1.

Introduction
Gas hydrates are defined as solid crystalline structures, which are formed by the
hydrogen bonded bond when the gas molecules are surrounded by water molecules
in the form of cages under high temperature and high pressure conditions (E.D.
Sloan,2008; K.Tumba,2011). As a result of low energy consumption, the
formation of hydrate crystals has been identified as a promising technology in the
industrial fields, especially in concentrating aqueous solutions. To develop low cost
industrial processes, a low pressure hydrate medium most be used (Y.Seo,2001;C.
Petticrew,2014).Most previous efforts aimed at finding ways to avoid the
formation by hydrate inhibition’s mechanism is a result of a change in activity of
water due to hydrogen bonding between hydrate inhibitors and water. But the focus
now is on finding ways to promote the formation of hydrate when hydrate
promotion’s mechanism is a result of the active mixed promoter’s formation of and
gas hydrates at moderate conditions of temperature and pressure (Sun,2011;
Eslamimanesh, 2012) .

2.Thermodynamic promoter of clatrate hydrate

A thermodynamic promoter is a component that is involved in activating hydrate
formation process and readily enters the hydrate to reduce the required hydrate
formation pressure and increase the formation rate and/or temperature (T.
Trueba,2011).Hydrate promoters forming hydrate structures (mainly sII), where
the promoter molecules partly enter the fitly sized cavities, have been considered.
Hydrate promoters such as the tetra-n-butyl ammonium halides (TBAB, TBACl,
TBAF etc.) ,organic component (Cyclopentane, cyclohexane ,benzene etc.)and
other component Tetrahydrofuran (THF),where the promoter actively contribute in
the formation of the lattice structure of water molecules
(P.J.Herslund,2013;Zhang,2009).The most used gas hydrate formation promoters
can be divided into two groups: (1) water “soluble”; (2) water “insoluble” ( K.M.
Sabil,2010; G.J. Witkamp,2010). The first group include two families of
substances:(i) do not take part in hydrate cages’s structures (normally form structure
II) such as tetrahydrofuran (THF), 1,4-dioxane and acetone;(ii) take part in the
structures of the hydrate cages such as tetra-n-butylammonium halides (TBAX)
especially, tetra-n-butylammonium bromide (TBAB) which form clathrate hydrates
(T.A. Strobel,2009; C.A. Koh,2009; Y. Kamata,2004). THF and TBAB can be
declared as two popular water “soluble” thermodynamic promoters currently used
(M.M. Mooijer-van den Heuvel,2001).Water “insoluble” organic promoters
contenting hydrocarbons such as cyclopentane, cylohexane, and methyl
cyclohexane (normally form structure II) ( C. Sun,2011; A.A. Khokhar,1998).

3.Experimental
3.1Matrial
Table 1 presents the details of the chemicals, as well as the purities of the
chemicals used in this study.

Compounds Formula Purity Wt% Supplier Phase

Distilled H2O Distilled Own liquid

water &demineralized

R134a CH2FCF3 ≥99 Frisco Gas

Belgium
Benzene C6H6 > 99 liquid

Acetone C3H6O > 99 liquid

Cyclohexane C6H12 > 99 liquid

3.2. Apparatus
Fig. 1 shows a schematic diagram of the experimental cell and the apparatus used in
this study. The cylindrical cell was constructed using glass and can withstand
pressures up to 6 bar (0.6 MPa). The equilibrium cell has an internal diameter of
140 mm and a length of 14.5 cm which results in a volume of approximately 1.5 L.
Carbon steel plates was covered the top and the bottom of cell . To ensure an
isothermal environment ,the cell surrounded by transparence plastic jacket filled
 with water supplied by water bath type Julabo F10-VC. A magnetic stirrer was
placed inside the cylindrical cell and, enabled agitation of the contents during the
experiments. Temperature sensor were used to measure equilibrium temperatures
that calibrated with mercury thermometer at different temperature. The interphase
used was type of (MAX6675 Temp Module Arduino) used to record the data that
is then transmitted to the computer .The pressure in the cell was measured using
digital Pressure Gauge that calibrated with tow Pressure Gauges with different
pressures.

(14)
(7)
(2)

(10) (9) (4)

(13)

(6)
(5)
(3)
(3)

(11)

(15) (1)
(12)

Fig.1 Schematic diagram of the clathrate hydrate system: (1)R134a refrigerant fig

Fig.1 gas cylinder;(2) needle valve;(3) gas compressor;(4) condenser;(5)

accumulator of gas;(6) Experimental cell;(7) magnetics stirrer;(9)digital pressure
gauges;(10) temperature sensor;(11) valve drain;(12) chiller;(13) interface
system;(14) computer;(15)water pump.
3.3 Experimental method
The isochoric system search method (C. Petticrew,2014; Sloan,2008) was used to
undertake hydrate formation data measurements presented in this study. At first, the
cell was washed with distilled water and then washed with acetone to rinse the
equilibrium cell. Washed water and acetone residual was drained . The cell was
evacuated to vacuum pressure for a period of 30 min at a constant temperature of
313.15 K(10 C0) to ensure that there were no traces of impurities. After loading the
200ml of aqueous solution into the cell, once again the compressor was quickly
used to remove the air inside the reactor. A certain amount of R-134a was
introduced into the cell to reach the desired pressure of 0.45 MPa (4.5 bar) . After
cell was pressurized with the gas, the electromotor with a speed of 200 rpm was
turned on. The pressure of cell decreased continuously due to hydrate formation
until reaching the steady state condition. During the experiments, the cell
temperature and pressure were recorded on the laptop computer.

4. Results and Discussion

Clathrate hydrate formation conditions for R-134a + water systems compared with
data from literature (Akiya,1999). The water soluble/insoluble promoter (acetone,
cyclohexane and benzene) is recommended to be added in the R-134a+ water
system, which can shift the equilibrium phase boundary closer to ambient
conditions. Table. 2 and figure.2 show the use of different concentrations of
acetone (soluble in water) in the system led to lower pressure to ambient conditions
compared with data from literature (Y. Saito,1996; T. Maekawa,2011).Acetone
can conceder no effect on structure of water cage (A. Eslimimanesh,2012).Table. 3
and figure.3 show the use of different concentrations of cyclohexane (CH)
(insoluble in water) in the system led to lower pressure to ambient conditions
compared with data from literature (D.L.Zhong,2016;X. Wang,2014). Table.4 and
figure.4 show the use of different concentrations of benzene (insoluble in water) in
the system led to lower pressure to ambient conditions compared with data from
literature (P.J.Herslund,2013;X. Wang,2014).All previous components (R134a,
aceton, cyclohexane and benzene) produce hydrates with a structure II
(P.J.Herslund,2013; A.H. Mohammadi,2012; Yu-Rui Wang,2016; Ngema,2016).
 4.5

3.5
P/bar

3
0%

2.5 2.50%
5%
2 7.50%
10%
1.5
4
277 5278 6
279 7
280 8
281 9
282 10
283
T/K

Figure.2 Experimental data of the equilibrium lines in the ternary system (H2O-
R134a-acetone) at different volume percentage of acetone.
R134a+ R134a+ R134a+ R134a+ R134a+
100%water+ 97.5%water+ 95%water+ 92.5%water+ 90%water+
0%aceton 2.5%aceton 5%aceton 7.5%aceton 10%aceton
T P T P T P T P T P
10 4.5 10 4.5 10 4.5 10 4.5 10 4.5
8.75 4.12 7.35 3.71 9 3.75 8.7 3.78 9.55 4.2
7.85 3.82 6.5 3.5 8.45 3.7 7.7 3.2 9.2 3.89
6.75 3.52 5.65 3.34 8.1 3.6 7.05 2.92 8.35 3.57
5.25 3.4 5.5 3.2 7.85 3.44 6.8 2.82 7.9 3.43
4.75 3.22 4.6 3.18 7.15 3.38 6.35 2.72 7.4 3.20
4.3 3 6.55 3.26 5.95 2.64 6.85 2.96
4.85 2.88 5.15 2.56 5.75 2.62
4.63 2.8 4.75 2.54 4.85 2.4
4.6 2.78 4.5 2.46 4.75 2.32
4.4 2.42 4.55 2.26
4.25 2.22 4.35 2.10
4.2 1.8
Table. 2 Experimental formation conditions of clathrate hydrates for the (R134a +
water +acetone) system at various volume percentage of acetone
 4.5

3.5
P/bar

2.5 0%
2.50%
2
5%
1.5 7.50%
10%
1
2
275 3
276 4
277 5
278 6
279 7
280 8
281 9
282 10
283
T/K

Figure.3 Experimental data of the equilibrium lines in the ternary system (H 2O-
R134a-cyclohexane) at different volume percentage of cyclohexane.
R134a+ R134a+ R134a+ R134a+ R134a+
100%water+ 97.5%water+ 95%water+ 92.5%water+ 90%water+
0%CH 2.5%CH 5%CH 7.5%CH 10%CH
T P T P T P T P T P
10 4.5 10 4.5 10 4.5 10 4.5 10 4.5
9.5 4.3 9.5 4.2 9.15 4.16 9.5 4.32 9.75 4.22
8.6 4.08 8.85 3.9 8.35 3.98 8.75 4.17 9.35 4
7.85 3.82 8.4 3.66 7.55 3.8 8.35 3.9 9.15 3.73
7 3.56 8.15 3.48 7.05 3.56 8.1 3.58 8.35 3.47
5.25 3.4 7.7 3.36 6.7 3.4 7.75 3.38 7.8 3.28
4.75 3.22 7.15 3.16 6.25 3.18 7.05 3.16 7.35 3.06
6 2.92 5.6 2.96 5.85 2.76 6.35 2.72
5.75 2.88 5.4 2.92 5.5 2.66 6.15 2.66
4.75 2.58 4.75 2.68 4.65 2.32 5.15 2.32
4.35 2.44 4.5 2.14 4.55 2.16
4.25 2.38 4.25 2.1 4.5 2.1
4 2.34 4.15 1.92 4.25 1.88
4 1.84 3.95 1.8
3 1.5
2.75 1.4
Table. 3 Experimental formation conditions of clathrate hydrates for the (R134a +
water +cyclohexane) system at various volume percentage of cyclohexane
 4.5

3.5
P/bar

3 0%
2.50%

2.5 5%
7.50%
10%
2
2 3 4 5 6 7 8 9 10
275 276 277 278 279 280 281 282 283
T/K

Figure.4 Experimental data of the equilibrium lines in the ternary system (H2O-
R134a-benzene) at different volume percentage of acetone.
R134a+ R134a+ R134a+ R134a+ R134a+
100%water+ 97.5%water+ 95%water+ 92.5%water+ 90%water+
0%CH 2.5%CH 5%CH 7.5%CH 10%CH
T P T P T P T P T P
10 4.5 10 4.5 10 4.5 10 4.5 10 4.5
9.5 4.3 9.15 4.12 9.5 3.96 9.45 4.26 9.45 4.06
8.6 4.08 8.2 3.82 9 3.78 8.85 4.16 9.1 3.58
7.85 3.82 7.15 3.5 8.25 3.48 8.25 3.88 8.5 3.18
7 3.56 6.1 3.22 7.25 3.18 7.75 3.46 8.1 2.98
5.25 3.4 5.25 3.12 6.25 3.1 7.25 3.16 7.55 2.8
5 3.25 4.25 3.08 5.85 2.92 7 3.08 7.25 2.68
4.75 3.22 3.85 2.92 5.25 2.8 6.75 2.96 7.1 2.62
3.25 2.78 4.75 2.7 6.15 2.68 6.75 2.46
3 2.76 4.5 2.6 5.85 2.58 6.5 2.36
4.25 2.46 5 2.42 6.15 2.26
4 2.3 4.6 2.3 5.9 2.22
4.15 2.2 5.5 2.1
4 2.2 5.25 2.08
4.75 2.06
Table. 4 Experimental formation conditions of clathrate hydrates for the (R134a +
water +benzene) system at various volume percentage of cyclohexane
5. Conclusion
Experimental hydrate formation data for systems consisting of(water+R134a) in the
presence of Promoters were measured at varying volume percent of the promoter.
The R134a + water + promoter system was measured at volume percent of (2.5, 5,
7.5 and 10)Vol%. The isochoric pressure-search was used for the hydrate formation
measurements.Water soluble/insoluble promoter (acetone, benzene and
cyclohexane) could be used, which when added to the( R134a + water ) system
would shift the equilibrium conditions closer to ambient conditions. The presence
of promoter in the aqueous solutions exhibits a thermodynamic promotion effect on
the refrigerant gas hydrates, in which the equilibrium phase boundary is shifted to
low formation pressure . Optimal conditions can be realized with insoluble
promoters (specially cyclohexane) where the lowest pressure formation (highest
value in pressure drop) is achieved compared with soluble promoter (aceton) used
as shown in the table.5 and figure.5. The insoluble promoter are considered more
industrially effective because the limited solubility makes it easier to separate the
water from the promoter (Cassandra Petticrew ,2014).

Type of Vol.% Start Formation Final Pressure

promoter pressure(bar) pressur(bar) pressur(bar) drop(bar)
No promoter - 4.5 3.4 3.22 1.28
Benzene 2.5% 4.5 3.08 2.76 1.74
5% 4.5 3.7 2.3 2.2
7.5% 4.5 2.7 2.2 2.3
10% 4.5 2.1 2.06 2.44
Cyclohexane 2.5% 4.5 2.88 2.47 2.03
5% 4.5 2.44 2.34 2.16
7.5% 4.5 2.1 1.84 2.66
10% 4.5 1.8 1.4 3.1
Acetone 2.5% 4.5 3.28 3 1.5
5% 4.5 2.88 2.78 1.72
7.5% 4.5 2.54 2.22 2.28
10% 4.5 2.26 1.8 2.7
Table.5 Experimental pressure data of clathrate hydrates for the (R134a + water
+promoter) system at various volume percentage of promoter.
 3.5

3
∆P/bar

2.5

Benzene
1.5 Cyclohexane

Acetone
1
0 2.5 5 7.5 10 12.5
Vol.%

Figure.5 Experimental pressure drop of the equilibrium phase in system (H2O-

R134a-promoter) at different volume percentage of promoters.
6. References
A. Eslimimanesh, A. H. Mohammadi, D. Richon, P. Naidoo, D. Ramjugernath,
Application of gas hydrate formation in separation processes: A review of
experimental studies, J. Chem.Thermodynamics, 46 (2012), 62-71.

A.A. Khokhar, J.S. Gudmundsson, E.D. Sloan, Gas storage in structure H hydrates,
Fluid Phase Equilib. 150 (1998) 383–392.

A.H. Mohammadi, V. Belandria, D. Richon, Use of an artificial neural network

algorithm to predict hydrate dissociation conditions for hydrogen + water and
hydrogen + tetra-n-butyl ammonium bromide + water systems, Chem. Eng. Sci. 65
(2010) 4302–4305.

Akiya, T.; Shimazaki, T.; Oowa, M.; Matsuo, M.; Yoshida, Y. Formation
conditions of clathrates between HFC alternativebrefrigerants and water. Int. J.
Thermophys. 1999, 20, 1753−1763.

C. Sun, W. Li, X. Yang, F. Li, Q. Yuan, L. Mu, J. Chen, B. Liu, G. Chen, Progress
in research of gas hydrate, Chin. J. Chem. Eng. 19 (2011) 151–162.

Cassandra Petticrew. An Investigation into the use of fluorinated Hydrating

agents in the desalination of Industrial wastewater. Chemical Engineering
Thermodynamic Stability Conditions of Clathrate Hydrates for Refrigerant (R134a
or R410a or R507) with MgCl2 Aqueous Solution, University of KwaZulu-
Natal,Durban, South Africa, 2014.

Dong-Liang Zhong, Yu-Rui Wang , Yi-Yu Lu , Wen-Chun Wang , Jia-Le Wang .

Phase equilibrium and kinetics of gas hydrates formed from CO2/H2 in the
presence of tetrahydrofuran and cyclohexane. Journal of Natural Gas Science and
Engineering xxx (2016) 1-7

E.D. Sloan, C.A. Koh, Clathrate Hydrates of Natural Gases, third ed., CRC
Press,Taylor & Francis Group, Boca Raton, 2008.

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. of Chem. Thermodynamics 46, 62-71.
gas hydrates of carbon dioxide in the presence of tetrahydropyran, cyclobutanone,

K. Tumba, P. Reddy, P. Naidoo, D. Ramjugernath, A. Eslamimanesh, A.H.

Mohammadi, D. Richon. Phase Equilibria of Methane and Carbon Dioxide
Clathrate Hydrates in the Presence of Aqueous Solutions of Tributyl methyl
phosphonium Methyl sulfate Ionic Liquid.J. Chem. Eng. Data 56 (2011) 3620-3629.

K.M. Sabil, A.R.C. Duarte, J. Zevenbergen, M.M. Ahmad, S. Yusup, A.A.

Omar,C.J. Peters, Kinetic of formation for single carbon dioxide and mixed carbon
dioxide and tetrahydrofuran hydrates in water and sodium chloride aqueous
solution, Int. J. Greenh. Gas. Con. 4 (2010) 798–805.

K.M. Sabil, G.J. Witkamp, C.J. Peters, Phase equilibria in ternary (carbondioxide +
tetrahydrofuran + water) system in hydrate-forming region: effects of carbon
dioxide concentration and the occurrence of pseudo-retrograde hydrate
phenomenon, J. Chem. Thermodyn. 42 (2010) 8–16.

M. Illbeigi, A. Fazlali, A.H. Mohammadi, Thermodynamic model for the prediction

of equilibrium conditions of clathrate hydrates of methane + water soluble or -
insoluble hydrate former, Ind. Eng. Chem. Res. 50 (2011) 9437–9450.

M.M. Mooijer-van den Heuvel, R. Witteman, C.J. Peters, Phase behaviour of gas
hydrates of carbon dioxide in the presence of tetrahydropyran, cyclobutanone
cyclohexane and methylcyclohexane, Fluid Phase Equilib. 182 (2001) 97–110.

N.I. Papadimitriou, I.N. Tsimpanogiannis, A.K. Stubos, A. Martín, L.J. Rovetto,

L.J. Florusse, C.J. Peters, Experimental and computational investigation of the sII
Binary He-THF hydrate, J. Phys. Chem. B 115 (2011) 1411–1415.

Peter Jørgensen Herslund, Kaj Thomsen, Jens Abildskov,Nicolas von,Solms,

Aurélie Galfré, Pedro Brântuas, Matthias Kwaterski, Jean-Michel Herri,
Thermodynamic Promotion of Carbon Dioxide Clathrate Hydrate Formation by
Tetrahydrofuran, Cyclopentane and their mixtures, International Journal of
Greenhouse Gas Control(2013),7, 397-41

Peterson Thokozani Ngema , Paramespri Naidoo , Amir H. Mohammadi

,Dominique Richon, Deresh Ramjugernath. Thermodynamic stability conditions of
clathrate hydrates for refrigerant (R134a or R410a or R507) with MgCl2 aqueous
solution . Fluid Phase Equilibria 413 (2016) 92-98

Peterson Thokozani Ngema, Cassandra Petticrew, Paramespri Naidoo, Amir H.

Mohammadi, and Deresh Ramjugernath, “Experimental Measurements and
Thermodynamic Modeling of the Dissociation Conditions of Clathrate Hydrates for
(Refrigerant + NaCl + Water) Systems,” Journal of Chemical & Engineering Data,
vol. 59, no. 2, pp. 466–475, 2014

Sun, C., Li, W., Yang, X., Li, F., Yuan, Q., Mu, L., Chen, J., Liu, B., Chen, G.,
2011. Progress in Research of Gas Hydrate, Chinese J. of Chemical Engineering
19(1), 151-162.

T. Maekawa, Equilibrium conditions of clathrate hydrates formed from carbon

dioxide and aqueous acetone solutions, Fluid Phase Equilibria, 303 (2011), 76-79.

T. Trueba, L.J. Rovetto, L.J. Florusse, M.C. Kroon, C.J. Peters, Phase equilibrium
measurements of structure II clathrate hydrates of hydrogen with various gas
promoters, Fluid Phase Equilib. 307 (2011) 6–10.

T.A. Strobel, C.A. Koh, E.D. Sloan, Thermodynamic predictions of various

tetrahydrofuran and hydrogen clathrate hydrates, Fluid Phase Equilib. 280 (2009)
61–67.

T.A. Strobel, K.C. Hester, C.A. Koh, A.K. Sum, E.D. Sloan Jr., Properties of the
clathrates of hydrogen and developments in their applicability for hydrogen storage,
Chem. Phys. Lett. 478 (2009) 97–109.

W. Shimada, M. Shiro, H. Kondo, S. Takeya, H. Oyama, T. Ebinuma, H. Narita,

Tetra-n-butylammonium bromide-water (1/38), Acta Crystallogr., Sect. C:Cryst.
Struct. Commun. 61 (2005) o65–o66.

Xiaolin Wang , Mike Dennis ,Liangzhuo Hou. Clathrate hydrate technology for
cold storage in air conditioning systems . Renewable and Sustainable Energy
Reviews 36 (2014) 34–51

Y. Kamata, H. Oyama, W. Shimada, T. Ebinuma, S. Takeya, T. Uchida, J. Nagao,

H. Narita, Gas separation method using tetra-n-butyl ammonium bromide semi-
clathrate hydrate, Jpn. J. Appl. Phys. Part 1: Regular Papers and Short Notes and
Review Papers 43 (2004) 362–365.

Y. Saito, T. Kawasaki, T. Okui, T. Kondo, R. Hiraoka, Methane storage in hydrate

phase with water soluble guests, Proceedings of the 2nd International Conference
on Natural Gas Hydrates,(1996), 459-465.

Y. Seo, H. Lee, A New Hydrate-Based Recovery Process for Removing

Chlorinated Hydrocarbons from Aqueous Solutions.J. Environmental . Sci. Technol.
35 (2001) 3386-3390.

Zhang, J. S., Lee, J. W., 2009a. Equilibrium of Hydrogen + Cyclopentane and

CarbonDioxide + Cyclopentane Binary Hydrates, J. Chem. Eng. Data 54, 659-661