹 = ∑ ∑ 𝑘 𝑖 ( 𝑥𝑒𝑥𝑝.
𝑖,𝑘 ― 𝑥𝑖,𝑘
𝑥𝑒𝑥𝑝.
𝑖,𝑘
) (17)
33
34 where npo is the number of phases to optimize. As in most mixtures in study the fitting is
35 obtained from SLE and VLE simultaneously, a weighted sum between the objective functions 17
36 and 15 or 16 was applied.
37
38
39
40 3. Results and discussion
41
42 Most compounds studied in this work have been previously parameterized with the modified
43 CPA. 4,12,16,19 Exceptions to this are diethylene glycol (DEG) and triethylene glycol (TEG). The pure
44 compound parameters for all compounds in this study are presented in Table 1. The association
45 schemes used in this work are 4C for water, 2B for methanol and ethanol, 2x2B for the glycols
46
and 3x2B for glycerol. The transferability approach, presented in a previous work 19 is applied
47
48 for the associative parameters of the hydroxyl groups.
49
50 Table 1 – Pure component parameters used in this work
51 Compound ac b. 105 c1 c2 c3 c4 c5 β.102 ε (J.mol-1)
52 (Pa.m6.mol-2) (m3.mol-1)
53 water 0.43 2.39 0.56 -2.54 -2.01 1.46 8.63 0.483 22013
54 MEG 1.72 6.87 1.10 -3.64 12.16 -37.1 42.5 0.162 24913
55
DEG 3.35 12.53 1.75 -9.66 43.77 -102.36 93.87 0.153 24913
56
57 TEG 5.08 17.57 2.35 -12.50 51.77 -111.32 94.40 0.113 24913
58 methanol 0.68 4.61 0.9 -2.47 3.26 0 0 0.465 24913
59 ethanol 1.13 6.40 1.04 -1.46 -0.79 3.76 0 0.162 24913
60

1
2
3 glycerol 2.59 9.11 0.45 4.16 -19.32 19.9 0 0.162 24913
4 methane 0.23 2.98 0.59 -1.47 9.02 -27.39 31.55
5
ethane 0.57 4.51 0.71 -1.17 7.00 -20.37 22.42
6
7 propane 0.95 6.27 0.82 -1.63 9.36 -24.39 23.68
8 isobutane 1.35 8.07 0.89 -1.94 11.12 -29.03 28.57
9 n-butane 1.41 8.07 0.88 -1.39 7.72 -20.51 21.48
10
n-pentane 1.94 10.05 1.00 -2.08 12.24 -32.87 32.84
11
12 N2 0.14 2.68 0.63 -1.45 9.42 -29.74 36.21
13 O2 0.14 2.21 0.89 -1.94 11.12 -29.03 28.57
14 CO2 0.37 2.97 0.90 -1.35 5.61 0.00 0.00
15
H2S 0.46 2.99 0.72 -1.07 4.82 -8.86 5.24
16
17 Xe 0.42 3.57 0.56 -0.51 1.60 -5.49 7.49
18
19
20 CPA is usually able to describe simultaneously the freezing point depressions of water + hydrate
21 inhibitors, as well as, hydrate dissociation curves, while using a single binary interaction
22
parameter (a constant kij). However, using this approach leads to an incorrect description of VLE
23
24 for these mixtures. The CPA model present on Multiflash is capable of describing these phase
25 equilibria simultaneously. Nevertheless, it requires a larger number of parameters, both for the
26 pure component and for the mixtures, than those used by the modified CPA.
27
28 In this work, for three of the six hydrate inhibitors in analysis a binary interaction parameter for
29 the volume of association (βij) was added. For the remaining compounds, either there was a
30
good description of the three types of phase equilibria, or there is a lack of data on one of these
31
32 equilibria. Thus for these mixtures the binary interaction parameters differ from those of the
33 previous study with water. 12 This should enable a better simultaneous description of hydrate
34 dissociation curves and VLE.
35
36 3.1 SLE and VLE of water + hydrate inhibitors.
37
38 Before looking at the quality of the hydrate dissociation curves, it is important to look at how
39 this approach works for both freezing point depressions and VLE. The binary interaction
40 parameters that were used are presented in Table 2. These are different from those used in
41 previous works, due to the simultaneous fitting to VLE and SLE equilibria. The remaining binary
42
43 interaction parameters were presented in previous works 4,12,16,19,20.
44
Table 2 – binary interaction parameters between water and the hydrate inhibitors
45
46 Inhibitor kij βij.102
47
48 methanol -0.115 -0.080
49 ethanol -0.100 -0.071
50 MEG -0.085 -0.040
51
52
DEG -0.130 0
53 TEG -0.185 0
54 glycerol -0.050 0
55
56
57 For methanol, ethanol and MEG there was a need to introduce a binary interaction parameter
58 for the volume of association to describe simultaneously SLE and VLE. The value of the volume
59
60 of association for water is 0.483 x 10-2, which is just one order of magnitude above the values

1
2
3 presented for the binary interaction parameters, which justifies their relevance for the present
4
equilibria calculations.
5
6 For glycerol and diethylene glycol mixtures with water, accurate results were obtained without
7
the need of a βij. For triethylene glycol mixtures with water, the binary interaction parameters
8
9 were fitted to the VLE data from Chouireb et al. 21 and to the hydrate dissociation curves with
10 xenon. This is due to the lack of availability of SLE data for this mixture. Xenon results are usually
11 accurate without the need to fit a binary interaction parameter between water and xenon (when
12 SLE data is used for water + other hydrate inhibitors), thus these data were used in place of the
13
14
SLE data. Tables S1 and S2 in the supporting information present the deviations on pressure and
15 composition for water + methanol and water + ethanol.
16
17 Results for the freezing point depression of water + MEG, water + glycerol and water + ethanol
18 are presented in Figure 1. It is important to note that these modelling results do not account for
19 the formation of solid complexes.
20
21 280 300
22
23 270 290
24
25 260 280
26 270
27 250
T/K
T/K
28 260
240
29
250
30 230
31 240
32 220
33 230
34 210
0 0.25 0.5 0.75 1 220
35
0 0.25 0.5 0.75 1
36 x ethylene glycol x glycerol
37
38
280
39
40
260
41
42 240
43
44 220
T/K
45
46 200
47
48 180
49
50 160
51
52 140
53 0 0.25 0.5 0.75 1
x ethanol
54
55
Figure 1 – Freezing point depressions for the mixtures: water + MEG, water + glycerol and
56
57 water + ethanol. Data taken from the TRC database 22 and Ott et al. 23
58
59
The present approach captures the description of most of the ethylene glycol and glycerol SLE
60 diagrams with water. In the case of ethanol it tends to overestimate the ice saturation line.

1
2
3
4
5 3.2 Single component gas hydrates
6
7 The simplest hydrate inhibition case is that of mixtures of water + hydrate inhibitor + a gas
8 containing a single compound. Starting by compounds known to form hydrates of type I, Figure
9 2 presents results for mixtures containing methane, water and one inhibitor (methanol, mono
10
11 ethylene glycol or DEG).
12
17
13 25
14 10 wt %
15
15 20 wt %
16 20 13
35 wt %
17
18 50 wt % 11
15
P/MPa
P/MPa
19 60 wt % 9
20
21 10 7
22
23 5
24 5 10 wt %
3 30 wt %
25 a) 50 wt %
b)
26
0 1
27
218 228 238 248 258 268 278 288 250 260 270 280 290
28 T/K T/K
29
30 46
31 6.6 wt % 10 wt %
14 41
32
10 wt % 20 wt %
33 36
12 35 wt %
34 20 wt %
35 31
10 35 wt % 40 wt %
36
P/MPa
P/MPa
26 50 wt %
37 50 wt %
8 21
38
39 16
40 6
41 11
42 4
43
c) 6 d)
44 2 1
45 255 265 275 285 265 275 285 295
T/K T/K
46
47
48
Figure 2 – Hydrate dissociation curves for mixtures of methane + water + inhibitor; Inhibitor a)
49 methanol, b) MEG, c) DEG, d) TEG. wt % refers to weight percentage of inhibitor in aqueous
50 solution. ○ – Ng and Robinson 24; Δ – Robinson and Ng 25; x – Mohammadi and Richon 26; ◊ –
51 Afzal et al. 27; □ – Mahmoodaghdam and Bishnoi 28; + – Mohammadi and Richon 29; * – Ross
52 and Toczylkin. 30; ∇ - Haghighi et al. 31
53
54 For the mixtures containing methanol, MEG and DEG, the modified CPA is capable of an accurate
55
description of the effect of inhibitor concentration up to 50 wt % (up to 60 % in the case of
56
57 methanol). There are some uncertainties for the mixture containing 50% of methanol, where
58 the two sets of experimental data differ, with the present approach being able to describe one
59 of the sets. Due to this, the deviations for the inhibition with methanol can reach up to 1.9 K. In
60 the case of diethylene glycol, the results at low pressures present higher deviations, due to the

1
2
3 slower growth of pressure with temperature at these conditions, which leads to a very
4
significant ΔT of around 6.5 K at the data point for the lowest pressure. For the case of TEG the
5
6 dissociation curves at lower compositions are well described by the model. At higher
7 compositions the data from the different authors are not consistent, with the present model
8 presenting good results when compared to the data of Mohammadi and Richon 26. The results
9 presented on Table 3 use the complete sets of data from the literature, thus the average
10
deviations obtained consider more data than the one presented on the Figures. Results for
11
12 methane hydrates in presence of ethanol and glycerol are also presented on Table 3 (as well as
13 on the supporting information).
14
15 Most xenon hydrates are correctly described, only considering binary interaction parameters
16 obtained from SLE, between water and the hydrate inhibitor. Figure 3 presents results for the
17 hydrate inhibition of xenon in presence of methanol and TEG. For the cases with the remaining
18 inhibitors results are reported in Table 3 and the supporting information.
19
20 1 1
21 10 wt %
22 0.9 0.9
20 wt % 20 wt %
23 0.8 30 wt % 0.8
24 40 wt %
25 0.7 0.7
26
P/MPa
0.6
P/MPa
0.6
27
28 0.5 0.5
29 0.4 0.4
30
31 0.3 0.3
32 0.2 a)
33 0.2 b)
34 0.1 0.1
35 260 270 280 290 0 50 100 150 200 250
T/K T/K
36
37
Figure 3 – Hydrate dissociation curves for mixtures of xenon + water + inhibitor; Inhibitor a)
38
39 methanol, b) TEG. wt % refers to weight percentage of inhibitor in the aqueous phase. ○ –
40 Maekawa. 32
41
42 The results for xenon hydrates are accurate for all cases in analysis.
43
44 To continue this analysis with hydrate type I formers, Figure 4 and 5 present results for
45 dissociation curves containing ethane hydrates.
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60

1
2
3
4
5
6
7
8 20 3 7.1 wt %
9
10 10 wt %
2.5
11 15 10 wt %
12 15 wt %
20 wt %
P/MPa
P/MPa
13 30 wt % 2
14 10 50 wt %
15
1.5
16
17 5
18 1
19 a) b)
20 0 0.5
21 242 252 262 272 282 274 276 278 280 282 284 286
22 T/K T/K
23
24
25 20 wt % 30 wt %
3
26
27 40 wt % 50 wt %
28 2.5
29
30
P/MPa
2
31
32
33 1.5
34
35 1
36
37
c)
38 0.5
39 261 266 271 276 281
T/K
40
41
42
Figure 4 – Hydrate dissociation curves for mixtures of ethane + water + inhibitor; Inhibitor a)
43 methanol, b), c) DEG. wt % refers to weight percentage of inhibitor in the aqueous phase. ○ –
44 Ng and Robinson 24; Δ – Mohammadi et al. 33; □ – Maekawa 34; ◊ – Mahmoodaghdam and
45 Bishnoi 28; x – Afzal et al. 27.
46
47 A very accurate description is obtained for the hydrate dissociation curves of ethane, when
48 inhibited with methanol or DEG, as is presented in Figure 4. In the case of the inhibition with
49
methanol, the model captures the water-liquid-hydrate transition and is able to describe this
50
51 section of the diagram with a maximum ΔT of 1.9 K. For the case of DEG the deviations are
52 always below 1.25 K. For MEG, TEG and glycerol similar results were obtained and are presented
53 on Figure 5.
54
55
56
57
58
59
60

1
2
3 3000 40
4 10 wt %
5 20 wt % 35 10 wt %
6 2500 30 wt %
7 40 wt % 30 20 wt %
8
2000 25 40 wt %
9
P/MPa
P/MPa
10 20
11
1500
12 15
13
14 10
1000
15
16 a) 5 b)
17 500 0
18 260 270 T/K 280 268 273 278 T/K 283 288 293
19
20 3.5 3.5
21 10 wt % 20 wt % 10 wt % 20 wt %
22 30 wt % 40 wt %
3 3 30 wt % 40 wt %
23 50 wt %
24 50 wt %
2.5 2.5
25
P/MPa
P/MPa
26
27 2 2
28
29 1.5 1.5
30
31 1 1
32 c) d)
33
0.5 0.5
34
262 267 272 277 282 287 0 50 100 150 200 250
35 T/K T/K
36
37 Figure 5 – Hydrate dissociation curves for mixtures of ethane + water + inhibitor; Inhibitor a)
38 MEG b), c) TEG, d) glycerol. wt % refers to weight percentage of inhibitor in aqueous solution.
39
40
○ – Ross and Toczylkin 30; □ – Maekawa. 34
41
As in the case of the ethane hydrate inhibition with methanol, the model is able to describe the
42
43 water-liquid-hydrate section of the diagram for the inhibition with TEG. For the remaining
44 compounds a very accurate description of the water-gas-hydrate section of the dissociation
45 curves is obtained.
46
47 For mixtures containing propane, a hydrate type II former, the results are presented on Figures
48 6 and 7.
49
50
51
52
53
54
55
56
57
58
59
60

1
2
3 7 0.2
4 35 wt %
5 0.19
6 5 wt %
6 0.18 40 wt %
7 5 0.17 45 wt %
8 10.39 wt %
9 4 0.16
P/MPa
P/MPa
10 0.15
11 3
0.14
12
13 2 0.13
14 0.12
1
15 a) 0.11 b)
16 0
17 0.1
1
3
5
-1
11
13
7
9
15
17
19
21
23
25
27
29
31
33
35
37
39
41
43
45
47
49
51
53
55
57
59
61
63
65
67
69
71
73
75
77
79
81
83
85
87
89
91
93
101
95
97
99
103
105
107
109
111
113
115
117
119
121
123
125
127
129
131
133
135
137
139
141
143
145
147
149
151
153
155
157
159
161
163
165
167
169
171
173
175
177
179
181
183
185
187
189
191
193
195
197
199
201
203
205
207
209
211
213
215
217
219
221
223
225
227
229
231
233
235
237
239
241
243
245
247
249
251
253
255
257
259
261
263
265
267
269
271
273
275
277
18 235 240 245 250 255
T/K T/K
19
20 0.55
10 wt %
21 0.5 20 wt %
22
30 wt %
23 0.45
35 wt %
24
0.4 40 wt %
25
26
P/MPa
0.35
27
0.3
28
29 0.25
30
31 0.2
32 0.15 c)
33
34 0.1
35 250 260 T/K 270 280
36
37 Figure 6 – Hydrate dissociation curves for mixtures of propane + water + inhibitor; Inhibitor a),
38 b) methanol c) MEG. wt % refers to weight percentage of inhibitor in aqueous solution. ○ – Ng
39
40
and Robinson 24; □ – Mohammadi and Richon 33; Δ – Maekawa. 35
41
Results for these hydrate dissociation curves are typically accurate, in most cases. For mixtures
42
43 containing methanol, the results present higher deviations for concentration of hydrate inhibitor
44 above 30 wt %. For the mixture containing MEG the results present a ΔT below 1 K up to 35 wt%.
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60

1
2
3 0.55 0.55
4 5 wt % 7.3 wt %
5 0.5 0.5
10 wt % 10 wt %
6 0.45 0.45
7 16.4 wt %
0.4 15 wt %
8 0.4 20 wt %
9 29.2 wt %
P/MPa
P/MPa
0.35 0.35
10
11 0.3 0.3
12 0.25 0.25
13
14 0.2 0.2
15 0.15 a) 0.15
16 b)
17 0.1 0.1
18 267 269 271 273 275 277 279 265 268 271 274 277
T/K T/K
19
20
0.55 0.50
21 10 wt % 10 wt %
22 0.5 20 wt % 0.45 20 wt %
23 30 wt %
24 0.45
0.40
25
0.4
26 0.35
P/MPa
P/MPa
27 0.35
28 0.30
29 0.3
30 0.25
31 0.25
32 0.20
33
0.2
c) d)
34 0.15 0.15
35 267 269 271 273 275 277 279 269 271 273 275 277
36 T/K T/K
37
38 Figure 7 – Hydrate dissociation curves for mixtures of propane + water + inhibitor; Inhibitor a)
39 ethanol, b) DEG, c) TEG, d) glycerol. wt % refers to weight percentage of inhibitor in aqueous
40 solution. ○ – Maekawa. 35; ◊ -Afzal et al. 27; x - Mahmoodaghdam and Bishnoi. 28; + - Servio and
41
Englezos. 36
42
43 For the TEG inhibition, there is an overestimation of the pressure effect for higher inhibition
44
compositions, leading to deviations up to 1.5 K. In the case of diethylene glycol, the results from
45
46 the different authors are not in accordance with each other, thus, while the model is accurate
47 for certain sets of experimental data, for the data of other authors the deviations may be higher.
48
49 To finish the analysis of mixtures containing a single hydrate former, Figure 8 presents the results
50 for the dissociation curves of H2S, while Figure 9 presents the results for mixtures containing CO2
51 hydrates.
52
53
54
55
56
57
58
59
60

1
2
3 20 0.55
4 30 wt %
18 0.5
5 50 wt %
6 16 10 wt %
0.45
7 14 20 wt %
8 0.4
12
9
P/MPa
P/MPa
10 10 0.35
11 8 0.3
12
6
13 0.25
14 4
15 2 a) 0.2 b)
16
0 0.15
17
265 275 285 295 305 250 260 270 280
18
T/K T/K
19
20
0.85 0.80
21
22 0.75 5 wt %
0.70 5 wt %
23 15 wt %
24 0.65 15 wt %
0.60
25
0.55
26 0.50
P/MPa
P/MPa
27 0.45
28 0.40
29 0.35
30 0.30
0.25
31
32 0.15 c) 0.20
33 d)
34 0.05 0.10
35 270 275 280 285 290 295 0 50 100 150 200 250
36 T/K T/K
37
38 Figure 8 – Hydrate dissociation curves for mixtures of H2S + water + inhibitor; Inhibitor a), b)
39 methanol, c) DEG, d) TEG. wt % refers to weight percentage of inhibitor in aqueous solution. ○
40 – Mohammadi and Richon 37; □ – Ng and Robinson 24; ◊ – Mohammadi and Richon. 38
41
42 The dissociation curves of H2S hydrates are accurately described, even at large inhibitor
43 concentrations, in mixtures containing methanol. For the cases of DEG and TEG the results are
44
accurate, in contrast with what happened for propane hydrates. This might have to do with the
45
46 difference of hydrate type (type I for H2S and type II for propane), the inhibitor effect of DEG
47 and TEG being better described for hydrates of type I.
48
49
50
51
52
53
54
55
56
57
58
59
60

1
2
3 25 4
4 10 wt % 20 wt %
5 35 wt % 50 wt % 5 wt %
6 20 3.5 10 wt %
7
8 20 wt %
15 3
9
P/MPa
P/MPa
10
11 2.5
10
12
13
14 2
5
15 b)
16 a) 1.5
17 0 265 270 275 280
18 230 240 250 T/K 260 270 280 T/K
19
20 4.5
10 wt %
21
4 20 wt %
22
23 30 wt %
24 3.5
25
3
P/MPa
26
27
2.5
28
29
2
30
31
1.5
32 c)
33 1
34
268 273 278 283
35 T/K
36
37 Figure 9 – Hydrate dissociation curves for mixtures of CO2 + water + inhibitor; Inhibitor a)
38 methanol, b) ethanol, c) glycerol. wt % refers to weight percentage of inhibitor in aqueous
39
solution. ○ – Robinson and Ng 25; ◊ – Ng and Robbinson 24; – Δ Mohammadi and Richon 38; □ –
40
41 Ferrari et al. 39; x – Maekawa 40; + – Breland and Englezos. 41
42
For CO2 (Figure 9), as in some previous cases, the accuracy of the hydrate dissociation curve for
43
44 mixtures containing methanol depends largely on which set of experimental data is being
45 analyzed. In this case there is a significant difference between the experimental sets, with
46 differences up to 6 K between two sets for the same inhibitor composition. The model describes
47 accurately the results of Mohammadi and Richon 38 and Maekawa 40 at lower inhibitor contents,
48
49
but clearly underpredicts the pressure results for the remaining sets, especially in the water-
50 liquid-hydrate section of the dissociation curve. As presented in a previous study 20 these
51 differences are already significant for the pure hydrate of CO2, introducing higher uncertainties
52 for the parameterization of this hydrate. For the remaining compounds in study there appear to
53 be slight underestimations of the hydrate dissociation curves, however, these are within a small
54
55 range of temperatures and ΔT are mostly below 1 K. Results for the remaining inhibitors in study
56 when applied to the CO2 hydrate are presented on Table 3 and on the supporting information.
57
58
59
60

1
2
3 3.3 Mixtures of hydrate formers
4
5 In this section, six different gas mixtures are analyzed in presence of hydrate inhibitors. The
6 compositions of these mixtures are presented on Table S3 of the supporting information.
7
Mixture 1 contains methane and ethane. The results for this mixture in contact with water +
8
9 glycerol and water + TEG solutions are presented in Figure 10.
10
11 5.0
12
4.5
13
14 4.0
15
16 3.5
P/MPa
17
3.0
18
19 2.5
20
21 2.0 30 wt % TEG
22 20 wt % TEG
1.5 a)
23 20 wt % glycerol
24 1.0
25 270 273 276 279 282 285
26 T/K
27
28 Figure 10 – Hydrate dissociation curves for mixtures of water + inhibitor + methane + ethane.
29 Full lines – results for TEG; Dashed lines – results for glycerol. Data from Wu and Englezos. 42
30
31 The description of the mixture containing ethane is very good at the concentrations of inhibitor
32 in analysis.
33
34 Figure 11 compares the results obtained with the modified CPA with the experimental data from
35 Lee and Kang, 43 for natural gas hydrate inhibition.
36
37
10 9
38 10 wt %
39 9 8
20 wt %
40 8 7
30 wt %
41
7 6
42 40 wt %
43 6
50 wt % 5
P/MPa
P/kPa
44 5
45 4
4
46 3
47 3
2 10 wt %
48 2
20 wt %
49
1 a) 1 b)
50 30 wt %
0 0
51
0 50 100 150 200 250 270.00 280.00 290.00
52 T/K T/K
53
54 Figure 11 – Hydrate dissociation curves for mixtures of water + natural gas + inhibitor; Inhibitor
55
56 a) MEG, b) methanol. wt % refers to weight percentage of inhibitor in the aqueous phase. Data
57 from Lee and Kang. 43 (experimental composition data for this mixture is presented in the
58 supporting information)
59
60

1
2
3 For the mixture containing MEG, the descriptions are accurate up to 30 wt % of inhibitor with a
4
higher ΔT above these concentrations. In the mixture containing methanol the results are also
5
6 accurate up to 30 wt% of inhibitor, however, there is no experimental data above this
7 concentration. For both cases ΔT is mostly below 2.0 K.
8
9 The last three mixtures being considered in this work are three sour gases + water + methanol.
10 These are analyzed in Figure 12.
11
12 9
13
SG 1 (15 wt%)
14 8
15 SG 2 (20 wt%)
16 SG 3 (30 wt%)
7
17
P/MPa
18
6
19
20
21 5
22
23 4
24
25 3
26 0 50 100 150 200 250
27 T/K
28
29 Figure 12 – Hydrate dissociation curves for mixtures of water + sour gas + methanol. wt %
30 refers to weight percentage of methanol in aqueous solution. SG is sour gas. Data from Liu et
31
al. 44 (experimental composition data for these mixtures are presented in the supporting
32
33 information)
34
35
The results obtained for the sour gases present an overestimation of the dissociation
36 temperatures, which for the first two sour gases is mostly below 1 K. For the third sour gas in
37 analysis the deviations can be as high as 1.8 K.
38
39 To finish this analysis, Table 3 presents the average ΔT for all mixtures investigated and
40 compares the present results with the results obtained through the Multiflash 10 hydrates
41 model, which also uses a CPA variant (Multiflash 6.1 was used for these calculations). The results
42
from the present work, while, in most cases, not as accurate as the results by Multiflash are still
43
44 quite good. The parameterization applied in this work tried to improve the description of VLE
45 while keeping a correct description of the hydrate phase. For this purpose, in the cases of
46 methanol, ethanol and MEG, there was a need to use two binary interaction parameters. The
47 Multiflash parameter sets are also capable of a good simultaneous description of hydrate
48
inhibition, SLE and VLE, but the CPA model used in this software, requires a higher number of
49
50 both pure component and binary interaction parameters. To test the thermodynamic
51 consistency of the results obtained by the model, as well as that of the experimental data, the
52 recent approach presented by Sa et al. 45 can be used. The first of these tests consists in a
53 verification of the linearity of the phase equilibrium data in relation to a fitting regression
54 1
55 correlating ln 𝑃 to 𝑇. The second test analysis the values of the hydrate dissociation enthalpy,
56 which should only depend on the hydrate structure and on the presence of guest species. The
57
third and last test checks the thermodynamic consistency of the activity of liquid water over a
58
59 small temperature range. More details on this methods are present on the original paper. 45
60

1
2
3 However, it important to note that one of the tests applied in this approach can affected by the
4
phase transition between hydrate and ice and the condensation of heavier alkanes and CO2.
5
6 Table 4 presents the results obtained using this approach for the methane hydrate in the
7 presence of high concentrations of inhibitor.
8
9 The results for tests 1 and 3 are mostly good, with the model being more consistent than the
10 experimental data in both of these tests. Due to the high inhibitor concentrations, a small
11 change in temperature promotes a large range in the dissociation pressure. Thus for the pure
12 hydrate, the range of temperatures to analyze will be large, which affects negatively the results,
13
14
especially for the second test. Thus, in general, the present results seem to be
15 thermodynamically consistent.
16
17 Conclusions
18
A modified CPA model was applied in combination with the van der Waals-Platteeuw hydrate
19
20 model for the description of hydrate dissociation curves of inhibited mixtures. For most mixtures
21 the descriptions of the experimental data are quite good and the average differences are in all
22 cases below 2 K.
23
24 The parameterization conducted for methanol, ethanol and ethylene glycol took into account
25 the description of SLE and a large range of VLE data. Thus, one extra binary interaction
26 parameter was needed to enable a correct overall description of phase equilibria. This approach
27
28 leads to higher deviations, especially at higher inhibitor compositions, but this is a necessary
29 compromise for a model capable of describing the different equilibria without a high number of
30 binary interaction parameters.
31
32 When compared to the CPA model present on Multiflash, the proposed approach compares well
33 on the deviations in temperature for the dissociation curves. Nevertheless, the model present
34 in Multiflash is capable of describing a broader range of phase equilibria with a single set of
35
parameters. This is, however, due to a higher number of parameters used by this model.
36
37 Supporting information
38
39 Deviations on pressure and composition for the Vapor Liquid Equilibria of water + methanol and
40
water + ethanol. Figures with some extra results for hydrate inhibition. Experimental
41
42 composition of the sour and natural gas mixtures.
43
44
Funding and Acknowledgments
45
This work was funded by KBC Advanced Technologies Limited (A Yokogawa Company) under
46
47 project "Extension of the CPA model for Polyfunctional Associating Mixtures”. André M. Palma
48
49 Acknowledges KBC for his Post-Doctoral grant. This work was developed within the scope of the
50
project CICECO-Aveiro Institute of Materials, FCT Ref. UID/CTM/50011/2019, financed by
51
52 national funds through the FCT/MCTES.
53
54
55
56
57
58
59
60

1
2
3
4 Table 3 – Differences in hydrate dissociation temperature between experiment and model for the presented model and the CPA hydrate model present in
5
6 Multiflash (version 6.1). 10
7
8 Gas/referenc ΔT (K)
9
10
11 es
12
13 methanol MEG ethanol DEG TEG glycerol
14
15
16 This work MFlash This work MFlash This work MFlash This work MFlash This work MFlash This work
17
18
19 methane24–30,46–48 0.82 0.78 0.49 0.53 0.43 0.22 0.71 1.66 0.98 1.31 0.82
20
21 ethane24,27,28,30,33,34 0.94 0.78 0.41 0.20 - - 0.35 0.82 0.64 1.35 0.20
22
23 propane24,27,28,30,33, 1.03 0.53 0.44 0.46 0.19 0.49 0.59 1.08 0.41 0.17 0.16
24
25 35
26
27
Xe32 0.10 0.24 0.17 0.33 0.31 0.34 0.31 1.35 0.14 1.20 0.21
28
29
30 H2S24,37,38 0.59 0.50 - - - - 0.44 0.41 0.40 0.48 -
31
32 CO225,38–41 2.17 1.43 0.73 0.25 0.43 0.16 0.70 0.40 0.41 0.75 0.67
33
34 CH4+C2H642 - - - - - - - - 0.44 0.29 0.16
35
36 0.67 0.90 1.18 0.92 - - - - - - -
natural gas43
37
38
39
40
41
42
43 ACS Paragon Plus Environment
44
45
46
1
2
3
4 0.94 0.75 - - - - - - - - -
5 sour gas44
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21 Table 4 – Results for the thermodynamic consistency test of Sa et al for methane hydrates. 45
22
23 EXP CALC
24 Inhibitor Reference
Test 1 Test 2 Test 3 Test 1 Test 2 Test 3
25
methanol (40%) 31 Good Average Average Good Good Good
26
27 methanol (50%) 31 Good Bad Good Good Average Good
28 methanol (60%) 31 Good Average Good Good Average Good
29 methanol (50%) 25 Good Bad Average Good Bad Average
30 methanol (50%) 29 Good Bad Good Good Bad Good
31
32 MEG (50%) 25 Good Bad Good Good Bad Good
33 MEG (50%) 29 Good Good Good Good Good Good
34 DEG (50%) 26 Good Good Good Good Average Good
35 TEG (40%) 30 Good Bad Average Good Bad Good
36
37 TEG (50%) 26 Good Average Good Good Good Good
38
39
40
41
42
44
45
46
1
2
3 Nomenclature
4
5 𝐴, 𝑎 = energy parameter of CPA. (𝐴(𝑇) = 𝑛2𝑎(𝑇))
6
7 𝑎𝑐 = value of the energy parameter at the critical point.
8
9 B, b = co-volume. (𝐵 = 𝑛𝑏)
10
11 c1 – c5 (cx)= alpha function parameters
12
13 cvs = volume shift
14
g = radial distribution function
15
16 kij = binary interaction parameter for the cubic term energy parameter
17
18 𝑚𝑖 = mole number of sites of type i
19
20 n = mole number
21
22 P = Pressure (Pa)
23
24 R = Gas constant
25
26 T = temperature (K)
27 𝑇
28 Tr = reduced temperature 𝑇𝑟 = 𝑇𝑐
29
30 T’= (1 ― 𝑇𝑟), Tr =T/Tc
31
32 v = molar volume (m3.mol-1)
33
34 v0 = molar volume before translation (m3.mol-1)
35
36 vt = molar volume after translation (m3.mol-1)
37
38 wt % = weight percentage
39
40 x = mole fraction
41
𝑋𝐴𝑖 = mole fraction of component i not bonded to site A
42
43
Z = compressibility factor
44
45
46
47 Subscripts and superscripts
48
49 c = critical
50
51 exp = experimental
52
53 calc = calculated
54
55 Chemical Formulas
56
57
CO2 = carbon dioxide
58
H2S = hydrogen sulfide
59
60

1
2
3 Abbreviations
4
5 CPA EoS = Cubic Plus Association Equation of State
6
7 DEG = diethylene glycol
8
9 MEG = ethylene glycol
10
11 OF = Objective Function
12
13 PC-SAFT = Perturbed Chain SAFT
14
SAFT = Statistical Associating Fluid Theory
15
16 SAFT-VR = SAFT Variable Range
17
18 SG = Sour gas
19
20 TEG = triethylene glycol
21
22 References
23
24 (1) Platteeuw, J. C.; van der Waals, J. H. Thermodynamic properties of gas hydrates. Mol.
25 Phys. An Int. J. Interface Between Chem. Phys. 1958, No. June 2013, 91–96.
26
27 (2) Parrish, W. R.; Prausnitz, J. M. Dissociation Pressures of Gas Hydrates Formed by Gas
28 Mixtures. Ind. Eng. Chem. Process Des. Dev. 1972, 11 (1), 26–35.
29
30 (3) Dadmohammadi, Y.; Gebreyohannes, S.; Abudour, A. M.; Neely, B. J.; Gasem, K. A. M.
31 Representation and Prediction of Vapor-Liquid Equilibrium Using the Peng-Robinson
32 Equation of State and UNIQUAC Activity Coefficient Model. Ind. Eng. Chem. Res. 2016,
33 55 (4), 1088–1101.
34
35 (4) Palma, A. M.; Oliveira, M. B.; Queimada, A. J.; Coutinho, J. A. P. Re-evaluating the CPA
36 EoS for improving critical points and derivative properties description. Fluid Phase
37 Equilib. 2017, 436, 85–97.
38
39 (5) Folas, G. K.; Froyna, E. W.; Lovland, J.; Kontogeorgis, G. M.; Solbraa, E. Data and
40 prediction of water content of high pressure nitrogen, methane and natural gas. Fluid
41 Phase Equilib. 2007, 252 (1–2), 162–174.
42
43 (6) Pedrosa, N.; Szczepanski, R.; Zhang, X. Integrated equation of state modelling for flow
44 assurance. Fluid Phase Equilib. 2013, 359, 24–37.
45
46 (7) Li, X. Sen; Wu, H. J.; Englezos, P. Prediction of gas hydrate formation conditions in the
47 presence of methanol, glycerol, ethylene glycol, and triethylene glycol with the
48 statistical associating fluid theory equation of state. Ind. Eng. Chem. Res. 2006, 45 (6),
49 2131–2137.
50
51 (8) Dufal, S.; Galindo, A.; Jackson, G.; Haslam, A. J. Modelling the effect of methanol, glycol
52 inhibitors and electrolytes on the equilibrium stability of hydrates with the SAFT-VR
53 approach. Mol. Phys. 2012, 110 (11–12), 1223–1240.
54
55 (9) Kondori, J.; Zendehboudi, S.; James, L. A.; James, L. Evaluation of Gas Hydrate
56 Formation Temperature for Gas/Water/Salt/Alcohol Systems: Utilization of Extended
57 UNIQUAC Model and PC-SAFT Equation of State. Ind. Eng. Chem. Res. 2018, 57, 13833–
58 13855.
59
60 (10) MULTIFLASH version 6.1, KBC Process Technology, London, United Kingdom.

1
2
3 (11) Kontogeorgis, G. M.; Yakoumis, I. V.; Meijer, H.; Hendriks, E.; Moorwood, T.
4 Multicomponent phase equilibrium calculations for water–methanol–alkane mixtures.
5
Fluid Phase Equilib. 1999, 160, 201–209.
6
7 (12) Palma, A. M.; Queimada, A. J.; Coutinho, J. A. P. Improved prediction of water
8 properties and phase equilibria with a modified CPA EoS. Ind. Eng. Chem. Res. 2017, 56,
9
15163−15176.
10
11 (13) Elliott, J. R.; Suresh, S. J.; Donohue, M. D. A Simple Equation of State for Nonspherical
12 and Associating Molecules. Ind. Eng. Chem. Res. 1990, 32 (1978), 1476–1485.
13
14 (14) Voutsas, E. C.; Yakoumis, I. V; Tassios, D. P. Prediction of phase equilibria in
15 water/alcohol/alkane systems. Fluid Phase Equilib. 1999, 158–160, 151–163.
16
17 (15) Kontogeorgis, G. M.; Michelsen, M. L.; Folas, G. K.; Derawi, S.; Von Solms, N.; Stenby, E.
18 H. Ten Years with the CPA (Cubic-Plus-Association) equation of state. Part 2. Cross-
19 Associating and Multicomponent Systems. Ind. Eng. Chem. Res. 2006, 45 (14), 4855–
20
4868.
21
22 (16) Palma, A. M.; Queimada, A. J.; Coutinho, J. A. P. Modeling of the Mixture Critical Locus
23 with a Modified Cubic Plus Association Equation of State: Water, Alkanols, Amines, and
24
Alkanes. Ind. Eng. Chem. Res. 2018, acs.iecr.8b01960.
25
26 (17) Palma, A. M.; Queimada, A. J.; Coutinho, J. A. P. Modeling of the Mixture Critical Locus
27 with a Modified Cubic Plus Association (CPA) EoS: Aromatics, Ketones, Ethers, Diethyl
28
Carbonate, and THF. Ind. Eng. Chem. Res. 2018, 57 (46), 15857–15868.
29
30 (18) Graboski, M. S.; Daubert, T. E. A Modified Soave Equation of State for Phase Equilibrium
31 Calculations. 1. Hydrocarbon Systems. Ind. Eng. Chem. Process Des. Dev. 1978, 17 (4),
32
443–448.
33
34 (19) Palma, A. M.; Oliveira, M. B.; Queimada, A. J.; Coutinho, J. A. P. Evaluating Cubic Plus
35 Association Equation of State Predictive Capacities: A Study on the Transferability of the
36
Hydroxyl Group Associative Parameters. Ind. Eng. Chem. Res. 2017, 56 (24), 7086–7099.
37
38 (20) Palma, A. M.; Queimada, A. J.; Coutinho, J. A. P. Modelling of hydrate dissociation
39
curves with a modified Cubic-Plus-Association equation of state. (Under Consideration
40
41
for Industrial and Engineering Chemistry Research).
42 (21) Chouireb, N.; Crespo, E. A.; Pereira, L. M. C.; Tafat-Igoudjilene, O.; Vega, L. F.; Coutinho,
43
J. A. P.; Carvalho, P. J. Measurement and Modeling of Isobaric Vapor-Liquid Equilibrium
44
45
of Water + Glycols. J. Chem. Eng. Data 2018, 63 (7), 2394–2401.
46 (22) Thermodynamics Research Center (TRC), ThermoData Engine, version 9.0, National
47
Institute of Standards and Technology, Boulder, Colorado, USA.
48
49 (23) Ott, J. B.; Goates, J. R.; Lamb, J. D. Solid-liquid phase equilibria in water + ethylene
50 glycol. J. Chem. Thermodyn. 1972, 4 (1), 123–126.
51
52 (24) Ng, H.-J.; Robinson, D. B. Hydrate formation in systems containing methane, ethane,
53 propane, carbon dioxide or hydrogen sulfide in the presence of methanol. Fluid Phase
54 Equilib. 1985, 21 (1–2), 145–155.
55
56 (25) Robinson, D. B.; Ng, H. J. Hydrate Formation and Inhibition in Gas or Gas Condensate
57 Streams. J. Can. Pet. Technol. 1986, 25 (4), 26–30.
58
59 (26) Mohammadi, A. H.; Richon, D. Gas hydrate phase equilibrium in methane + ethylene
60 glycol, diethylene glycol, or triethylene glycol + water system. J. Chem. Eng. Data 2011,

1
2
3 56 (12), 4544–4548.
4
5 (27) Afzal, W.; Mohammadi, A. H.; Richon, D. Experimental Measurements and Predictions
6 of Dissociation Conditions for Methane, Ethane, Propane, and Carbon Dioxide Simple
7 Hydrates in the Presence of Diethylene Glycol Aqueous Solutions. J. Chem. Eng. Data
8 2008, 53 (3), 663–666.
9
10 (28) Mahmoodaghdam, E.; Bishnoi, P. R. Equilibrium Data for Methane, Ethane, and
11 Propane Incipient Hydrate Formation in Aqueous Solutions of Ethylene Glycol and
12 Diethylene Glycol. J. Chem. Eng. Data 2002, 47 (2), 278–281.
13
14 (29) Mohammadi, A. H.; Richon, D. Phase Equilibria of Methane Hydrates in the Presence of
15 Methanol and/or Ethylene Glycol Aqueous Solutions. Ind. Eng. Chem. Res. 2010, 49 (2),
16 925–928.
17
18 (30) Ross, M. J.; Toczylkin, L. S. Hydrate dissociation pressures for methane or ethane in the
19 presence of aqueous solutions of triethylene glycol. J. Chem. Eng. Data 1992, 37 (4),
20
488–491.
21
22 (31) Haghighi, H.; Chapoy, A.; Burgess, R.; Mazloum, S.; Tohidi, B. Phase equilibria for
23 petroleum reservoir fluids containing water and aqueous methanol solutions:
24
Experimental measurements and modelling using the CPA equation of state. Fluid
25
26
Phase Equilib. 2009, 278 (1–2), 109–116.
27 (32) Maekawa, T. Equilibrium Conditions of Xenon Hydrates in the Presence of Aqueous
28
Solutions of Alcohols, Glycols, and Glycerol. J. Chem. Eng. Data 2016, 61 (1), 662–665.
29
30 (33) Mohammadi, A. H.; Richon, D. Phase equilibria of propane and ethane simple hydrates
31 in the presence of methanol or ethylene glycol aqueous solutions. Ind. Eng. Chem. Res.
32
2012, 51 (6), 2804–2807.
33
34 (34) Maekawa, T. Equilibrium Conditions of Ethane Hydrates in the Presence of Aqueous
35 Solutions of Alcohols, Glycols, and Glycerol. J. Chem. Eng. Data 2012, 57 (2), 526–531.
36
37 (35) Maekawa, T. Equilibrium conditions of propane hydrates in aqueous solutions of
38 alcohols, glycols, and glycerol. J. Chem. Eng. Data 2008, 53 (12), 2838–2843.
39
40 (36) Servio, P.; Englezos, P. Incipient equilibrium propane hydrate formation conditions in
41 aqueous triethylene glycol solutions. J. Chem. Eng. Data 1997, 42 (4), 800–801.
42
43 (37) Mohammadi, A. H.; Richon, D. Phase Equilibria of Clathrate Hydrates in Hydrogen
44 Sulfide + Diethylene Glycol or Triethylene Glycol + Water System. Chem. Eng. Commun.
45 2014, 201 (2), 225–232.
46
47 (38) Mohammadi, A. H.; Richon, D. Phase equilibria of hydrogen sulfide and carbon dioxide
48 simple hydrates in the presence of methanol, (methanol + NaCl) and (ethylene glycol +
49 NaCl) aqueous solutions. J. Chem. Thermodyn. 2012, 44 (1), 26–30.
50
51 (39) Ferrari, P. F.; Guembaroski, A. Z.; Marcelino Neto, M. A.; Morales, R. E. M.; Sum, A. K.
52 Experimental measurements and modelling of carbon dioxide hydrate phase
53 equilibrium with and without ethanol. Fluid Phase Equilib. 2016, 413, 176–183.
54
55 (40) Maekawa, T. Equilibrium Conditions for Carbon Dioxide Hydrates in the Presence of
56 Aqueous Solutions of Alcohols, Glycols, and Glycerol. J. Chem. Eng. Data 2010, 55 (3),
57 1280–1284.
58
59 (41) Breland, E.; Englezos, P. Equilibrium hydrate formation data for carbon dioxide in
60 aqueous glycerol solutions. J. Chem. Eng. Data 1996, 41 (1), 11–13.

1
2
3 (42) Wu, H.-J.; Englezos, P. Inhibiting Effect of Triethylene Glycol and Glycerol on Gas
4 Hydrate Formation Conditions. J. Chem. Eng. Data 2006, 51, 1811–1813.
5
6 (43) Lee, J. W.; Kang, S. P. Phase equilibria of natural gas hydrates in the presence of
7 methanol, ethylene glycol, and NaCl aqueous solutions. Ind. Eng. Chem. Res. 2011, 50
8 (14), 8750–8755.
9
10 (44) Liu, H.; Guo, P.; Du, J.; Wang, Z.; Chen, G.; Li, Y. Experiments and modeling of hydrate
11 phase equilibrium of CH4/CO2/H2S/N2 quaternary sour gases in distilled water and
12 methanol-water solutions. Fluid Phase Equilib. 2017, 432, 10–17.
13
14 (45) Sa, J. H.; Hu, Y.; Sum, A. K. Assessing thermodynamic consistency of gas hydrates phase
15 equilibrium data for inhibited systems. Fluid Phase Equilib. 2018, 473, 294–299.
16
17 (46) Sloan, E. D.; Koh, C. Clathrate Hydrates of Natural Gases; 2007.
18
19 (47) Ng., H.-J. .; Robinson, D. B. (First) International Conference on Natural Gas Hydrates. In
20 Ann. N.Y. Acad. Sci.; 1994; pp 715, 450.
21
22 (48) Youn, Y.; Seol, J.; Cha, M.; Ahn, Y. H.; Lee, H. Structural transition induced by CH4
23 enclathration and cage expansion with large guest molecules occurring in amine
24 hydrate systems. J. Chem. Eng. Data 2014, 59 (6), 2004–2012.
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