Fluid Phase Equilibria 361 (2014) 208–214

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Fluid Phase Equilibria

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Phase equilibrium and morphology characteristics of hydrates formed

by tetra-n-butyl ammonium chloride and tetra-n-butyl phosphonium
chloride with and without CO2
N. Ye, P. Zhang ∗
Institute of Refrigeration and Cryogenics, MOE Key Laboratory for Power Machinery and Engineering, Shanghai Jiao Tong University, Shanghai 200240,
China

a r t i c l e i n f o a b s t r a c t

Article history: In this study, experimental investigations on hydrate equilibrium conditions of hydrates formed by
Received 6 September 2013 tetra-n-butyl ammonium chloride (TBAC: C16 H36 ClN) and tetra-n-butyl phosphonium chloride (TBPC:
Received in revised form 23 October 2013 C16 H36 ClP) with and without CO2 are carried out using isochoric experimental method at mass frac-
Accepted 30 October 2013
tions w = 0.05, 0.10, 0.20, 0.35 and 0.50. The equilibrium data of CO2 + TBAC and CO2 + TBPC hydrates
Available online 6 November 2013
are measured at pressures of 0.6 to 4.1 MPa and at temperatures from 279.0 to 292.0 K. Meanwhile,
the equilibrium data of TBAC and TBPC hydrates without CO2 are measured at atmospheric pressure
Keywords:
and at temperatures from 279.0 to 286.0 K. Moreover, the visualization is conducted to characterize the
Phase equilibrium
Hydrate
morphologies of hydrate crystals forming at subcoolings of 4.0 to 6.0 K, and the results are discussed
Tetra-n-butyl ammonium chloride in comparison with those of tetra-n-butyl ammonium bromide (TBAB) and tetra-n-butyl phosphonium
Tetra-n-butyl phosphonium chloride bromide (TBPB) hydrate crystals forming with and without CO2 presented in our previous papers.
Morphology © 2013 Elsevier B.V. All rights reserved.

1. Introduction
Gas hydrates or clathrate hydrates are inclusion compounds
with crystalline appearance similar to that of ice. Gas hydrates
can form with water as host component and suitable gas as
guest component at low temperature and high pressure. Within
the structure of hydrate molecule, water molecules are strongly
hydrogen-bonded to construct cage of hydrate molecule in which
some cavities are occupied by guest molecules. More than 130 guest
components are known being able to form gas hydrate with water,
and gas hydrates are mainly categorized into three types of struc-
ture: SI , SII and SH [1] depending on the size, shape and nature of
guest molecules. Since 1934, gas hydrate was regarded as the rea-
son for blockage by the oil and gas industries because the formation
of gas hydrates can block pipelines [2]. However, with gradual dis-
covery of huge reserve of natural gas hydrate, a new natural energy
resource, in the earth, more attentions were focused on gas hydrate.
In modern society, hydrate is also a promising medium to separate
the greenhouse gas like CO2 from flue gas emitted by industries. In
addition, CO2 hydrate can be used as two-phase secondary refriger-
ant for cold storage and transport in order to improve the efficiency
of cold production system because the dissociation enthalpy of CO2
hydrate is larger than that of ice [3].
∗ Corresponding author. Tel.: +86 21 34205505; fax: +86 21 34206814.
E-mail address: zhangp@sjtu.edu.cn (P. Zhang).
Fowler et al. [4] first identified new hydrate forming from water
as the host component and tetra-n-butyl ammonium salts as the
guest component at atmospheric pressure and room temperature.
Unlike gas hydrate, this kind of hydrate can form without the pres-
ence of gas, and it was named as semiclathrate hydrate due to
its different molecular structure from the above-mentioned three
usual structures of gas hydrates. The cage of gas hydrate molecule is
solely comprised of water molecules; but for semiclathrate hydrate,
one water molecule is replaced by one anion from tetra-n-butyl
ammonium salt to construct a cage with many water molecules,
and one cation from tetra-n-butyl ammonium salt is trapped in
four cavities in the cage [5]. Among these semiclathrate hydrates,
tetra-n-butyl ammonium bromide (TBAB) semiclathrate hydrate
has been most investigated. As the phase equilibrium tempera-
ture is higher than that of ice, and the formation condition is
milder than that of gas hydrate, TBAB semiclathrate hydrate is
deemed as a promising medium for cold storage [6,7]. Further-
more, semiclathrate hydrate can also incorporate suitable gas in
empty cavities under moderate condition, and it is named as double
hydrate, for example, CO2 + TBAB double hydrate, where there are
two kinds of guest components, i.e., the gas and TBAB in the hydra-
tion formation. Such double hydrate can be used as the medium
for gas storage and separation [8,9]. Recently, there are intensive
researches on CO2 + TBAB double hydrate because CO2 is regarded
as a main contributor to the greenhouse effect in modern society
with high fossil fuel consumption. As a result, the technology based
on double hydrate for CO2 capture and separation [10–12] has a

0378-3812/$ – see front matter © 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.fluid.2013.10.055
 N. Ye, P. Zhang / Fluid Phase Equilibria 361 (2014) 208–214
Table 1
List of experimental materials adopted in the current study.
Component Purity Supplier
CO2 >0.999 mole fraction Shanghai Cheng Gong Gas
Industry Co., Ltd., China
TBAC 0.99 mass fraction Shanghai Richness Chemical
Co., Ltd., China
TBPC 0.99 mass fraction Shanghai Weifang Fine
Chemical Co., Ltd., China
Water Distilled
good prospect for large-scale industrial application, in which phase
equilibrium data is one of the key parameters. The hydrate with
a higher equilibrium temperature at specified pressure is much
more favorable for energy saving in industrial application. There-
fore, to measure the phase equilibrium data of different hydrates
is very necessary. Many studies have reported the phase equilib-
rium data of similar double hydrates with CO2 , such as CO2 + TBPB
and CO2 + TBAC double hydrates [13–15]. However, it is found
that the published equilibrium data of CO2 + TBAC double hydrate
are only in a narrow mass fraction range, and there are even no
equilibrium data for CO2 + TBPC double hydrate reported in open
literature.
In this study, equilibrium data of TBAC and TBPC hydrates form-
ing with and without CO2 have been measured systematically in a
wide mass fraction range. Moreover, in order to characterize TBAC
and TBPC hydrate crystals, the visualization is also carried out, and
the results are discussed in comparison with those of TBAB and
TBPB hydrate crystals forming with and without CO2 [16,17].
2. Experiments and methods
2.1. Materials
Table 1 shows the purities and suppliers of chemicals used in the
current study. Distilled water as solvent and TBAC or TBPC as solute
were used for solution preparation. TBAC and TBPC were supplied
by Shanghai Richness Chemical Co., Ltd and Shanghai Weifang Fine
Chemical Co., Ltd, respectively, and the purities of them were all
0.99 (mass fraction). In addition, carbon dioxide with a purity larger
than 0.999 (mole fraction) was purchased from Shanghai Cheng
Gong Gas Industry Co., Ltd. All the above-mentioned chemicals
were used without further purification.
2.2. Apparatus and preparations
The experimental apparatus used for the phase equilibrium con-
dition measurements and visualization is shown in Fig. 1, which has
been described in detail in our previous works [16,17]. The main
Fig. 1. Schematic diagram of the experimental apparatus. PT, pressure transducer;
T, thermometer; V1 to V4, valves [16, 17].
209
part of the apparatus was an in-house made cylindrical crystallizer
(CR) made of stainless steel with inner volume of 1030.0 ml. The CR
can provide a sealed high-pressure condition for hydration up to
15.0 MPa. In addition, the formation and dissociation of hydrate can
be observed through two optic windows made of aluminosilicate
glass embedded in CR. The images of hydrate crystals were taken by
a charge-coupled device (CCD) camera (Grasshopper GRAS-50S5C,
Point Gray Research, Inc., Canada). A magnetic stir bar in CR was
used for agitating the aqueous solution. The stir bar was driven and
controlled by an electric motor (H03-A, Shanghai Meiyinpu Instru-
ment, Ltd., China) placed directly under CR. The CR was immersed
in a thermostat bath covered by thermal insulation material. Eth-
ylene glycol/water mixture (40:60 wt%) as coolant was circulated
between a thermostat (DC2020, Shanghai Hengping Instrument
Co., Ltd., China) and the thermostat bath to control the tempera-
ture of CR. The temperatures of the gas and liquid phases in CR were
measured by two PT100 thermometers (WZP-270S, Shanghai Insti-
tute of Process Automation Instrumentation) with an uncertainty
of 0.1 K, and the pressure in CR was measured by a pressure trans-
ducer (YSZK-311, Dinkey Instrument Co. Ltd., China, (0 to 15.0 MPa)
F.S., uncertainty: 0.1%).
An electronic balance with a high accuracy was used to weigh
TBAC or TBPC and distilled water for aqueous solution preparation
with the designated mass fraction. The uncertainty of this balance
was 0.01 g (JM10002, Zhejiang Yuyao Jingming Weighing Sclae Co.,
Ltd., China). The mass fractions of TBAC and TBPC aqueous solutions
adopted in this work were w = 0.05, 0.10, 0.20, 0.35 and 0.50. Each
time before charging the specified mass fraction aqueous solution,
the CR was rinsed with aqueous solution at the same mass frac-
tion. After solution charging, the CR was flushed with low-pressure
CO2 to remove any residual air. When CO2 was introduced to CR
at a designated pressure, the CR was sealed and the preparation
procedure was completed.
2.3. Experimental procedure
2.3.1. Measurements of hydrate phase equilibrium condition
The temperature of coolant was set low enough and the solu-
tion within CR was continuously agitated with a magnetic stir
bar at a speed of 600 rpm to accelerate the formation of hydrate.
The hydrate formation can be observed directly through the optic
windows. There was a rapid drop in pressure and a rapid rise in tem-
perature when hydrate formed. When there was no more change
in the pressure and temperature versus time, the temperature of
the system was increased at a step of 0.1 K h−1 to dissolve hydrate.
When infinitesimal amount of hydrate was detected in CR, the tem-
perature increase rate was decreased to 0.0333 K h−1 . The heating
up was stopped until there was no hydrate left in aqueous solution
by observation, and the pressure and temperature were considered
as the phase equilibrium data.
2.3.2. Crystal morphologies of hydrate with and without CO2
In the experiments, the hydrate crystals morphologies with and
without CO2 were observed and recorded by a CCD camera. The
time when the first crystal was observed in the experiments was set
as 0 s for determining the crystal growth. The subcooling Tsub =
Teq − Tex is in the range of 4.0 to 6.0 K, where Teq is the equi-
librium temperature of TBAC and TBPC semiclathrate hydrates or
CO2 + TBAC and CO2 + TBPC double hydrates corresponding to the
equilibrium pressure p, and Tex is the bath temperature.
3. Results and discussion
The measurements of the phase equilibrium data of TBAC and
TBPC semiclathrate hydrates forming at atmospheric pressure were
conducted using the isochoric experimental method at different
210 N. Ye, P. Zhang / Fluid Phase Equilibria 361 (2014) 208–214

290 Table 2
Equilibrium data for TBAC and TBPC semiclathrate hydrates at atmospheric
pressure.a
288
w T (K)
286
TBAC TBPC

284 0.10 280.42 279.04

0.20 284.74 281.82
282 Current study 0.35 286.89 283.45
T/K

0.50 285.59 282.30

Nakayama [18]
280 Aladko and Dyadin [19] a
Standard uncertainties u in the isochoric experiments are u(w) = 0.00003, and
Sato et al. [20] u(T) = 0.1 K.
278 Sun et al. [21]
276 the congruent melting point, i.e., the maximum melting temper-
ature, and the equilibrium temperature decreases when the mass
274
0.0 0.1 0.2 0.3 0.4 0.5 0.6 fraction exceeds wTBAC = 0.35.
Fig. 3 shows the comparison between the phase equilibrium
wTBAC data of TBPC semiclathrate hydrate measured in the current study
and those measured by Sakamoto et al. [22]. The results mea-
Fig. 2. Phase diagram of TBAC semiclathrate hydrate at atmospheric pressure. 䊉, sured in the current study are consistent with those measured by
current study; , Nakayama [18];♦, Aladko and Dyadin [19]; , Sato et al. [20]; ,
Sakamoto et al. within ± 0.3 K except for that at low mass fraction
Sun et al. [21].
of wTBPC = 0.10. The phase equilibrium temperature at wTBPC = 0.10
is higher than that measured by Sakamoto et al. by about 0.8 K. The
mass fractions w = 0.10, 0.20, 0.35 and 0.50. There are several meth-
phase diagram is qualitatively similar to that of TBAC semiclathrate
ods that can be used to determine the phase equilibrium data
hydrate in which the equilibrium temperature increases with the
of clathrate hydrate, such as isochoric method, differential scan-
increase of mass fraction of TBPC up to about wTBPC = 0.35 and then
ning calorimetry (DSC) and differential thermal analysis (DTA).
decreases. As reported by Sakamoto et al. [22], the congruent melt-
The isochoric method can afford a higher pressure than DSC and
ing point is at wTBPC = 0.36 and reaches the highest equilibrium
DTA, which allows for wider pressure range for the experiments.
temperature of 283.3 K.
Therefore, we adopted this method in the experiments. Shown in
The above results measured in the current study show that TBAC
Figs. 2 and 3 are the measuring results, where T is the phase equi-
and TBPC semiclathrate hydrates forming at atmospheric pressure
librium temperature of semiclathrate hydrates and w is the mass
with equilibrium temperature above 273.0 K are the promising
fraction of aqueous solution. Meanwhile, the measuring results are
media for cold storage and transport. Meanwhile, the dissociation
summarized in Table 2.
enthalpy of TBAC semiclathrate hydrate (about 169.2 kJ kg−1 ) [21]
Fig. 2 shows the comparison between the phase equilibrium
is slightly smaller than that of TBPC semiclathrate hydrate (about
data of TBAC semiclathrate hydrate measured in the current study
194.0 kJ kg−1 ) [22], but TBAC semiclathrate hydrate shows a rela-
and those reported in literature [18–21]. As shown in the fig-
tively higher equilibrium temperature.
ure, the equilibrium temperatures measured in the current study
The similar measurements of the phase equilibrium data of
are consistently lower than those in literature by about 0.7–2.1 K
CO2 + TBAC and CO2 + TBPC double hydrates were performed at dif-
except those by Sun et al. [21]. The equilibrium temperatures at
ferent mass fractions at w = 0.05, 0.10, 0.20, 0.35 and 0.50. The
wTBAC = 0.10 and wTBAC = 0.20 measured in the current study are
results are presented in the form of p–T diagrams in Figs. 4 and 5,
higher than those measured by Sun et al. by about 0.8 and 0.2 K,
where p and T are pressure and temperature, respectively. In addi-
respectively, but lower by about 1.2 K at wTBAC = 0.35. The equi-
tion, the experimental results are listed in Tables 3 and 4 as well.
librium temperature increases with the increase of mass fraction
when the mass fraction of TBAC is smaller than 0.35. As reported
in literature [20,21], the equilibrium temperature at wTBAC = 0.35 is
4.5
284 4.0

283 3.5
3.0
282
2.5
p/MPa

281
2.0
280 1.5
T/K

Current study
279 Sakamoto et al. [22] 1.0

278 0.5
0.0
277 278 280 282 284 286 288 290 292 294
276 T/K
0.0 0.1 0.2 0.3 0.4 0.5
wTBPC Fig. 4. Phase diagram of CO2 + TBAC double hydrate. The symbols denote the experi-
mental data at different TBAC mass fractions. 䊉, carbon dioxide hydrate, our previous
study [16]; , w = 0.05, current study; , w = 0.0434, Li et al. [14]; , w = 0.10, cur-
Fig. 3. Phase diagram of TBPC semiclathrate hydrate at atmospheric pressure. 䊉, rent study; , w = 0.0875, Li et al. [14]; , w = 0.20, current study; , w = 0.35, current
current study; , Sakamoto et al. [22]. study; ♦, w = 0.3401, Makino et al. [15]; , w = 0.50, current study.
 N. Ye, P. Zhang / Fluid Phase Equilibria 361 (2014) 208–214 211

Table 4
4.0 Equilibrium data for CO2 + TBPC double hydrate.a

3.5 W T (K) p (MPa)

0.05 285.53 3.9713

3.0 285.14 3.4796
284.58 2.9898
2.5
p/MPa

283.91 2.5142
282.91 1.9479
2.0
281.79 1.4036
280.64 1.0344
1.5
279.04 0.6719
0.10 288.24 3.9637
1.0
287.88 3.5171
0.5 287.37 3.0087
286.64 2.4217
278 280 282 284 286 288 290 292 285.68 1.9139
284.86 1.5124
T/K 283.79 1.0735
282.20 0.6984
Fig. 5. Phase diagram of CO2 + TBPC double hydrate. The symbols denote the experi- 0.20 290.39 3.9675
mental data at different TBPC mass fractions. 䊉, carbon dioxide hydrate, our previous 290.13 3.4901
study [16]; , w = 0.05, current study; , w = 0.10, current study; , w = 0.20, current 289.75 3.0678
study; , w = 0.35, current study; , w = 0.50, current study. 289.16 2.6161
288.47 2.0953
287.46 1.5781
Fig. 4 shows the phase equilibrium data of CO2 + TBAC double 286.43 1.1103
285.05 0.7097
hydrate measured in the current study. In addition, a number of
0.35 290.85 3.9864
experimental results presented by Li et al. [14] and Makino et al. 290.45 3.4072
[15] are also shown in the figure. It is observed that the equilib- 289.88 2.9671
rium temperatures measured in the current study are consistently 289.45 2.5028
lower than those of Li et al. and Makino et al. by about 0.3–2.3 K. The 288.70 2.0364
287.84 1.5679
equilibrium data of Li et al. at w = 0.0434 above p = 2.0 MPa is quite 286.77 1.1224
285.22 0.6848
0.50 289.66 3.9600
289.11 3.2811
Table 3
288.17 2.5859
Equilibrium data for CO2 + TBAC double hydrate.a
286.97 1.7963
W T (K) p (MPa) 285.95 1.2404
284.55 0.6606
0.05 285.27 3.9713
a
284.90 3.5145 Standard uncertainties u in the isochoric experiments are u(w) = 0.00003,
284.61 3.1597 u(T) = 0.1 K, and u(p) = 0.015 MPa.
283.99 2.6500
283.34 2.1631
282.36 1.6723 close to our data at w = 0.05. However, the discrepancy of equilib-
281.10 1.1740 rium temperature increases with the decrease of pressure. There
279.42 0.7097 are discrepancies of equilibrium temperatures between our data at
0.10 287.95 3.9713 w = 0.10 and 0.35 and those of Li et al. at w = 0.0875 and Makino
287.61 3.5410
287.24 3.1446
et al. at w = 0.3401.
286.63 2.5827 Comparing with the phase equilibrium data of CO2 hydrate
286.03 2.1518 in our previous study [16], it is clear that adding even a small
285.21 1.6912 amount of TBAC is able to decrease the equilibrium pressure of CO2
284.42 1.2344
hydrate. For example, the equilibrium temperature increases from
283.24 0.7323
0.20 290.05 3.9298 about 279.0 K for CO2 hydrate to about 284.0 K for TBAC double
289.92 3.4881 hydrate at 2.5 MPa, and the equilibrium pressure decreases from
289.64 3.0577 about 4.0 MPa for CO2 hydrate to about 2.0 MPa for TBAC dou-
289.25 2.5217 ble hydrate at 283.0 K for CO2 + TBAC double hydrate at w = 0.05.
288.86 1.9705
It is shown that CO2 + TBAC double hydrate is more stable than
288.23 1.4949
287.53 1.0419 CO2 hydrate. In addition, the difference between equilibrium tem-
286.57 0.6266 perature of CO2 hydrate and CO2 + TBAC double hydrate at a
0.35 291.18 4.0128 specified pressure increases when the mass fraction of TBAC in
290.91 3.2050
aqueous solution increases from w = 0.05 to 0.35. At w = 0.35, the
290.40 2.4311
289.70 1.6912 equilibrium temperature of CO2 + TBAC double hydrate is higher
289.27 1.2637 than that of CO2 hydrate by about 11.5 K at 2.5 MPa. However,
288.47 0.7965 the equilibrium temperatures of double hydrate at w = 0.50 are
0.50 290.15 4.0355 slightly lower than those at w = 0.35 and almost overlap the data at
289.66 3.3182
w = 0.20. When the mass fraction exceeds w = 0.35, the stability of
289.25 2.6198
288.67 1.9630 CO2 + TBAC double hydrate decreases compared to that at w = 0.35,
287.83 1.2420 which is similar to that of TBAC hydrate forming at atmospheric
286.82 0.6321 pressure.
a
Standard uncertainties u in the isochoric experiments are u(w) = 0.00003, However, there is almost no hydrate equilibrium data in the lit-
u(T) = 0.1 K, and u(p) = 0.015 MPa. erature for CO2 + TBPC double hydrate. As presented in Fig. 5, the
212 N. Ye, P. Zhang / Fluid Phase Equilibria 361 (2014) 208–214

4.5 w = 0.20 because of lower equilibrium temperature of CO2 + TBPC

double hydrate forming at w = 0.50 than that at w = 0.20, which is
4.0
different from that of CO2 + TBAC double hydrate. The equilibrium
3.5 temperature of TBPC semiclathrate hydrate forming at atmospheric
pressure is consistently lower than that of TBAC semiclathrate
3.0
hydrate at mass fraction from w = 0.05 to 0.50; but in the presence
2.5 of CO2 , this behavior is partially changed. As shown in Fig. 6, the
p/MPa

equilibrium temperature of CO2 + TBPC double hydrate is even close

2.0
to that of CO2 + TBAC double hydrate at high pressure at w = 0.05,
1.5 0.10 and 0.20. At all mass fractions adopted in the current study, the
equilibrium temperature of CO2 + TBAC double hydrate is higher
1.0
than that of CO2 + TBPC double hydrate in lower pressure range.
0.5 This fact indicates that CO2 + TBAC double hydrate forming in lower
pressure range at w = 0.05, 0.10 0.20, 0.35 and 0.50, might have
278 280 282 284 286 288 290 292
advantage over CO2 + TBPC double hydrate in CO2 gas storage and
T/K separation.
In the present study, TBAC and TBPC aqueous solutions with dif-
Fig. 6. Phase diagrams of CO2 + TBAC and CO2 + TBPC double hydrates at w = 0.05 ferent mass fractions at w = 0.05, 0.10, 0.20, 0.35 and 0.50 were all
(,), 0.10 (䊉,) and 0.20 (,). The solid symbols denote the experimental data adopted to form hydrate with and without CO2 for visual observa-
of CO2 + TBAC hydrate and the open symbols denote the experimental data of
CO2 + TBPC hydrate.
tion. In addition, the subcooling for hydration was set in the range
of 4.0 to 6.0 K. When the first crystal was observed by the CCD cam-
era, the recording began and the time was set as 0 s, which was
taken for the starting time of hydration process. As shown in Fig. 7,
advantage in stability of CO2 + TBPC double hydrate in comparison some needle-like hydrate crystals with large length–width ratios
with CO2 hydrate is obvious because the equilibrium tempera- appear in TBAC aqueous solution at w = 0.10, Tsub = 5.1 K and
ture at a specified pressure is higher than that of CO2 hydrate. The atmospheric pressure (Fig. 7a, t = 62 s). Then these hydrate crys-
equilibrium temperature at a specified pressure increases with the tals grow into a regular columnar shape and are accumulated by
increase of mass fraction and reaches the peak at w = 0.35. Then, newly-born crystals (Fig. 7b, t = 1573 s) and the transmittance of
the equilibrium temperature decreases at w = 0.50. The variation of the crystals is high (Fig. 7c, t = 3806 s). The morphology of TBAC
equilibrium temperature of CO2 + TBPC double hydrate at w = 0.05, semiclathrate hydrate crystal presented in Fig. 7 is similar to that
0.10, 0.20, 0.35 and 0.50 is similar to that of CO2 + TBAC double of type A TBAB semiclathrate hydrate forming at atmospheric
hydrate. However, CO2 + TBPC double hydrate forming at w = 0.50 pressure as reported in our previous study [16]. Furthermore,
shows comparatively low stability compared to that forming at no changes are found in morphologies of TBAC semiclathrate

Fig. 7. Sequential photos of TBAC semiclathrate hydrate crystal growth at w = 0.10, Tsub = 5.1 K and atmospheric pressure.

Fig. 8. Sequential photos of CO2 + TBAC double hydrate crystal growth at w = 0.10, Tsub = 4.6 K and p = 3.1446 MPa.
 N. Ye, P. Zhang / Fluid Phase Equilibria 361 (2014) 208–214
Fig. 9. Sequential photos of TBPC semiclathrate hydrate crystal growth at w = 0.10, Tsub
hydrate crystals forming at atmospheric pressure at other mass
fractions.
Fig. 8 shows a sequence of photos of CO2 + TBAC double hydrate
crystals forming in aqueous solution at w = 0.10, Tsub = 4.6 K
and p = 3.1446 MPa. Initially, hydrate crystals with two quite differ-
ent morphologies are observed, which are displayed a needle-like
shape and hexagonal plate shape, respectively (Fig. 8a, t = 87 s). The
needle-like shape is similar to that of TBAC semiclathrate hydrate
crystals shown in Fig. 7a and the other is similar to that of TBPB
semiclathrate hydrate crystals forming at atmospheric pressure
presented in our previous study [17], but the transmittance is
much lower than that of TBPB semiclathrate hydrate crystals. How-
ever, only a short time later at t = 579 s, as shown in Fig. 8b, many
CO2 + TBAC double hydrate crystals with columnar shape appear
and no plate-shaped crystals are observed anymore. This behav-
ior is similar to that of CO2 + TBPB double hydrate [17], but the
newly-born needle-like crystals are always accompanied with the
formation of the crystals with columnar shape. Gradually, the size of
the needle-like crystal does not change significantly; but the crys-
tals with columnar shape grow apparently in length direction and
becomes irregular at the end of hydration (Fig. 8c, t = 3914 s). The
similar behavior is also observed at w = 0.05 and w = 0.20. However,
when the mass fractions are w = 0.35 and w = 0.50, only needle-like
CO2 + TBAC double hydrate crystals appear and the growth pro-
cess is similar to that of TBAC semiclathrate hydrate crystals shown
in Fig. 7.
Because the morphologies of TBPC hydrate crystals do not
change by the presence of CO2 but change with the mass fraction,
we only present the morphologies of TBPC semiclathrate hydrate
crystals forming at atmospheric pressure for brevity. Fig. 9 shows a
sequence of photos of TBPC semiclathrate hydrate crystals form-
ing at w = 0.10, Tsub = 5.0 K and atmospheric pressure. At
the initial time of hydration (Fig. 9a, t = 35 s), TBPC semiclathrate
hydrate crystals with hexagonal plate shape form. This kind of
crystal shows plate shape with very small thickness and high trans-
mittance, which are similar to those of TBPB semiclathrate hydrate
crystals forming at atmospheric pressure [17]. Then, the size of
crystal increases apparently along with crystal growth and the
hexagonal shape becomes irregular (Fig. 9b, t = 1317 s). Moreover,
when the size of the hexagonal plate crystals increases to a certain
extent, a portion of crystals break into small pieces, but the trans-
mittance is still high (Fig. 9c, t = 2200 s). The morphologies of TBPC
hydrate crystals forming with and without CO2 at w = 0.05 and 0.20
are almost the same as those presented in Fig. 9. But at w = 0.35 and
0.50, TBPC semiclathrate hydrate and CO2 + TBPC double hydrate
crystals show similar morphologies to those of TBAC semiclathrate
hydrate crystals forming at atmospheric pressure, as shown
in Fig. 7.
213
= 5.0 K and atmospheric pressure.
4. Conclusions
The measurements of the phase equilibrium data of TBAC and
TBPC hydrates with and without CO2 at w = 0.05, 0.10, 0.20, 0.35 and
0.50 were experimentally conducted in the present study; in addi-
tion, the morphologies of these hydrates forming with and without
CO2 at subcoolings of 4.0 to 6.0 K were visually observed. The equi-
librium temperatures of TBAC semiclathrate hydrates are higher
than those of TBPC semiclathrate hydrates forming at atmospheric
pressure, but in the presence of CO2 at high pressure, the equilib-
rium temperatures of CO2 + TBPC double hydrates at w = 0.05, 0.10
and 0.20 are close to those of CO2 + TBAC double hydrates.
The morphologies of TBAC hydrate crystals with and without
CO2 are similar at w = 0.35 and 0.50; but they are different at
w = 0.05, 0.10 and 0.20. However, the morphologies of TBPC semi-
clathrate hydrate crystals are similar to those of CO2 + TBPC double
hydrate crystals at all mass fractions in the current study. More-
over, the morphologies of TBPC semiclathrate hydrate crystals at
w = 0.05, 0.10 and 0.20 are different from those at w = 0.35 and 0.50.
Acknowledgments
This research is jointly supported by the National Natural
Science Foundation of China under the Contract No. 51176109
and the NSFC-JSPS cooperative project under the Contract No.
51311140169. This research is also partially supported by the
Specialized Research Fund for the Doctoral of High Education of
China under the Contract No. 20100073110039 and 985 project of
Shanghai Jiao Tong University.
References
[1] E.D. Sloan, C.A. Koh, Clathate Hydrates of Natural Gas, third ed, CRC Press, Boca
Raton, FL, 2008.
[2] E.G. Hammerschmidt, Ind. Eng. Chem. 26 (1934) 851–855.
[3] S.P. Kang, H. Lee, B.-J. Ryu, J. Chem. Thermodyn. 33 (2001) 513–521.
[4] D.L. Fowler, W.V. Loebenstein, D.B. Pall, C.A. Kraus, J. Am. Chem. Soc. 62 (1940)
1140–1142.
[5] D.W. Davidson, in: F. Franks (Ed.), Water—A Comprehensive Treatise, 7, Plenum
Press, New York, NY, 1982, p. 115 (Chapter 3).
[6] I. Tanasawa, S. Takao, Clathrate hydrate slurry of tetra-n-butylammonium bro-
mide as a cold-storage material, in: Proceedings of the Fourth International
Conference on Gas Hydrates, Yokohama, Japan, 2002 May 19–23, pp. 963–967.
[7] M. Darbouret, M. Cournil, J. Herri, Int. J. Refrig. 28 (2005) 663–671.
[8] T.A. Strobel, C.A. Koh, E.D. Sloan, Fluid Phase Equilib. 261 (2007) 382–389.
[9] X.L. Wang, G.J. Chen, L.Y. Yang, L.W. Zhang, Sci. China, Ser. B Chem. 51 (2008)
171–178.
[10] S.S. Fan, S.F. Li, J.Q. Wang, X.M. Lang, Y.H. Wang, Energy Fuels 23 (2009)
4202–4208.
[11] S.F. Li, S.S. Fan, J.Q. Wang, X.M. Lang, D.Q. Liang, J. Nat. Gas Chem. 18 (2009)
15–20.
[12] X.S. Li, H. Zhan, C.G. Xu, Z.Y. Zeng, Q.N. Lv, K.F. Yan, Energy Fuels 26 (2012)
2518–2527.
214 N. Ye, P. Zhang / Fluid Phase Equilibria 361 (2014) 208–214

[13] N. Mayoufi, D. Dalmazzone, A. Delahaye, P. Clain, L. Fournaison, W. Fürst, J. [17] P. Zhang, N. Ye, H. Zhu, X. Xiao, J. Chem. Eng. Data 58 (2013) 1781–1786.
Chem. Eng. Data 56 (2011) 2987–2993. [18] H. Nakayama, Bull. Chem. Soc. Jpn. 60 (1987) 839–843.
[14] S.F. Li, S.S. Fan, J.Q. Wang, X.M. Lang, Y.H. Wang, J. Chem. Eng. Data 55 (2010) [19] L.S. Aladko, Y.A. Dyadin, Mendeleev Commun. (1996) 198–200.
3212–3215. [20] K. Sato, H. Tokutomi, R. Ohmura, Fluid Phase Equilib. 337 (2013) 115–118.
[15] T. Makino, T. Yamamoto, K. Nagata, H. Sakamoto, S. Hashimoto, T. Sugahara, K. [21] Z.G. Sun, C.G. Liu, B. Zhou, L.Z. Xu, J. Chem. Eng. Data 56 (2011) 3416–3418.
Ohgaki, J. Chem. Eng. Data 55 (2010) 839–841. [22] H. Sakamoto, K. Sato, K. Shiraiwa, S. Takeya, M. Nakajima, R. Ohmura, RSC Adv.
[16] N. Ye, P. Zhang, J. Chem. Eng. Data 57 (2012) 1557–1562. 1 (2011) 315–322.