Chemical Engineering Science 81 (2012) 319–328

Contents lists available at SciVerse ScienceDirect

Chemical Engineering Science

journal homepage: www.elsevier.com/locate/ces

Thermodynamic modeling of phase equilibria of semi-clathrate hydrates

of CO2, CH4, or N2 þ tetra-n-butylammonium bromide aqueous solution
Ali Eslamimanesh a, Amir H. Mohammadi a,b,n, Dominique Richon b,c
a
MINES ParisTech, CEP/TEP—Centre Énergétique et Procédés, 35 Rue Saint Honoré, 77305 Fontainebleau, France
b
Thermodynamics Research Unit, School of Chemical Engineering, University of KwaZulu-Natal, Howard College Campus, King George V Avenue, Durban 4041, South Africa
c
Technical University of Denmark, Center for Energy Resources Engineering (CERE), Department of Chemical and Biochemical Engineering, DK-2800 Kgs. Lyngby, Denmark

H I G H L I G H T S

c A thermodynamic model is proposed for investigation of semi-clathrate hydrates.

c The studied systems include CO2, CH4, or N2 þTBAB aqueous solution.
c The vdW–P theory along with two modifications are used for hydrate phase.
c The PR EoS and NRTL activity model are applied for modeling the fluid phases.
c Promotion/inhibition effects of TBAB can be well determined using the model.

a r t i c l e i n f o abstract

Article history: Prediction of phase equilibria of semi-clathrate hydrates has been very rarely investigated in the
Received 10 May 2012 literature. In this work, a thermodynamic model is proposed for representation/prediction of phase
Accepted 6 July 2012 equilibria of semi-clathrate hydrates of the CO2, CH4, or N2 þtetra-n-butylammonium bromide (TBAB)
Available online 16 July 2012
aqueous solution. For modeling the hydrate phase, the van der Waals–Platteeuw (vdW–P) solid solution
Keywords: theory is used, revised with two modifications for evaluations of Langmuir constants and vapor pressure of
Semi-clathrate hydrate water in the empty hydrate lattice, in which these values are supposed to be a function of TBAB
TBAB concentration in aqueous solution. The Peng–Robinson (PR-EoS) equation of state along with re-tuned
Thermodynamic model parameters of Mathias–Copeman alpha function is applied for calculation of the fugacity of gaseous hydrate
Carbon dioxide
former. For determination of the activity coefficient of the non-electrolyte species in the aqueous phase, the
Methane
Non-Random Two-Liquid (NRTL) activity model is used. To calculate the mean activity coefficients of the
Nitrogen
electrolyte portion, a correlation on the basis of existing osmotic coefficient and activity coefficient values is
employed. It is shown that the presented model results are in acceptable agreement with the experimental
semi-clathrate hydrate dissociation data investigated in this work.
& 2012 Elsevier Ltd. All rights reserved.

1. Introduction common clathrate hydrate structures: structure I (sI), structure II

Gas hydrates, or clathrate hydrates, are crystalline solid structures
consisting of small molecules (guests), which are generally low
molecular diameter gas molecules (or particular volatile liquids).
Hydrogen bonds between water molecules make cage-like networks
trapping the guest molecules, which are stable at appropriate
temperature and pressure conditions (normally at high pressures
and low temperatures) (Sloan and Koh, 2008). There are three
n
Corresponding author at: MINES ParisTech, CEP/TEP - Centre Énergétique et
Procédés, 35 Rue Saint Honoré, 77305 Fontainebleau, France.
Tel.: þ33 1 64 69 49 70; fax: þ 33 1 64 69 49 68.
E-mail address: amir-hossein.mohammadi@mines-paristech.fr
(A.H. Mohammadi).
(sII), and structure H (sH) (Sloan and Koh, 2008). Hydrate structure
(or type) depends mostly on the size of the guest molecule(s) (Sloan
and Koh, 2008).
The main issue about gas hydrates was reported in the 1930s
including blockages of natural gas transportation pipelines due to
formation of these compounds (Hammerschmidt, 1934). However,
positive applications of gas hydrates such as gas separation including
greenhouse gases etc. (Eslamimanesh et al., 2012; Feron and
Hendricks, 2005; Kang and Lee, 2000; Linga et al., 2007; Belandria
et al., 2011a, b) gas storage e.g. hydrogen storage (Tsuda et al., 2009;
Strobel et al., 2009; Florusse et al., 2004), water desalination and
treatment technology (Javanmardi and Moshfeghian, 2003;
Delyannis and Delyannis, 1978), air-conditioning systems (Ogawa
et al., 2006), separation of ionic liquids from the relevant mixtures

0009-2509/$ - see front matter & 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.ces.2012.07.006
320 A. Eslamimanesh et al. / Chemical Engineering Science 81 (2012) 319–328
(Peng et al., 2010), concentration of dilute aqueous solutions e.g. in
food industry (Huang et al., 1965, 1966), have recently gained great
attention.
Many scientific reports reveal that large amounts of
greenhouse gases including carbon dioxide, methane, carbon
monoxide, hydrogen sulphide, etc. (Eslamimanesh et al., 2012;
Feron and Hendricks, 2005; Kang and Lee, 2000; Linga et al., 2007;
Belandria et al., 2011a, b; Hall et al., 2003; International Panel on
Climate Control (IPCC), 2005) have been accumulated in the
earth’s atmosphere, which result in unpleasant universal effects
mainly in the form of global warming (Eslamimanesh et al., 2012;
Feron and Hendricks, 2005; Kang and Lee, 2000; Linga et al., 2007;
Belandria et al., 2011a,b; Hall et al., 2003; International Panel on
Climate Control (IPCC), 2005). In addition, nitrogen is found in
great amounts in flue gas streams from power plants (Belandria
et al., 2011b; Lee et al., 2010). Therefore, separation of the
aforementioned gases from the corresponding gas flows has been
always of drastic importance for the industry from the past
century up to now. Cryogenic distillation, membrane purification,
and absorption with liquids are among the processes, which are
being currently applied for this purpose (International Panel on
Climate Control (IPCC), 2005). A novel technology that has been
recently proposed is separation of these gases through utilizing
gas hydrate formation (crystallization) technique (Eslamimanesh
et al., 2012; Kang and Lee, 2000; Linga et al., 2007; Belandria
et al., 2011a, b; Lee et al., 2010). The difference in gas hydrate
properties of various gases including the chemical affinity of the
hydrate cages to enclathrate specific gases, and the difference in
the corresponding phase behaviors can determine the possibility
of such separation processes. For instance, the hydrate phase can
be enriched in component(s) of interest while the concentration
of other gas(s) can be increased in the gas phase at equilibrium
(Mohammadi et al., 2011). The hydrate phase can be then
dissociated by depressurization or heating. As a result, the desired
component(s) can be recovered as separated gas streams (Kang
and Lee, 2000; Linga et al., 2007; Belandria et al., 2011a, b; Lee
et al., 2010; Mohammadi et al., 2011).
However, high pressure/low temperature conditions are gen-
erally the main concern about the described separation technol-
ogy. In order to deal with this problem, special chemical
compounds (namely as ‘‘gas hydrate promoters’’) are applied in
crystallization processes to improve the operational conditions
and/or simultaneously modify the selectivity of the hydrogen-
bonded water networks for trapping the molecules of interest
(like CO2 molecules). Different kinds of gas hydrate promoters can
be used including those, which form sI, sII, or sH like tetrahy-
drofuran (THF), and the ones, which generally form ‘‘semi-
clathrate hydrates’’ e.g. tetra-n-butylammonium salts (TBAX), in
which ‘‘X’’ can stand for halogen elements such as bromide,
chloride, fluoride etc. The latter hydrate promoters may be able
to modify the selectivity of hydrate cages for absorption of gas
molecules as well (Eslamimanesh et al., 2012; Mohammadi et al.,
2011; Shimada et al., 2005; Fukushima et al., 1999; Duc et al.,
2007; Shin et al., 2009; Makino et al., 2010; Wenji et al., 2009;
Deschamps and Dalmazzone, 2009; Fan et al., 2009). In semi-
clathrate hydrates, a part of the cage structure is broken in order
to trap the large non-gaseous hydrate former ion species (e.g.
TBA þ in the case of semi-clathrate hydrates in the presence of
TBAX aqueous solution) (Eslamimanesh et al., 2012; Mohammadi
et al., 2011; Shimada et al., 2005; Fukushima et al., 1999; Duc
et al., 2007; Shin et al., 2009; Makino et al., 2010; Wenji et al.,
2009; Deschamps and Dalmazzone, 2009; Fan et al., 2009). More
gas storage capacity, improved selectivity of the cages for trap-
ping the gas molecules, and moderate stability pressure–
temperature conditions may be among the significant advantages
of the semi-clathrate hydrates compared with the clathrate ones,
as already mentioned (Eslamimanesh et al., 2012; Mohammadi
et al., 2011; Shimada et al., 2005; Fukushima et al., 1999; Duc
et al., 2007; Shin et al., 2009; Makino et al., 2010; Wenji et al.,
2009; Deschamps and Dalmazzone, 2009; Fan et al., 2009). TBAB
is perhaps the most-widely proposed hydrate promoter, which
may possess the described advantages.
Accurate and reliable phase equilibrium data should be
obtained to design the efficient separation processes using
hydrate formation technology. Comprehensive literature survey
(Eslamimanesh et al., 2012; Mohammadi et al., 2011) indicates
that most of the corresponding phase equilibrium data for the
semi-clathrate hydrates of pure gases in the presence of TBAB
aqueous solutions have been generated since the last decade only.
A recent research project (SECOHYA, 2007) argues that the phase
behavior of semi-clathrate hydrates may be complicated and
difficult to analyze, which requires long time of careful and
accurate experiments. This is mainly because the semi-clathrate
structures can be changed from type A to type B (explained in the
next sections) or vice versa (Mohammadi et al., 2011; Shimada
et al., 2005; Duc et al., 2007; SECOHYA, 2007) by increasing/
decreasing the amounts of TBAB in aqueous solutions or by
increasing/decreasing the dissociation pressure of the system
(Mohammadi et al., 2011, 2012a; Shimada et al., 2005; Duc
et al., 2007; SECOHYA, 2007).
Therefore, proposing reliable and predictive models to repre-
sent/predict the corresponding phase equilibria seems to be
essential. The related theoretical attempts are limited to two
recent studies. Mohammadi et al. (2012b) studied the application
of Artificial Neural Networks (ANNs) for acceptable representa-
tion/prediction of the hydrate dissociation conditions of the
systems including H2 þTBAB aqueous solutions. Application of
these kinds of numerical models requires enough expertise in
mathematics. Moreover, development of these models generally
requires the use of many experimental data in order to be capable
of predicting the structural changes of the cavities. Recently,
Paricaud (2011) presented a thermodynamic model based on
the use of the statistical associating fluid theory with variable
range for electrolytes (SAFT-VRE) (Galindo et al., 1999) to model
the aqueous phase and van der Waals–Platteeuw (vdW–P) (van
der Waals and Platteeuw, 1959; Platteeuw and van der Waals,
1959) solid solution theory for dealing with the solid (hydrate)
phase for the hydrates formed in the carbon dioxideþ TBAB
aqueous solution system. The latter model requires enough
expertise in SAFT molecular theory to make its extension to
account for the representation/prediction of phase behavior of
semi-clathrate systems formed from other hydrate formers/pro-
moters. Since the relevant studies are still at the demonstrating
stage, it is of much significance to develop an easy-to-use and
reliable thermodynamic model for calculation/estimation of the
corresponding phase equilibria.
2. Modeling
2.1. Development of the thermodynamic model
The liquid water–hydrate–gas/vapor (Lw–H–G/V) equilibrium
conditions are calculated by equating the fugacity of water in the
L H
aqueous ðf w Þ and in the hydrate (f w ) phases (Sloan and Koh, 2008;
Mohammadi and Richon, 2008, 2009; Eslamimanesh et al., 2011a;
Tumba et al., 2011; Pahlavanzadeh et al., 2012):
L H
fw ¼ fw ð1Þ
where f is fugacity, subscript w denotes water, and superscripts L
and H represent the liquid and hydrate phases, respectively.
The fugacity of water in the hydrate phase is related to the
 A. Eslamimanesh et al. / Chemical Engineering Science 81 (2012) 319–328 321

chemical potential difference of water in the filled and empty an electrolyte solution (aqueous solution of TBAB), the concentra-
hydrate lattice (DmMTH
w ) by the following relation (Sloan and Koh, tion of water in aqueous phase can be determined applying the
2008; Mohammadi and Richon, 2008, 2009; Eslamimanesh et al., following equation (Paricaud, 2011):
2011a; Tumba et al., 2011; Pahlavanzadeh et al., 2012): 1
  xLw ¼ xLg ð9Þ
H MT DmMTH
w
1 þ0:001  2  m  M w
f w ¼ f w exp ð2Þ
RT where m stands for the molality of aqueous solution in mol kg  1,
The superscript MT represents empty hydrate lattice, R and T Mw is the molecular weight of water in g mol  1 and xLg stands for the
are universal gas constant and temperature, respectively, and m is solubility of the gaseous hydrate former in the aqueous phase, and
chemical potential. The fugacity of the hypothetical empty hydrate subscript g represents the gaseous hydrate former. Eq. (9) is
MT obtained assuming total dissociation of TBAB in water, which yields
lattice (f w ) is given by the following equation (Sloan and Koh,
2008; Mohammadi and Richon, 2008, 2009; Eslamimanesh et al., anions of Br  and cations of TBA þ . The molality of the solution
2011a; Tumba et al., 2011; Pahlavanzadeh et al., 2012): (defined as number of moles of TBAB per kg mass of water) can be
Z P  MT  calculated by the following relation (Paricaud, 2011):
MT vw dP
f w ¼ P MT MT
w jw exp ð3Þ 18:0153xðTBA þ Þ
P MT
w
RT m¼ ð10Þ
1000xw
where P stands for pressure, j and v are fugacity coefficient and
The solubility of gases in the aqueous phase is calculated using
molar volume, respectively, and P MT
w is the vapor pressure of water
the Krichevsky–Kasarnovsky (Krichevsky and Kasarnovsky, 1935)
in empty hydrate lattice. The fugacity coefficient of water in empty
equation (Tumba et al., 2011; Pahlavanzadeh et al., 2012):
hydrate lattice (jMTw ) is taken to be unity because the vapor
pressure of the water phase is low. The partial molar volume of G
fg
water in the empty hydrate lattice (vMT xLg ¼ ð11Þ
w ) in the Poynting correction Hgw expððv1 sat
g =RTÞðPP w ÞÞ
term of Eq. (3) is assumed to be pressure independent. Hence, the
preceding equation can be written as follows (Sloan and Koh, 2008; where Hg w is the Henry’s constant of gas in water, and the
Mohammadi and Richon, 2008, 2009; Eslamimanesh et al., 2011a; superscripts N and G represent infinite dilution condition and gas
Tumba et al., 2011; Pahlavanzadeh et al., 2012): phase, respectively. An experimental study has argued that the
! effects of the existing ions in the aqueous phase on the gas
MT
MT vMT
w ðP P w Þ
f w ¼ P MT
w exp ð4Þ solubility are relatively small for the systems similar to those
RT
investigated in this work (Lin et al., 2008).
In Eq. (2), DmMH is calculated using the vdW–P model The fugacity of gaseous hydrate former in the gas phase has been
w
(van der Waals and Platteeuw, 1959; Platteeuw and van der evaluated using the Peng–Robinson (PR) equation of state (EoS)
Waals, 1959): (Peng and Robinson, 1976) accompanied by Mathias–Copeman
" !# alpha function (Mathias and Copeman, 1983) with re-tuned para-
mHW mMT X X meters, as discussed later. This alpha function has been proven to
W 0
¼ vi ln 1 Y ki ð5Þ
RT i k
improve the performance of the equations of state especially at high
pressures (Mathias and Copeman, 1983). Additionally, the water
where v0 i is the number of cages of type i per water molecule in content of the gas phase is assumed to be negligible at the pressure–
a unit hydrate cell and Yki (the fractional occupancy of the temperature conditions studied in this work.
hydrate cavity i by guest molecule type k) is expressed using the Experimental study on crystal growth of semi-clathrate hydrate
following equation (Sloan and Koh, 2008; Mohammadi and Richon, of TBAB (Shimada et al., 2005) shows that each hydrate cell unit of
2008, 2009; Eslamimanesh et al., 2011a; Tumba et al., 2011; the investigated semi-clathrate is composed of 2 TBA þ and 2 Br 
Pahlavanzadeh et al., 2012): along with 76 water molecules. Furthermore, TBA þ also plays the
C ki f k role of a guest species (along with the gaseous hydrate former) in
Y ki ¼ P ð6Þ
1þ k C ki f k
the hydrate cavities, where the TBA þ is encaged in tetrakaideca-
hedra and pentakaidecahedra (large) cages (50% of each) and the
where fk is the fugacity of the hydrate former and Cki stands for gaseous component is trapped in dodecahedral small cages
Langmuir constant. By substituting Eq. (6) into Eq. (5), the following (Shimada et al., 2005). The subsequent structures could be either
equation is obtained (Sloan and Koh, 2008; Mohammadi and Richon, type A or type B with different hydration numbers that are
2008, 2009; Eslamimanesh et al., 2011a; Tumba et al., 2011; described in the next section. As a consequence, fugacity of the
Pahlavanzadeh et al., 2012): hydrate promoter in the aqueous phase needs to be determined as
mHw mMT X 0 well. Eq. (12) can be applied for this purpose:
w
¼ lnð1 þ C ij f j Þvi ð7Þ !
RT vLp ðPPsat
i L p Þ
f p ¼ xLp gp P sat
p exp ð12Þ
The aqueous phase of the systems of interest contains liquid RT
water, low concentrations of dissolved gas, and TBAB (hydrate
L where gp represents the activity coefficient of the hydrate promo-
promoter). The fugacity of water in the aqueous phase (f w ) can be
ter in the aqueous (electrolyte) solution, and the subscript p stands
determined using the following equation (Sloan and Koh, 2008;
for the hydrate promoter.
Mohammadi and Richon, 2008, 2009; Eslamimanesh et al., 2011a;
Substitution of the preceding equations in Eq. (1), leads to
Tumba et al., 2011; Pahlavanzadeh et al., 2012): " #
 L  P MT MT MT
vw ðPPsat w expðvw ðPP w Þ=RTÞ
L w Þ
f w ¼ xLw gw P sat
w exp ð8Þ xLw gLw Psat L sat
RT w expðvw ðPP w Þ=RTÞ
 v0 small type  v0large
where xLw , gw, P sat L
w , and vw stand for mole fraction of water in the  ln 1þ C small f g
G A=B L
 1þ C large1 f p 1type A=B

aqueous phase, activity coefficient of water, water vapor pressure, 

 v0large
and molar volume of liquid water, respectively, and superscript L
 1 þ C large2 f p 2type A=B
¼0 ð13Þ
sat represents the saturation condition. Since we are dealing with
322 A. Eslamimanesh et al. / Chemical Engineering Science 81 (2012) 319–328

where superscripts/subscripts: ‘‘small and large’’ stand for small and interactions between the large molecules of TBAB (or their
and large cavities, respectively, and subscript type A/B represents dissociated ions in aqueous solution) with each other as follows:
the formation of types A or B semi-clathrate hydrates, respec- For tetrakaidecahedra cages:
tively. Furthermore, subscripts 1 and 2 refer to occupation of large   
c d 
tetrakaidecahedra and pentakaidecahedra cages by TBA þ cations. C large1 ¼ exp 1 þ e  wp ð15Þ
T T
The hydrate dissociation pressure can be determined from
Eq.(13), calculating the parameters at a specified temperature For pentakaidecahedra cages:
and trial and error to obtain the pressure.  0 g 
f
C large2 ¼ exp 1þ i  wp ð16Þ
T T
2.2. Model parameters In addition, the expression proposed by Parrish and Prausnitz
(1972) has been used for the dodecahedral small cages, which
A typical structure of a TBAB semi-clathrate hydrate is depicted include the gas molecules:
in Fig. 1 (Shimada et al., 2005). Existence of TBAB in the system has  
non-negligible effects on the vapor pressure of water in empty aa bb
C small ¼ exp ð17Þ
hydrate lattice consequently, in this work, the method of T T
Dharmawardhana et al. (1980) for evaluation of the saturated In the preceding equations, c, d, and e are adjustable para-
vapor pressure of water in empty hydrate lattice has been modified meters for tetrakaidecahedra cavities, f 0 , g, and i are those related
on the basis of the assumption that the vapor pressure is inversely to pentakaidecahedra cages, and aa and bb are the parameters
proportional to TBAB concentration in aqueous phase because the recommended by Parrish and Prausnitz (1972) for each gaseous
hydrogen bonds, which form the cavities networks elongate (Br  hydrate former encaged in dodecahedral small cages (reported in
takes part in the hydrate hydrogen-bonded network, as mentioned Table 1).
earlier). As a result, the following equation is proposed: On the basis of the so far knowledge about the structures of
  the semi-clathrate hydrates formed in the presence of the aqu-
6003:9
P MT
w ¼ 0:1 exp 17:44 þ h  wp ð14Þ eous solutions of TBAB (Shimada et al., 2005; Oyama et al., 2005),
T
the following assumptions have been made for determination of
where the units of P MT
w and T are, respectively, MPa and K, h is an the Langmuir constants:
adjustable parameter, and wp is the weight fraction of the TBAB in
aqueous solution. It seems, from the structural formation of semi- 1. Hydration numbers: type A ¼26 and type B¼38;
clathrate hydrates, that the values of h may be generally a reverse 2. The enclathrated gas molecules are located in the dodecahe-
function of wp. dral small cages;
To determine the Langmuir constants, the method proposed by 3. The TBA þ cation is trapped in two large tetrakaidecahedra and
Parrish and Prausnitz (1972) has been applied along with a two large pentakaidecahedra.
correction factor to account for the disorders in the structures 4. Each type of semi-clathrates have two large cavities and one
of the cavities resulted from Br  bond to the molecules of water small cavity. As a result, the number of cages of the specified

Br-

gas molecules

TBA+

Fig. 1. The schematic picture of a typical semi-clathrate hydrate formed from a gaseous hydrate former þ TBAB aqueous solution (reproduced from Shimada et al. (2005)
with permission of Crystallography Journals Online, http://journals.iucr.org/).
 A. Eslamimanesh et al. / Chemical Engineering Science 81 (2012) 319–328 323

Table 1 Table 3
Constants aa and bb in Eq. (17) (Parrish and Prausnitz, 1972). Constants A–D in Eqs. (25) (Mohammadi and Richon, 2008, 2009; Tumba et al.,
2011; Pahlavanzadeh et al., 2012; Eslamimanesh et al., 2011c).
Hydrate former aa (K MPa  1) bb (K)
Solute A B (K) C0 D (K  1)
CO2 0.0011978 2860.5
CH4 0.0037237 2708.8 CO2 21.6215  1499.8  5.6495 0.000206
N2 0.0038087 2205.5 CH4 147.788  5768.3  52.295 0.018616
N2 78.852  3745  24.832 0.000291

Table 2
The interaction parameters of the NRTL (Renon and Prausnitz, 1968) model used leads to obtaining the following correlation to calculate the
in this work. activity coefficient of the utilized hydrate promoter (TBAB):
Compound A12 (kJ mole  1) A21 (kJ mole  1) a gp ¼ 0:5057wp 3 þ1:1603wp 2 1:3689wp þ 0:7655 ð26Þ

CO2 5.82 6.81 0.3 It should be noted that at the time of preparation of this
CH4 4.00 2.15 0.6 manuscript, no experimental data of activity coefficient of TBAB
N2 7.11 7.12 0.3
in aqueous solution at various temperatures or pressures are
available.
The density (r) of the TBAB aqueous solution (and conse-
type per water molecule in a unit hydrate cell is calculated as quently the molar volume (vLp)) has been determined using the
follows: correlation of Söhnel and Novotny (1985) with the recommended
values by Belandria and co-workers (Belandria et al., 2009; Chen
v0large1
type A ¼ 4=ð2  26Þ ¼ 1=13 ð18Þ et al., 2009):

v0large2
rp ¼ rw þ o1 ð100wp Þ þ o2 ð100wp Þ2 þ o3 ð100wp Þ3 ð27Þ
type A ¼ 4=ð2  26Þ ¼ 1=13 ð19Þ
where
v0small
type A ¼ 6=ð2  26Þ ¼ 3=26 ð20Þ
oi ¼ qi þr i ðTÞ þsi ðTÞ2 ð28Þ

v0small
type B ¼ 6=ð2  38Þ ¼ 3=38
v0large1
type B ¼ 4=ð2  38Þ ¼ 1=19
v0large2
type B ¼ 4=ð2  38Þ ¼ 1=19
The value of vMT
W is obtained using the following expression,
assuming that the volume of the empty hydrate lattice is similar
to that of for hydrate structure I (as the gaseous hydrate former
occupies only dodecahedral cages) (Klauda and Sandler, 2000;
Eslamimanesh et al., 2011b):
1030 NA
vMT
w ¼ ð11:835 þ 2:217  10
5
T þ 2:242  106 T 2 Þ
NMT
w CH4, and N2) from triple point to the critical point. The probable
8:006  109 P þ 5:448  1012 P 2
where NA is Avogadro’s number, NMT w stands for the number of
water molecules per hydrate cell. The unit of pressure in Eq. (24)
is MPa and the unit of temperature is K.
The activity coefficient of water in aqueous phase has been
determined using the NRTL (Renon and Prausnitz, 1968) model
with the interaction parameters reported in Table 2. The follow-
ing expression for Henry’s constant of gas water can be used in
Krichevsky–Kasarnovsky (Krichevsky and Kasarnovsky, 1935)
equation (Mohammadi and Richon, 2008; Eslamimanesh et al.,
2011a,c; Tumba et al., 2011; Pahlavanzadeh et al., 2012)
1
þ C 0 logðTÞ þ DT
Hgw ¼ ð10A þ BðTÞ Þ  0:1
where the Henry’s constant is calculated in MPa and T is in K. The
parameters in Eq. (25) are reported in Table 3. The values of
partial molar volumes at infinite dilution (and at 298.15 K) to be
applied in Eq. (11) for CO2, CH4, and N2 have been considered as
33.9, 34.5, and 35.7 (cm3 mol  1), respectively, from the experi-
mental work of Moore et al. (1982).
The activity coefficient of TBAB salt is calculated through the
corresponding values proposed by Lindenbaum and Boyd (1964),
and Amado and Blanco (2005), as function of molality of the
aqueous solution at 298.15 K and 0.101 MPa and applying Eq. (10)
ð21Þ In Eqs. (27) and (28), rp is calculated in g cm  3 and T is in K;
subscript i stands for three sets of parameters reported in Table 4.
In addition, partial molar volume of water has been calculated
ð22Þ
using Eq. (29), on the basis of the available experimental values
for a wide range of temperatures (Component Plus, 2001):
ð23Þ
0:081
vLw ¼ ð5:459=0:30542ð1 þ ðð1TÞ=647:13Þ Þ1 ð29Þ
3 1
where the unit of molar volume is cm mol and T is in K.
As already mentioned, the fugacity of the gaseous hydrate
former is calculated by the PR EoS (Peng and Robinson, 1976). The
values of the Mathias–Copeman alpha function (Mathias and
Copeman, 1983) parameters have been herein re-tuned to accu-
rately represent the vapor pressure of the pure compounds (CO2,
ð24Þ global optimum values of these parameters are reported in
Table 5 and the applied critical properties and acentric factors
of the studied gases are indicated in Table 6.
To determine the optimal values of the model parameters
including those in Eqs. (14)–(16) and also the Mathias–Copeman
alpha function (Mathias and Copeman, 1983) parameters, the
Differential Evolution (DE) optimization strategy (Price and Storn,
1997; Babu and Angira, 2006) has been herein used. This optimiza-
tion technique has been previously shown to have high capability in
phase equilibrium calculations (Eslamimanesh, 2009; Eslamimanesh
and Shariati, 2009; Eslamimanesh and Esmaeilzadeh, 2010;
Yazdizadeh et al., 2011, 2012; Eslamimanesh et al., 2011d). The
ð25Þ probable global optimum of the parameters are obtained on the
basis of the minimization of the following objective function:
diss:=vp diss:=vp
100 X 9Pi,cal: Pi,exp: 9
ndp
f unction ¼ diss:=vp
ð30Þ
ndp i P i,exp:
where ndp is the number of data points used in the optimization
procedure, superscript diss./vp denotes the hydrate dissociation
pressure or vapor pressure of pure compound, and subscripts i, cal.
and exp. stand for ith calculated or experimental value, the calcu-
lated, and the experimental hydrate dissociation pressure or vapor
pressure values, respectively. The above objective function has been
324 A. Eslamimanesh et al. / Chemical Engineering Science 81 (2012) 319–328

Table 4
Constants in Eq. (28) (Belandria et al., 2009).

Constants q1 q2 r1 r2 r3 s1 s2 s3

Values  1.707  10  8 4.570  10  9 5.693  10  6  3.099  10  6 4.088  10  8 4.549  10  4 5.304  10  4  7.091  10  6

Table 5 Table 7
The optimal values of the Mathias–Copeman alpha function (Mathias and Optimal values of the parameters in Eqs. (14)–(16).
Copeman, 1983) parameters obtained and used in this study.
Parameter Valuesa
Component Temperature range (K) Optimal values of parameters
Type Ab Type Bc
CC1 CC2 CC3 AARD (%)a
c (K MPa  1) 0.501813 0.998105
CO2 217–304 0.709  0.317 1.91 0.5 d (K) 3835.7 6999.5
N2 64–126 0.449  0.158 0.469 0.6 e  0.7342  0.0076
CH4 91–190 0.416  0.173 0.348 0.4 f 0 (K MPa  1) 0.619810 0.738929
g (K) 6518.8 4940.5
a
 PN vp vp vp
AARD ¼ 100=N i 9P i,cal: P i,exp: 9=P i,exp: , where N is the number of the i  0.971250  0.040894
experimental data points. h 0.2078 0.3606

a
The numbers of the digits of the parameters have been determined by a
Table 6 sensitivity analysis of the final results to their values and their orders of
Critical properties and acentric factor of the applied pure compounds (gases) used magnitudes are in agreement with the corresponding values proposed by
in this study (Component Plus, 2001). Parrish and Prausnitz (1972) for clathrate hydrates.
b
Calculations were performed assuming formation of semi-clathrate hydrate
Compound Pca (MPa) Tcb (K) xc of type A.
c
Calculations were performed assuming formation of semi-clathrate hydrate
CH4 4.599 190.56 0.0114 of type B.
CO2 7.377 304.13 0.2239
N2 3.399 126.20 0.0377

a
Critical pressure.
b
Critical temperature. where PF is the penalized function, ggl (Pvp) is the inequality
c
Acentric factor. constraint, hhm(Pvp) represents the equality constraint, L and M are
the number of inequality and equality constraints, respectively, and
subjected to the following constraints (only for optimizing the PP denotes the penalty parameter which can be defined by the user.
Mathias-Copeman alpha function parameters): The value of this parameter depends on the order of magnitude of
the functions values involved in the problem and normally lies
ðZbÞ 4 0 ð31Þ
between 1 and 106 (Yazdizadeh et al., 2011, 2012; Deb, 2002).
pffiffiffi ! Greater values of PP leads to more penalized effects of the con-
Z þ ð1 2Þb
pffiffiffi 40 ð32Þ straints on the values of the objective function. In the present work,
Z þ ð1 þ 2b the penalty parameter has been set to 10. The bracket-operator /S
where Z is the compressibility factor and represents the absolute value of the operand, if operand is negative.
Therefore, the final formulation of the objective function is written
bP vp as follows:
b¼ ð33Þ
RT
In the preceding equation, b is the repulsive parameter of the PR X
2
OFðPdiss:=vp Þ ¼ f unctionðP diss:=vp Þ þ 10 /gg l ðPvp ÞS ð35Þ
EoS (Peng and Robinson, 1976). It should be noted that no constraint l¼1
was used for optimizing the hydrate model parameters. These two
constraints have been taken into account to avoid trivial results where
from the exponential terms of the fugacity expressions during the
calculation steps because the DE algorithm (Price and Storn, 1997; gg 1 ðPvp Þ ¼ maxf0,ðZbÞg ð36Þ
Babu and Angira, 2006) is a population-based optimization method
on the basis of random search algorithm and may consequently ( pffiffiffi !)
contribute to obtaining negative values of the corresponding argu- Z þð1 2Þb
gg 2 ðPvp Þ ¼ max 0, pffiffiffi ð37Þ
ments (Eqs. (31) and (32)). The penalty functions are generally Z þ ð1 þ 2Þb
employed in the case of constrained optimization, which penalize
infeasible solutions (eliminate the unexpected results) (Yazdizadeh Obviously, the last terms of (Eqs. (34) and (35)) are dropped
et al., 2011, 2012; Deb, 2002). The penalty function takes a finite during optimizing our hydrate model. The vapor pressure values
value when a constraint is violated and zero value when it is of the DIPPR 801 (Project 801, 2006) database have been used in
satisfied (Yazdizadeh et al., 2011, 2012; Deb, 2002). The penalized the optimization procedure of the Mathias–Copeman (Mathias
function (objective function after imposing the penalty criteria) can and Copeman, 1983) alpha function. Moreover, selected experi-
be expressed as follows (Yazdizadeh et al., 2011, 2012; Deb, 2002) mental dissociation pressures of semi-clathrate hydrates of CO2 in
" the presence of TBAB aqueous solutions (Mohammadi et al., 2011;
X
L  
PFðPdiss:=vp Þ ¼ f unctionðP diss:=vp Þ þ PP gg l ðP vp Þ Oyama et al., 2008) at various concentrations (mostly generated
l¼1 in our laboratory) (Mohammadi et al., 2011) have been utilized
# for obtaining the optimal values of the parameters in Eqs.
X
M
þ hhm ðP vp Þ ð34Þ (14)–(16). The probable global optimum values of the aforemen-
m¼1 tioned parameters are reported in Table 7.
 A. Eslamimanesh et al. / Chemical Engineering Science 81 (2012) 319–328 325

3. Results and discussion experimental values have been applied to designate which type
of semi-clathrate hydrate is formed at the conditions of interest
The performance of the model for prediction of the clathrate (i.e. pressure–temperature–concentration of TBAB in aqueous
hydrate dissociation conditions for the CO2/CH4/N2 þwater sys- solution).
tems in the liquid water–hydrate–vapor/gas equilibrium region Fig. 2 shows the predicted/represented clathrate/semi-clathrate
has been first examined. The obtained results are shown in hydrate dissociation conditions for the CO2 þTBAB aqueous solution
Table 8, which demonstrate acceptable accuracy of the model systems. It should be noted that only these semi-clathrate hydrate
results in wide ranges of temperatures and pressures compared dissociation data (Mohammadi et al., 2011; Oyama et al., 2008)
with selected experimental data (available in the NIST gas shown in Fig. 2) have been applied for obtaining the optimal values
hydrate database) (NIST gas hydrate database, 2009). of the model parameters. These parameters have been later utilized
It is worth pointing out that the phase behavior calculations for prediction of the dissociation conditions of CO2/CH4/N2 semi-
of the studied semi-clathrate hydrates have been undertaken clathrate hydrates in the presence of TBAB aqueous solution. In
in two steps assuming formation of type A and type B, respec- other words, the parameters in Eqs. (14)–(16) for evaluation of the
tively. Later, the represented/predicted hydrate dissociation vapor pressure of water in empty hydrate lattice and the Langmuir
pressures possessing the lowest values of the objective funct- constants in large hydrate cavities remain as global values for other
ion or average absolute relative deviation (AARD) from the gases (CH4 and N2) for further calculations.
The predicted phase equilibria of the CO2/CH4/N2 þwater/
TBAB aqueous solution systems are sketched in Figs. 3–5 (it
Table 8 should be again pointed out that no experimental hydrate
Summary of the model results for prediction of the hydrate dissociation conditions dissociation data for the CH4/N2 þTBAB aqueous solution systems
of CO2/CH4/N2 in the presence of water in the Lw–H–V equilibrium region. have been used in tuning process). A summary of the obtained
results are reported in Table 9. It is interpreted that the developed
Number of Temperature Pressure range AARDa
System model can reliably represent/predict the TBAB hydrate promotion
data range (K) (MPa) (%)
effects for the three investigated systems i.e. shifting the hydrate
CO2 þwater 160 273.3–283.0 1.35–4.40 1.8 phase boundaries to lower pressures and higher temperatures.
CH4 þ water 107 273.2–291.2 2.65–18.55 2.3 A recent comprehensive research study (SECOHYA, 2007) argues
N2 þ water 14 273.2–292.0 16.27–101 4.0
that the phase behavior of semi-clathrate hydrates may be compli-
 PN diss:
a
AARD ¼ 100=N diss: diss:
i 9P i,pred: P i,exp: 9=P i,exp: , where N is the number of the
cated and difficult to analyze, as stated earlier (Eslamimanesh et al.,
experimental data points, and subscript pred. stands for the predicted values. 2012). This is mainly because the semi-clathrate structure can be

5 5

4 4

3 3
p/MPa
P/ MPa

2 2

1 1

0 0
273 275 277 279 281 283 285 287 289 291 274 276 278 280 282 284 286 288 290 292
T/K T/K

Fig. 2. Dissociation conditions of clathrate/semi-clathrate hydrates for the carbon
dioxide þwater/TBAB aqueous solution systems. Symbols stand for the experi-
mental data and curves (lines) refer to the predicted/represented values using the
developed thermodynamic model. ’, CO2 þwater system (Mohammadi et al.,
2005; Fan et al., 2000; Ohgaki et al., 1993; Ng and Robinson, 1985); D, CO2 in the
presence of 0.01 mass fraction TBAB aqueous solution (Oyama et al., 2008); &,
CO2 in the presence of 0.02 mass fraction TBAB aqueous solution (Oyama et al.,
2008); B, CO2 in the presence of 0.05 mass fraction TBAB aqueous solution
(Mohammadi et al., 2011); n, CO2 in the presence of 0.50 mass fraction TBAB
aqueous solution (Mohammadi et al., 2011); J, CO2 in the presence of 0.10 mass
fraction TBAB aqueous solution (Mohammadi et al., 2011); þ, CO2 in the presence
of 0.167 mass fraction TBAB aqueous solution (Mohammadi et al., 2011);  , CO2
in the presence of 0.25 mass fraction TBAB aqueous solution (Mohammadi et al.,
2011); and  , CO2 in the presence of 0.35 mass fraction TBAB aqueous solution
(Mohammadi et al., 2011). Bold solid Curve, model predicted results for the
CO2 þ water system; Solid curves, model represented results assuming the forma-
tion of type B semi-clathrate hydrates (AARD¼ 3.1%); Dashed curves, model
represented results assuming the formation of type A semi-clathrate hydrates
(AARD¼ 3.2%).
Fig. 3. Dissociation conditions of clathrate/semi-clathrate hydrates for the carbon
dioxide þwater/TBAB aqueous solution systems. Symbols stand for experimental
data and curves (lines) refer to the predicted values using the developed
thermodynamic model. &, CO2 þ water system (Mohammadi et al., 2005; Fan
et al., 2000; Ohgaki et al., 1993; Ng and Robinson, 1985); m, CO2 in the presence of
0.0443 mass fraction TBAB aqueous solution (Lin et al., 2008); ~, CO2 in the
presence of 0.05 mass fraction TBAB aqueous solution (Li et al., 2010); B, CO2 in
the presence of 0.05 mass fraction TBAB aqueous solution (Duc et al., 2007);
K, CO2 in the presence of 0.0702 mass fraction TBAB aqueous solution (Lin et al.,
2008);  , CO2 in the presence of 0.0901 mass fraction TBAB aqueous solution (Lin
et al., 2008); þ, CO2 in the presence of 0.10 mass fraction TBAB aqueous solution
(Arjmandi et al., 2007); J, CO2 in the presence of 0.10 mass fraction TBAB aqueous
solution (Li et al., 2010); ’, CO2 in the presence of 0.427 mass fraction TBAB
aqueous solution; (Arjmandi et al., 2007);  , CO2 in the presence of 0.40 mass
fraction TBAB aqueous solution (Deschamps and Dalmazzone, 2009); Solid curves,
model predicted results assuming the formation of type B semi-clathrate hydrates
(AARD¼ 7.7%); Dashed curves, model predicted results assuming the formation of
type A semi-clathrate hydrates (AARD¼ 8.2%).
326 A. Eslamimanesh et al. / Chemical Engineering Science 81 (2012) 319–328
45
40
35
30
25
p/MPa
20
15
10
5 20
0
280 282 284 286 288 290 292 294 296 298 300
T/K
Fig. 4. Dissociation conditions of clathrate/semi-clathrate hydrates for the metha-
ne þwater/TBAB aqueous solution systems. Symbols stand for experimental data
and curves (lines) refer to the predicted values using the developed thermo-
dynamic model. &, CH4 þwater system (Mohammadi et al., 2005); n, CH4 in the
presence of 0.05 mass fraction TBAB aqueous solution (Mohammadi and Richon
2010); J, CH4 in the presence of 0.05 mass fraction TBAB aqueous solution (Sun
and Sun 2010); K, CH4 in the presence of 0.10 mass fraction TBAB aqueous
solution (Mohammadi et al., 2011); D, CH4 in the presence of 0.10 mass fraction
TBAB aqueous solution (Arjmandi et al., 2007); m, CH4 in the presence of 0.50 mass
fraction TBAB aqueous solution (Mohammadi et al., 2011); þ , CH4 in the presence
of 0.20 mass fraction TBAB aqueous solution (Arjmandi et al., 2007); B, CH4 in the
presence of 0.45 mass fraction TBAB aqueous solution (Sun and Sun 2010); þ , CH4
in the presence of 0.20 mass fraction TBAB aqueous solution (Arjmandi et al.,
2007); ’, CH4 in the presence of 0.25 mass fraction TBAB aqueous solution
(Mohammadi et al., 2011);  , CH4 in the presence of 0.30 mass fraction TBAB
aqueous solution (Arjmandi et al., 2007); Solid curves, model predicted results
assuming the formation of type B semi-clathrate hydrates (AARD¼ 5.6%); Dashed
curves, model predicted results assuming the formation of type A semi-clathrate
hydrates (AARD ¼13%).
changed from type A to type B (SECOHYA, 2007) or vice versa
(Eslamimanesh et al., 2012; Mohammadi et al., 2011; SECOHYA,
2007). The type of the structure depends normally on the hydration
number of the hydrate which results from particular gases investi-
gated in the presence of TBAB aqueous solutions (Eslamimanesh
et al., 2012; Mohammadi et al., 2011; SECOHYA, 2007). Generally,
the deviations of the calculated/estimated results of the proposed
model in this work from the experimental data seem to be less
assuming formation of semi-clathrate hydrates of type B with
respect to those obtained assuming formation of semi-clathrate
hydrates of type A. It is worth it to point out that the model seems to
be capable of prediction of the structural change of the investigated
semi-clathrates at some (limited) conditions of ‘‘temperature–pres-
sure–concentration of TBAB’’ triplets. For instance, at around 283 K
and 0.4 MPa, there may be a structural change from type A to
B in the phase equilibrium of the CO2 þ0.0702 mass fraction TBAB
aqueous solution system. It may be also the case at about 289 K
and 7 MPa for the hydrate dissociation conditions of the N2 þ 0.40
mass fraction TBAB aqueous solution system. However, various
experimental studies such as RAMAN spectroscopy and calorimetry
have revealed that there may be much more occasions where
the structural changes happen for the investigated systems
(SECOHYA, 2007). On the other hand, the former experimental
technique has also proposed formation of a new type of semi-
clathrates in the N2 þTBAB aqueous solution system. In addition,
some evidences have shown (Mohammadi et al., 2011; SECOHYA,
2007) that there are some discrepancies even in the produced
experimental data for the semi-clathrate hydrate systems so far.
120
100
80
p/MPa
60
40
0
280 282 284 286 288 290 292 294
T/K
Fig. 5. Dissociation conditions of clathrate/semi-clathrate hydrates for the nitro-
gen þwater/TBAB aqueous solution systems. Symbols stand for experimental data
and curves (lines) refer to the predicted values using the developed thermo-
dynamic model. ’, N2 þ water system (Sugahara et al., 2002);  , N2 in the
presence of 0.05 mass fraction TBAB aqueous solution (Lee et al., 2010); K, N2 in
the presence of 0.05 mass fraction TBAB aqueous solution (Mohammadi et al.,
2011); B, N2 in the presence of 0.10 mass fraction TBAB aqueous solution
(Arjmandi et al., 2007); þ, N2 in the presence of 0.10 mass fraction TBAB aqueous
solution (Duc et al., 2007); m, N2 in the presence of 0.10 mass fraction TBAB
aqueous solution (Mohammadi et al., 2011); &, N2 in the presence of 0.60 mass
fraction TBAB aqueous solution (Lee et al., 2010); ~, CH4 in the presence of 0.50
mass fraction TBAB aqueous solution (Mohammadi et al., 2011); n, N2 in the
presence of 0.20 mass fraction TBAB aqueous solution (Lee et al., 2010); J, N2 in
the presence of 0.40 mass fraction TBAB aqueous solution (Lee et al., 2010); Solid
curves, model predicted results assuming the formation of type B semi-clathrate
hydrates (AARD ¼11%); Dashed curves, model predicted results assuming the
formation of type A semi-clathrate hydrates (AARD¼ 11%).
Therefore, we do not generally expect our developed model to be
able to predict such structural changes, proposed by the experi-
mental efforts.
Another element to consider is that, the developed model can
acceptably predict the hydrate inhibition effects of TBAB at the
concentrations greater than that of stoichiometric ratios (around
0.427 mass fraction TBAB in aqueous solution) (Shimada et al.,
2005; SECOHYA, 2007; Paricaud, 2011).
One significant factor should not be omitted from our discus-
sion. Our main goal here has been to determine the phase
behavior of semi-clathrate hydrates formed from gaseous hydrate
formerþ TBAB aqueous solution. The developed model may not be
able to represent/predict the solid (S)–liquid (L) equilibria of the
TBABþwater system (TBAB hydrate þTBAB aqueous solution
phase equilibria). In other words, it seems not to be applicable
for determination of the ‘‘temperature–composition’’ diagram of
the aforementioned system at a specified pressure. However,
this is not the case for the model developed on more powerful
(and more complex) theoretical approaches like the one proposed
by Paricaud (2011), which employs the (SAFT-VRE) (Galindo
et al., 1999) for accurate prediction of the mentioned phase
equilibria.
To recapitulate, there is still a need to conduct considerable
efforts for developing accurate and predictive models for represen-
tation/prediction of the phase equilibria of semi-clathrate hydrates.
In addition, extension of the models to the multi-component
systems (like binary mixtures of carbon dioxide with other gases)
seems to be necessary, which is the subject of the future studies.
 A. Eslamimanesh et al. / Chemical Engineering Science 81 (2012) 319–328
Table 9
Summary of the model results for prediction of the dissociation conditions of semi-clathrate hydrates of CO2/CH4/N2 þ TBAB aqueous solution in the Lw–H–V equilibrium
region.
System Number Temperature
of data range (K)
CO2 þTBAB aqueous solution 54 279.3–291.2
CH4 þ TBAB aqueous solution 66 281.75–
298.15
N2 þ TBAB aqueous solution 55 279.84–
292.95
a
 PN diss: diss: diss:
AARD ¼ 100=N i 9P i,pred: P i,exp: 9=P i,exp: , where N is the number of the experimental data points, and subscript pred. stands for the predicted values.
b
Calculations were performed assuming formation of semi-clathrate hydrate of type A.
c
Calculations were performed assuming formation of semi-clathrate hydrate of type B.
4. Conclusions
In this communication, a thermodynamic model was proposed
to calculate/estimate the dissociation conditions of the semi-
clathrate hydrates of CO2/CH4/N2 in the presence of TBAB aqueous
solution. The model was developed on the basis of the solid
solution theory of the vdW–P (van der Waals and Platteeuw,
1959; Platteeuw and van der Waals, 1959) with modification of
the expressions to determine the vapor pressure of water in empty
hydrate lattice and the Langmuir constants. Additionally the PR EoS
(Peng and Robinson, 1976) along with the Mathias–Copeman alpha
function (Mathias and Copeman, 1983) containing re-tuned para-
meters were applied for calculation of the fugacity of the gaseous
hydrate former in the gas phase. The capability of the model for
prediction of the phase equilibria of the corresponding simple
clathrate hydrates in the presence of water has been successfully
checked prior to extension to the semi-clathrate hydrates. The
optimal values of the model parameters were obtained minimizing
the deviation of the calculated model results compared to the data
of the CO2 þTBAB aqueous solution systems. The tuned parameters
were later used to estimate the semi-clathrate hydrate dissociation
conditions of CO2/CH4/N2 in the presence of TBAB aqueous solu-
tion. Acceptable agreement between the model results and
selected experimental data from the literature was observed. In
addition, the following factors can be interpreted:
1. The developed model may not be capable of prediction of the
possible structural changes of the semi-clathrate hydrates in
wide ranges of temperature–pressure–composition of the
TBAB in aqueous solution.
2. The promotion or inhibition effects of the TBAB can be well-
represented/predicted using the proposed model.
3. Easy-to-use model parameters and its straight-forward develop-
ment are among the advantages of the studied model in this work.
4. The thermodynamic model may not be applicable for predic-
tion of the S–L equilibria of the TBABþ water system.
5. There is a possibility for the extension of the model to calculate/
estimate the phase behaviors of the semi-clathrate hydrates
formed from binary mixtures of the investigated gases.
Acknowledgment
Ali Eslamimanesh is grateful to MINES ParisTech for providing
him with a Ph.D. scholarship. This work was financially supported
by the Agence Nationale de la Recherche (ANR) as part of the
SECOHYA project. The financial supports of Orientation Stratégique
des Ecoles des Mines (OSEM) and INSTITUT CARNOT MINES are also
acknowledged. The authors thank Dr. Patrice Paricaud for fruitful
discussions on the issue.
327
Pressure range TBAB concentration in aqueous AARDa (%)
(MPa) solution/mass fraction
b c
Type A Type B
0.273–4.09 0.0443, 0.05, 0.0702, 0.0901, 0.1, 0.4, 0.427, 0.65 8.2 7.7
0.235–35.853 0.05, 0.1, 0.2, 0.25. 0.3, 0.45, 0.50
13 5.6
0.47–35.503 0.05, 0.10, 0.20, 0.25, 0.40, 0.50, 0.60
11 11
References
Amado, G.E, Blanco, L.H., 2005. Isopiestic determination of the osmotic and activity
coefficients of dilute aqueous solutions of symmetrical and unsymmetrical
quaternary ammonium bromides with a new isopiestic cell at 298.15 K. Fluid
Phase Equilibr. 233, 230–233.
Arjmandi, M., Chapoy, A., Tohidi, B., 2007. Equilibrium data of hydrogen, methane,
nitrogen, carbon dioxide, and natural gas in semi-Clathrate hydrates of
tetrabutyl ammonium bromide. J. Chem. Eng. Data 52, 2153–2158.
Babu, B.V., Angira, R., 2006. Modified Differential Evolution (MDE) for optimization
of non-linear chemical processes. Comput. Chem. Eng. 30, 989–1002.
Belandria, V., Mohammadi, A.H., Richon, D., 2009. Volumetric properties of the
(tetrahydrofuranþ water) and (tetra-n-butyl ammonium bromide þwater)
systems: experimental measurements and correlations. J. Chem. Thermodyn.
41, 1382–1386.
Belandria, V., Eslamimanesh, A., Mohammadi, A.H., Théveneau, P., Legendre, H.,
Richon, D., 2011a. Compositional analysis and hydrate dissociation conditions
measurements for carbon dioxide þmethane þwater system. Ind. Eng. Chem.
Res. 50, 5783–5794.
Belandria, V., Eslamimanesh, A., Mohammadi, A.H., Richon, D., 2011b. Gas hydrate
formation in carbon dioxide þ nitrogenþwater system: compositional analysis
of equilibrium phases. Ind. Eng. Chem. Res. 50, 4722–4730.
Chen, L.-F., Soriano, A.N., Li, M.-H., 2009. Vapour pressures and densities of the
mixed-solvent desiccants (glycols þ waterþsalts). J. Chem. Thermodyn. 41,
724–730.
Component Plus, Version 3.0.0.0, Pure component database manager, ProSim SA,
Released 2001.
Deb, K., 2002. Multi-Objective Optimization Using Evolutionary Algorithms. Wiley,
West Sussex, England.
Delyannis, A., Delyannis, E., 1978. Fresh water from the sea. In: 6th Proceedings of
the International Symposium on Fresh Water from Sea, Las Palmas, Gran
Canaria, Spain.
Deschamps, J., Dalmazzone, D., 2009. Dissociation enthalpies and phase equili-
brium for TBAB semi-clathrate hydrates of N2, CO2, N2 þCO2 and CH4 þCO2.
J. Therm. Anal. Calorim. 98, 113–118.
Dharmawardhana, P.B., Parrish, W.R., Sloan, E.D., 1980. Experimental thermody-
namic parameters for the prediction of natural gas hydrate dissociation
conditions. Ind. Eng. Chem. Fundam. 19, 410–414.
Duc, N.H., Chauvy, F., Herri, J.M., 2007. CO2 capture by hydrate crystallization—a
potential solution for gas emission of steelmaking industry. Energy Convers.
Manage. 48, 1313–1322.
Eslamimanesh, A., 2009. A Semicontinuous Thermodynamic Model for Prediction
of Asphaltene Precipitation in Oil Reservoirs. M.Sc. Thesis, Shiraz University,
Shiraz, Iran (in Persian).
Eslamimanesh, A., Esmaeilzadeh, F., 2010. Estimation of the solubility parameter
by the modified ER equation of state. Fluid Phase Equilibr. 291, 141–150.
Eslamimanesh, A., Shariati, A., 2009. A semicontinuous thermodynamic model for
prediction of asphaltene precipitation. Presented at the VIII Iberoamerican
Conference on Phase Equilibria and Fluid Properties for Process Design
(Equifase), Praia da Rocha, Portugal, October 2009.
Eslamimanesh, A., Mohammadi, A.H., Richon, D., 2011a. Thermodynamic model
for predicting phase equilibria of simple clathrate hydrates of refrigerants.
Chem. Eng. Sci. 66, 5439–5445.
Eslamimanesh, A., Mohammadi, A.H., Richon, D., 2011b. An improved Clapeyron
model for predicting liquid water–hydrate–liquid hydrate former phase
equilibria. Chem. Eng. Sci. 66, 1759–1764.
Eslamimanesh, A., Mohammadi, A.H., Richon, D., 2011c. Thermodynamic consis-
tency test for experimental solubility data in carbon dioxide/methane þwater
system inside and outside gas hydrate formation region. J. Chem. Eng. Data 56,
1573–1586.
Eslamimanesh, A., Mohammadi, A.H., Richon, D., 2011d. Thermodynamic consis-
tency test for experimental data of sulfur content of hydrogen sulfide. Ind. Eng.
Chem. Res. 50, 3555–3563.
328 A. Eslamimanesh et al. / Chemical Engineering Science 81 (2012) 319–328
Eslamimanesh, A., Mohammadi, A.H., Richon, D., Naidoo, P., Ramjugernath, D.,
2012. Application of gas hydrate formation in separation processes: a review
of experimental studies. J. Chem. Thermodyn. 46, 62–71.
Fan, S., Li, S., Wang, J., Lang, X., Wang, Y., 2009. Efficient capture of CO2 from
simulated flue gas by formation of TBAB or TBAF semiclathrate hydrates.
Energy Fuels 23, 4202–4208.
Fan, S.S., Chen, G.J., Ma, Q.L., Guo, T.M., 2000. Experimental and modeling studies
on the hydrate formation of CO2 and CO2-rich gas mixtures. Chem. Eng. J. 78,
173–178.
Feron, P.H.M., Hendricks, C.A., 2005. CO2 capture process principles and costs; Les
différents procédés de capture du CO2 et leurs coûts. Oil Gas Sci. Technol.—Rev.
IFP 60, 451–459.
Florusse, L.J., Peters, C.J., Schoonman, J., Hester, K.C., Koh, C.A., Dec, S.F., Marsh,
K.N., Sloan, E.D., 2004. Stable low-pressure hydrogen clusters stored in a
binary clathrate hydrate. Science 306, 469–471.
Fukushima, S., Takao, S., Ogoshi, H., Ida, H., Matsumoto, S., Akiyama, T., Otsuka, T.,
1999. NKK Technical Report, vol. 166, p. 65 (in Japanese).
Galindo, A., Gil-Villegas, A., Jackson, G., Burgess, A.N.J., 1999. SAFT-VRE: phase
behavior of electrolyte solutions with the statistical associating fluid theory
for potentials of variable range. J. Phys. Chem. B 103, 10272–10281.
Hall, C., Tharakan, P., Hallock, J., Cleveland, C., Jefferson, M., 2003. Hydrocarbons
and the evolution of human culture. Nature 426, 318–322.
Hammerschmidt, E.G., 1934. Formation of gas hydrates in natural gas transmission
lines. Ind. Eng. Chem. 26, 851–855.
Huang, C.P., Fennema, O., Powrie, W.D., 1965. Gas hydrates in aqueous-organic
systems: I. Preliminary studies. Cryobiology 2, 109–115.
Huang, C.P., Fennema, O., Powrie, W.D., 1966. Gas hydrates in aqueous-organic
systems: II. Concentration by gas hydrate formation. Cryobiology 2, 240–245.
International Panel on Climate Control (IPCC), 2005. Carbon dioxide capture and
storage. Special report. International Panel on Climate Control (IPCC), February
5, 2007. Climate Change 2007: The Physical Science Basis—Summary for
Policy Makers.
Javanmardi, J., Moshfeghian, M., 2003. Energy consumption and economic evalua-
tion of water desalination by hydrate phenomenon. Appl. Therm. Eng. 23,
845–857.
Kang, S.P., Lee, H., 2000. Recovery of CO2 from flue gas using gas hydrate:
thermodynamic verification through phase equilibrium measurements.
Environ. Sci. Technol. 34, 4397–4400.
Klauda, J.B., Sandler, S.I., 2000. A fugacity model for gas hydrate phase equilibria.
Ind. Eng. Chem. Res. 39, 3377–3386.
Krichevsky, I.R., Kasarnovsky, J.S., 1935. Thermodynamical calculations of solubi-
lities of nitrogen and hydrogen in water at high pressures. J. Am. Chem. Soc.
57, 2168–2172.
Lee, H.J., Lee, J.D., Linga, P., Englezos, P., Kim, Y.S., Lee, M.S., Kim, Y.D., 2010. Gas
hydrate formation process for pre-combustion capture of carbon dioxide.
Energy 35, 2729–2733.
Li, S., Fan, S., Wang, J., Lang, X., Wang, Y., 2010. Clathrate hydrate capture of CO2
from simulated flue gas with cyclopentane/water emulsion. Chin. J. Chem. Eng.
18, 202–206.
Lin, W., Delahaye, A., Fournaison, L., 2008. Phase equilibrium and dissociation
enthalpy for semi-clathrate hydrate of CO2 þTBAB. Fluid Phase Equilibr. 264,
220–227.
Lindenbaum, S., Boyd, G.E., 1964. Osmotic and activity coefficients for the
symmetrical tetraalkyl ammonium halides in aqueous solution at 25 1C.
J. Phys. Chem. 68, 911–917.
Linga, P., Kumar, R., Englezos, P., 2007. The clathrate hydrate process for post and
pre-combustion capture of carbon dioxide. J. Hazard. Mater. 149, 625–629.
Makino, T., Yamamoto, T., Nagata, K., Sakamoto, H., Hashimoto, S., Sugahara, T.,
Ohgaki, K., 2010. Thermodynamic stabilities of tetra-n-butyl ammonium
chloride þH2, N2, CH4, CO2, or C2H6 semiclathrate hydrate systems. J. Chem.
Eng. Data 55, 839–841.
Mathias, P.M., Copeman, T.W., 1983. Extension of the Peng  Robinson equation of
state to complex mixtures: evaluation of the various forms of the local
composition concept. Fluid Phase Equilibr. 13, 91–108.
Mohammadi, A.H., Richon, D., 2008. Thermodynamic model for predicting liquid
water-hydrate equilibrium of the water–hydrocarbon system. Ind. Eng. Chem.
Res. 47, 1346–1350.
Mohammadi, A.H., Richon, D., 2009. Development of predictive techniques for
estimating liquid water-hydrate equilibrium of water hydrocarbon system.
J. Thermodyn., 1–12.
Mohammadi, A.H., Richon, D., 2010. Phase equilibria of semi-clathrate hydrates of
tetra-n-butylammonium bromide þhydrogen sulfide and tetra-n-butylammo-
nium bromide þmethane. J. Chem. Eng. Data 55, 982–984.
Mohammadi, A.H., Anderson, R., Tohidi, B., 2005. Carbon monoxide clathrate hydrates:
equilibrium data and thermodynamic modeling. AIChE J. 51, 2825–2833.
Mohammadi, A.H., Eslamimanesh, A., Belandria, V., Richon, D., 2011. Phase
equilibria of semiclathrate hydrates of CO2, N2, CH4, or H2 þ Tetra-n-butylam-
monium bromide aqueous solution. J. Chem. Eng. Data 56, 3855–3865.
Mohammadi, A.H., Eslamimanesh, A., Belandria, V., Richon, D., Naidoo, P., Ramju-
gernath, D., 2012a. Phase equilibrium measurements for semi-clathrate
hydrates of the (CO2 þN2 þ tetra-n-butylammonium bromide) aqueous solu-
tion system. J. Chem. Thermodyn. 46, 57–61.
Mohammadi, A.H., Belandria, V., Richon, D., 2012b. Use of an artificial neural
network algorithm to predict hydrate dissociation conditions for hydrogen þ
water and hydrogen þ tetra-n-butyl ammonium bromideþ water systems.
Chem. Eng. Sci. 65, 4302–4305.
Moore, J.C., Battino, R., Rettich, T.R., Handa, Y.P., Wilhelm, E., 1982. Partial molar
volumes of ‘‘gases’’ at infinite dilution in water at 298.15 K. J. Chem. Eng. Data
27, 22–24.
Ng, H.-J., Robinson, D.B., 1985. Hydrate formation in systems containing methane,
ethane, propane, carbon dioxide or hydrogen sulfide in the presence of
methanol. Fluid Phase Equilibr. 21, 145–155.
NIST gas hydrate database, 2009. Thermodynamics Research Center (TRC),
Thermophysical Properties Division, NIST, Boulder, CO.
Ogawa, T., Ito, T., Watanabe, K., Tahara, K.I., Hiraoka, R., Ochiai, J.I., Ohmura, R.,
Mori, Y.H., 2006. Development of a novel hydrate-based refrigeration system:
a preliminary overview. Appl. Therm. Eng. 26, 2157–2167.
Ohgaki, K., Makihara, Y., Takano, K., 1993. Formation of CO2 hydrate in pure and
sea waters. J. Chem. Eng. Jpn. 26, 558–564.
Oyama, H., Shimada, W., Ebinuma, T., Kamata, Y., Takeya, S., Uchida, T., Nagao, J.,
Narita, H., 2005. Phase diagram, latent heat, and specific heat of TBAB
semiclathrate hydrate crystals. Fluid Phase Equilibr. 234, 131–135.
Oyama, H., Ebinuma, T., Nagao, J., Narita, H., Shimada, W., 2008. Phase behavior of
TBAB semiclathrate hydrate crystal under several vapor components, Proceed-
ings of the 6th International Conference on Gas Hydrates (ICGH). Vancouver,
Canada.
Pahlavanzadeh, H., Kamran-Pirzaman, A., Mohammadi, A.H., 2012. Thermody-
namic modeling of pressure-temperature phase diagrams of binary clathrate
hydrates of methane, carbon dioxide or nitrogen þ tetrahydrofuran, 1,4-diox-
ane or acetone. Fluid Phase Equilibr. 320, 32–37.
Paricaud, P., 2011. Modeling the dissociation conditions of salt hydrates and gas
semiclathrate hydrates: application to lithium bromide, hydrogen iodide, and
tetra-n-butylammonium bromideþ carbon dioxide systems. J. Phys. Chem. B
115, 288–299.
Parrish, W.R., Prausnitz, J.M., 1972. Dissociation pressures of gas hydrates formed
by gas mixtures. Ind. Eng. Chem. Process Des. Dev. 11, 26–35.
Peng, D.Y., Robinson, D.B., 1976. A new two-constant equation of state. Ind. Eng.
Chem. Fundam. 15, 59–64.
Peng, X., Hu, Y., Liu, Y., Jin, C., Lin, H., 2010. Separation of ionic liquids from dilute
aqueous solutions using the method based on CO2 hydrates. J. Nat. Gas Chem.
19, 81–85.
Platteeuw, J.C., van der Waals, J.H., 1959. Thermodynamic properties of gas
hydrates II: phase equilibria in the system H2S–C3H8–H2O at  3 1C. Recl.
Trav. Chim. Pays-Bas 78, 126–133.
Price, K., Storn, R., 1997. Differential evolution. Dr. Dobb’s J. 22, 18–24.
Project 801, Evaluated Process Design Data, Public Release Documentation, Design
Institute for Physical Properties (DIPPRs). American Institute of Chemical
Engineers (AIChE), 2006.
Renon, H., Prausnitz, J.M., 1968. Liquid–liquid and vapor–liquid equilibria for
binary and ternary systems with dibutyl ketone, dimethyl sulfoxide, n-hexane,
and 1-hexene. Ind. Eng. Chem. Process Des. Dev. 7, 220–225.
SECOHYA (Separation of CO2 by HYdrate Adsorption) project of Agence Nationale
de la Recherche (ANR), internal reports, France, 2007–2011.
Shimada, W., Shiro, M., Kondo, H., Takeya, S., Oyama, H., Ebinuma, T., Narita, H.,
2005. Tetra-n-butylammonium bromide-water (1/38). Acta Crystallogr. Sect.
C: Cryst. Struct. Commun. 61, o65–o66.
Shin, K., Kim, Y., Strobel, T.A., Prasad, P.S.R., Sugahara, T., Lee, H., Sloan, E.D., Sum,
A.K., Koh, C.A., 2009. Tetra-n-butylammonium borohydride semiclathrate:
a hybrid material for hydrogen storage. J. Phys. Chem. A 113, 6415–6418.
Sloan, E.D., Koh, C.A., 2008. Clathrate Hydrates of Natural Gases, third edition CRC
Press, Taylor & Francis Group, Boca Raton.
Söhnel, O., Novotny, P., 1985. Densities of Aqueous Solutions of Inorganic
Substances. Elsevier Science Pub. Co, Amsterdam.
Strobel, T.A., Hester, K.C., Koh, C.A., Sum, A.K., Sloan Jr., E.D., 2009. Properties of the
clathrates of hydrogen and developments in their applicability for hydrogen
storage. Chem. Phys. Lett. 478, 97–109.
Sugahara, K., Tanaka, Y., Sugahara, T., Ohgaki, K., 2002. Thermodynamic stability
and structure of nitrogen hydrate crystal. J. Supramol. Chem. 2, 365–368.
Sun, Z.G., Sun, L., 2010. Equilibrium conditions of semi-clathrate hydrate dissocia-
tion for methaneþ tetra-n-butyl ammonium bromide. J. Chem. Eng. Data 55,
3538–3541.
Tsuda, T., Ogata, K., Hashimoto, S., Sugahara, T., Moritoki, M., Ohgaki, K., 2009.
Storage capacity of hydrogen in tetrahydrothiophene and furan clathrate
hydrates. Chem. Eng. Sci. 64, 4150–4154.
Tumba, K., Reddy, P., Naidoo, P., Ramjugernath, D., Eslamimanesh, A., Mohammadi,
A.H., Richon, D., 2011. Phase equilibria of methane and carbon dioxide
clathrate hydrates in the presence of aqueous solutions of tributylmethylpho-
sphonium methylsulfate ionic liquid. J. Chem. Eng. Data 56, 3620–3629.
van der Waals, J.H., Platteeuw, J.C., 1959. Clathrate solutions. In: Prigogine, I. (Ed.),
Advances in Chemical Physics. Interscience, pp. 1–57.
Wenji, S., Rui, X., Chong, H., Shihui, H., Kaijun, D., Ziping, F., 2009. Experimental
investigation on TBAB clathrate hydrate slurry flows in a horizontal tube:
forced convective heat transfer behaviors. Int. J. Refrig. 32, 1801–1807.
Yazdizadeh, M., Eslamimanesh, A., Esmaeilzadeh, F., 2011. Thermodynamic mod-
eling of solubilities of various solid compounds in supercritical carbon dioxide:
effects of equations of state and mixing rules. J. Supercrit. 55, 861–875.
Yazdizadeh, M., Eslamimanesh, A., Esmaeilzadeh, F., 2012. Applications of cubic
equations of state for determination of the solubilities of industrial solid
compounds in supercritical carbon dioxide: a comparative study. Chem. Eng.
Sci. 71, 283–299.