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Ind. Eng. Chem. Res.

2005, 44, 7373-7379 7373

NMR and Viscosity Investigation of Clathrate Hydrate Formation
and Dissociation
Shuqiang Gao,† Walter G. Chapman,*,† and Waylon House*,‡
Chemical Engineering Department, Rice University, Houston, Texas 77251, and Petroleum Engineering
Department, Texas Tech University, Lubbock, Texas 79406

To better understand clathrate hydrate mechanisms, nuclear magnetic resonance (NMR) and
viscosity measurements were employed to investigate tetrahydrofuran (THF) hydrate formation
and dissociation processes. In NMR experiments, the proton spin lattice relaxation time (T1) of
THF in deuterium oxide (D2O) was measured as the sample was cooled from room temperature
down to the hydrate formation region. The D2O structural change around THF during this process
was examined by monitoring the rotational activation energy of THF, which can be obtained
from the slope of ln(1/T1) vs 1/T. No evidence of hydrate precursor formation in the hydrate
region was found. T1 measurements of THF under constant subcooling temperature indicate
that THF hydration shells do not undergo much structural rearrangement during induction.
The T1 of THF was also measured as the sample was warmed back to room temperature after
hydrate dissociation. T1 values of THF after hydrate dissociation were consistently smaller than
those before hydrate formation and never returned to original values. It was proposed that this
difference in T1 after hydrate dissociation indicates that the THF-D2O solution is more
microscopically homogeneous than before hydrate formation. In viscosity experiments, a
Champion Technologies hydrate rocking cell (CTHRC) was used to probe the residual viscosity
phenomenon after Green Canyon (GC) gas hydrate as well as THF hydrate dissociation. The
residual viscosity reported in the literature was observed after GC hydrate dissociation but not
after THF hydrate dissociation. Because GC hydrate behavior involves significant amounts of
gas mass transfer while THF hydrate does not, one might conclude that the residual viscosity
observed after GC hydrate dissociation was likely caused by the supersaturated gas concentration
and its general effect on solvent viscosity, not necessarily by a clathrate water structure lingering
from the solid.

1. Introduction ate experimental techniques capable of probing dynamic
structural information on the molecular level. The
Gas hydrates, also known as clathrate hydrates, are actual formation and dissociation mechanisms have
nonstoichiometric crystalline compounds composed of important impacts on all hydrate applications. Clarifi-
cooperative hydrogen-bonded water molecules forming cation of the formation mechanism is especially impor-
nanoscale cage-like structures, which accommodate tant for designing kinetic inhibitors or antiagglomerant
smaller guest molecules in nearly spherical cavities. hydrate inhibitors that are expected to intervene with
Depending on the size and the composition of the guest the hydrate formation process on the molecular scale.
molecules, gas hydrates usually form in at least three
types of crystal structures, I, II, and H.1 It has been Current hypotheses1 about hydrate formation and
widely recognized that gas hydrates are significant dissociation involve hydrate precursor and postcursor
factors in flow assurance,2 global warming,3 and seafloor structures. The hypothesis states that, prior to hydrate
stability4 and are a potential energy supply.5 Gas formation, water molecules form individual clathrate
hydrates have also been proposed for use in gas separa- cages (hydrate precursors) around the dissolved guest
tion,6 transportation, and storage.7 molecules with one guest molecule inside each cage.
Under favorable conditions, these cages will agglomer-
Since the first discovery that water forms clathrate
hydrate with chloride in 1810 by Sir Humphrey Davy, ate and form solid clathrate hydrate. The hypothesis
about 200 years of research has been devoted to also suggests that, upon melting, the solid hydrate
understanding hydrate phenomenon. This continuous phase dissolves into hydrate cage clusters. Those clus-
effort has well-established the thermodynamic, physical, ters, also known as residual structures or postcursors,
and structural properties of gas hydrates and discovered persist in the liquid phase over a long period of time
a rich collection of hydrate formers. However, clathrate provided the temperature stays within certain limits.8
hydrate formation and decomposition mechanisms and To understand hydrate formation and dissociation
kinetics are still far from clear due to a lack of appropri- mechanisms, many researchers have studied hydrates
with a particular emphasis on the precursor and post-
cursor hypotheses. Molecular simulations generated
* To whom correspondence should be addressed. W.G.C:
phone, (713) 348-4900; fax, (713) 348-5478; e-mail, wgchap@ voluminous numerical data on the elemental molecular W.H.: phone, (806) 742-3573; fax, (806) 742-3502; detail of hydrophobic hydration processes, which is
e-mail, important for evaluating the precursor hypothesis. A

Rice University. vigorous debate continues on whether hydrophobic

Texas Tech University. solutes structure the water molecules around them. One
10.1021/ie050464b CCC: $30.25 © 2005 American Chemical Society
Published on Web 08/09/2005
7374 Ind. Eng. Chem. Res., Vol. 44, No. 19, 2005

view argues that nonpolar solutes enhance the order of
the hydrogen-bonding network and create structured
hydration shells around them.9-20 On the other hand,
some simulation results showed no indication of en-
hanced structure around hydrophobic solutes.21,22 Even
though computer simulation studies have reached con-
flicting conclusions on whether nonpolar solutes struc-
ture water network around them, they all seem to agree
that long-lived clathrate cages in solution do not exist.
The orientation of hydrogen bonds in the hydration shell
is qualitatively the same as in hydrate clathrate cages,
but the organization of the hydrogen bonds is less
ordered and the number of water molecules involved in
each hydration shell is also different from that in a
clathrate hydrate cage. Experimental work has also
been carried out to probe the water structures around
dissolved nonpolar solutes. Data seem to agree with
those from computer simulation; that is, only loosely
organized hydration cages form around hydrophobic
Figure 1. Schematic of the Champion Technologies hydrate
solutes, with no evidence of regular clathrate cages in rocking cell apparatus.
The fact that no regular clathrate cages have been dissociation, it is very likely there is still a large amount
experimentally confirmed in the water phase before of methane dissolved in water solution due to mass
hydrate formation indicates that the actual hydrate transfer rate limitations. Since dissolved methane struc-
formation process may be much more complicated than tures the hydrogen-bonding network in water,32 water
the hypothesis suggests. Studies of molecular hydrate supersaturated with methane will have a higher viscos-
formation mechanisms present great experimental chal- ity than water simply saturated with methane under
lenges due to the low equilibrium concentrations of the same pressure and temperature. Therefore, it is not
gases in water and the high pressures required. Experi- clear whether the observed residual viscosity is caused
ments usually require specially designed sample cells by remnant clathrate structures or an excess amount
and high sensitivity instruments capable of providing of dissolved methane.
structural information on a molecular scale. To eliminate the complication of mass transfer phe-
NMR T1 measurement has been shown to be a nomenon on the experimental results mentioned above
powerful technique in studying microdynamic behavior and obtain a better understanding of the residual
of liquids28 and providing local molecular-level struc- hydrate structure hypothesis, in this work we chose to
tural information surrounding the NMR responding study the possibility of residual viscosity after THF
guest molecules. THF and water form structure II hydrate dissociation. THF is miscible with water at the
hydrate at ∼4.5 °C under ambient pressure. It is a good concentration of solid THF hydrate;33,34 thus, experi-
model system to study clathrate hydrate mechanisms ments can be performed at constant concentration
because its formation conditions are mild and THF is before, during, and after hydrate formation. Stangret
miscible with water at the conditions of interest. In this and Gampe35 recently demonstrated that the hydropho-
work, proton T1 of THF in D2O was measured as the bic hydration of THF definitely dominates the hydro-
sample was cooled from room temperature to hydrate philic one at low THF concentrations. This is the case
formation conditions. This allowed us to monitor the at hydrate composition THF:H2O ) 1:17 (molar), so
structural change of the hydration shells around THF water-THF hydrogen bonds are not very important for
molecules as a function of temperature and provided an the fluid structure of dilute solutions. Therefore, in
opportunity to examine whether hydrate precursors terms of water structure change, THF is not far from
form under hydrate conditions. other nonpolar solutes.
The residual structure dissociation hypothesis is not Viscosity of the sample was monitored before hydrate
as widely studied as the hydrate precursor hypothesis. formation and after dissociation using a Champion
It has been observed that re-formation of gas hydrates Technologies hydrate rocking cell (CTHRC) (Figure 1)
from this “hydrate melt” requires less subcooling and to detect the reported residual viscosity phenomenon.30
less induction time. This phenomenon is called the Since THF concentration in water is constant, if the
memory effect. Vysniauskas and Bishnoi29 proposed that residual viscosity phenomenon is observed, it would be
it is the existence of residual clathrate structure in a strong demonstration of the existence of residual
water after hydrate dissociation that is responsible for clathrate hydrate structures, i.e., postcursors.
the memory effect. Fleyfel et al.36 combined macroscopic hydrate experi-
More recently, Sloan et al.30 discovered that the ments (visual rocking cell) with microscopic hydrate
viscosity of water after methane hydrate dissociation experiments (NMR) to investigate clathrate residual
is initially higher than that before hydrate formation structure at the point where hydrate particles become
under the same pressure and temperature. The viscosity invisible. They found that some clathrate cages might
returns to normal only after a long period of time. This still exist in solution after hydrates visually disappear.
macroscopic residual viscosity phenomenon is argued In this work, to investigate the molecular evidence of
as evidence of residual structure, i.e., clathrate ag- residual structure for THF hydrate, we measured T1
gregates remaining in water after gas molecules are values of THF as a function of temperature after THF
released.31 However, it is well-known that the diffusion hydrate dissociation in the NMR experiment mentioned
rate of methane in water is very small. After hydrate earlier. Results were compared with that before hydrate
Ind. Eng. Chem. Res., Vol. 44, No. 19, 2005 7375

liner was used to contain the deoxygenated THF:D2O
) 1:17 (molar ratio) mixture. A LUXTRON fluoroptic
thermometer was mounted into the glass container
through the cap to monitor system temperature. Its
output reading resolution is 0.1 °C.
Since trace amounts of oxygen may alter the T1 of
THF significantly, we deoxygenated pure D2O and THF
liquids separately in Teflon containers by periodically
flushing the gas above the liquid phase with pure
nitrogen gas while periodically shaking the sample
containers to accelerate the diffusion of oxygen from the
liquid samples. After flushing six or seven times over
Figure 2. Schematic of the NMR experimental setup. about 12 h, THF and D2O were mixed on the molar basis
of 1:17. All these processes were operated within a
formation to detect any difference caused by the history closed glovebox with nitrogen environment. After al-
of hydrate formation. lowing the sample to stabilize for half a day, we put the
sample into the NMR probe for T1 measurements. (The
2. Experimental Section success of deoxygenation was demonstrated by that fact
that, after deoxygenation, T1 increased about 2 s
2.1. NMR Microscopic Measurements. 2.1.1. Theo- compared to the sample without deoxygenation). T1
retical Background. Spin lattice relaxation mecha- values were measured using the inversion recovery
nisms for THF are composed of two parts, intermolecu- technique. All samples’ 90° and 180° pulses were
lar dipole-dipole and intramolecular dipole-dipole calibrated before every measurement. VNMR software,
interactions. When the THF to D2O molar ratio is 1:17 given inputs of possible minimum and maximum T1
(the same composition as in THF hydrate), most of the values, automatically generates standard 180°-τ-90°
THF molecules are completely surrounded by D2O pulse sequences with various values of τ. It took 4-6
hydration shells, and intra-dipole-dipole is the main min to take a T1 data point.
spin relaxation mechanism. Orientational structures of
The sample was cooled from room temperature (∼25
D2Os in hydration shells have direct impact on the
rotational motion of enclosed THF molecules. On the °C) to subzero temperatures with an average cooling
basis of NMR theory,37 T1 is inversely proportional to rate of ∼0.5 C°/h until hydrate formation occurred.
the rotational correlation time τc. τc is usually believed Hydrate formation was indicated by a jump in the
to follow the Arrhenius behavior sample temperature. Oyama et al.38 proposed that,
during the induction period, water around dissolved CO2
1 takes time to rearrange into individual clathrate cages
∝ τc (1) before hydrate formation. To test this hypothesis, we
T1 measured T1 as a function of time while the temperature
was kept constant in subcooling state. If the hydration
τc ) τoeEa/RT (2) shell structures around THF experience rearrange-
ments, the T1 of THF would vary. After hydrate forma-
where τo is a constant preexponential factor; Ea is the tion, temperature was raised to completely dissociate
rotational activation energy, a manifestation of hydra- the hydrate. T1 was also measured as the sample was
tion cage structure around THF and not sensitive to heated back to about 25 °C.
temperature; T is the temperature in kelvin; and R is 2.2. Viscosity Macroscopic Measurements. The
the molar gas constant. Combining eqs 1 and 2 yields viscosity experiments for the THF (99+%, Aldrich)-
eq 3. deionized (DI) water system were performed on a state-
of-the-art CTHRC, which is an apparatus with high-
d ln(1/T1) Ea pressure sapphire tubes placed on a rack. It is capable
) (3)
d(1/T) R of handling pressures up to 5000 psi. The rack is
immersed in a temperature-controlled thermal bath and
The slope of ln(1/T1) versus (1/T) gives the rotational it rocks (45° from horizontal position through a com-
activation energy Ea. Therefore, by tracking the changes puter-controlled step motor. As the rack rocks, a ball
in the slope of ln(1/T1) versus (1/T), we can measure Ea inside the tube rolls from one end to the other, and each
and evaluate the changes in hydration shell structure tube functions such as a rolling ball viscometer. The
around dissolved THF molecules as a function of tem- motion of the ball is detected through two sensors
perature. mounted on both ends of each tube. The time that the
2.1.2. Experimental Details. T1 measurements of ball takes to travel from one sensor to the other is
THF (Aldrich, 99+%) in D2O (Cambridge Isotope Labo- recorded as an indication of the fluid viscosity inside
ratories, D 99.9%) at various temperatures were per- the tube. Changes of the fluid viscosity in the tubes can
formed on an 85-MHz Oxford horizontal 31 cm wide bore be sensitively detected by measuring the ball travel
NMR with imaging capability, using a LITZ RF Volume speeds. Hydrate formation is indicated by an increase
Coil (with 14 cm internal diameter) from Doty Scientific, in fluid apparent viscosity while system temperature
Inc. (Figure 2). Data were acquired and processed using and pressure were kept constant. The ball was eventu-
Varian VNMR software and INOVA hardware systems. ally immobilized by the hydrate blockage. Hydrate onset
An Air-Jet temperature controller blew dry and cold air can also be detected by visual observation of hydrate
to control the sample temperature. It is capable of crystal deposit on the tube’s inside wall. Ball travel time,
controlling temperature from -40 to 100 °C with (0.1 temperature, and pressure data are collected every
°C stability. A glass bottle with a cap that has a Teflon minute into a terminal computer using LabView.
7376 Ind. Eng. Chem. Res., Vol. 44, No. 19, 2005

Figure 4. T1 of THF in D2O during induction time at -1.7 °C.
Figure 3. T1 of THF in D2O before hydrate formation and after
hydrate dissociation, plotted as ln(1/T1/s) vs 1/T/K. The activation activation energy reflects local water structure around
energies (Ea) were calculated from the slopes.
THF, the result indicates that THF hydration shells in
the aqueous phase are dissimilar in nature from the
Green Canyon (GC) gas hydrate experiments were
regular clathrate cages in the hydrate phase, even under
first performed on CTHRC to duplicate the residual
hydrate formation conditions. The suggested hydrate
viscosity phenomenon reported in the literature30 in
precursors were not found and the proposed hydrate
order to ensure that the rocking cell we use is sensitive
formation hypothesis1 is not supported.
enough. GC gas is composed of 87.2% (mol) CH4, 7.6%
To compare with the time-dependent results reported
C2H6, 3.1% C3H8, 0.8% n-C4H10, 0.5% i-C4H10, 0.2%
by Oyama et al.,38 we measured T1 as a function of time
n-C5H12, 0.2% i-C5H12, and 0.4% N2. Every tube was first
while the temperature was kept constant under hydrate
charged with 9 mL of DI water. After the system was
conditions. As shown in Figure 4, T1 does not change
purged three times with 50 psi of GC gas, 1000 psi of
much with respect to time during the induction period.
GC gas was introduced into the tubes. The pressure was
This implies that the hydration shells around THF have
kept constant at 1000 psi during the experiment. Once
no dramatic structural change and they do not rear-
charged, the cell temperature was initially raised to 30
range themselves into regular clathrate cages during
°C to eliminate any possible preexisting extra structure
induction time.
in water. The system was then lowered to 20 °C and
equilibrated for ∼2 h to establish a viscosity baseline One interesting feature is that even though the slope
at this temperature. The temperature was then further of ln(1/T1) vs 1/T does not change dramatically as
cooled to 15 °C to initiate hydrate formation. The temperature goes from ∼25 °C to hydrate formation
predicted hydrate equilibrium temperature by CSM- regions, it does show a slight increase at around 8-9
HYD1 is 17.8 °C for this pressure and gas composition. °C. In this experiment, the activation energy changes
To ensure complete hydrate formation, the temperature from 19.97 to 23.83 kJ/mol at ∼8.5 °C. This transition
was lowered to 5 °C before it was raised to dissociate in the slope is reproducible and it is under further
the hydrate. Then the system was slowly warmed back investigation.
to 20 °C until complete hydrate dissociation occurred. After hydrate dissociation, even though the slope is
The system was equilibrated to establish the viscosity similar to that before hydrate formation, there is a
baseline at this temperature again. consistent shift of T1, which never returned to the
Viscosities of the THF-water system were measured original value. This variation of T1 implies a structural
in a similar fashion. DI water and THF were added in change of water molecules around THF due to hydrate
a H2O:THF ) 17:1 molar ratio, the composition in THF formation and dissociation. However, this structural
hydrate. The tubes were then sealed and heated to 30 change is not caused by residual clathrate structure,
°C to eliminate any preexisting extra structure in the because the effect still exists above 25 °C. There are
water. The system temperature was then lowered to possible microscopic heterogeneities40 in fresh THF-
hydrate formation conditions. During this cooling pro- D2O solution, even though THF and D2O are miscible
cess, the system was allowed to equilibrate at 10 and 6 at all concentrations under conditions of interest. Since
°C for about 300 min in order to establish the viscosity THF becomes perfectly distributed as a result of hydrate
baselines at these temperatures. After complete hydrate formation, subsequent dissociation would result in a
formation, the system was warmed to dissociate the more microscopically homogeneous THF-D2O solution.
hydrate. The system was equilibrated again at 10 and Therefore, the T1 shift is probably caused by a more
6 °C to establish the viscosity lines. uniform distribution of THF in D2O after THF hydrate
dissociation than before hydrate formation. It was also
observed that before hydrate formation the THF-D2O
3. Results and Discussion
solution had a slight milky appearance and after
3.1. NMR Results. As shown in Figure 3, the ln(1/ hydrate dissociation the solution became crystal clear.
T1) vs 1/T slope does not change dramatically as the Without external disturbance, the milky appearance can
sample is cooled from room temperature into the last over 2 weeks at room temperature.
hydrate region. This indicates that the hydration cage 3.2. Viscosity Results. In the GC gas hydrate
structure around THF in the hydrate region before the viscosity experiment, shown in Figure 5, the viscosity
phase transition is not very different from that at room baseline after hydrate dissociation is obviously higher
temperature. The slope gives the average rotational than that before hydrate formation at temperature 20
activation energy of 21.18 kJ/mol for THF in water °C and pressure 1000 psi. The residual viscosity phe-
solution, which is very different from that in the solid nomenon reported in the literature30 was successfully
hydrate phase, 4.14 kJ/mol.39 Since the rotational reproduced.
Ind. Eng. Chem. Res., Vol. 44, No. 19, 2005 7377

Figure 5. Residual viscosity phenomenon observed at 20 °C after Green Canyon gas hydrate dissociation. The pressure was kept constant
at 1000 psi.

Figure 6. No residual viscosity is observed at 6 and 10 °C after THF hydrate dissociation.

However, results from THF-water hydrate experi- and it stays constant under all conditions. Since residual
ments (Figure 6) do not demonstrate this residual viscosity was absent after THF hydrate dissociation, the
viscosity effect. Viscosities baselines established at 6 and observed residual viscosity phenomenon in GC hydrate
10 °C before hydrate formation are the same as those experiment was probably caused by supersaturated
after hydrate dissociation. Macroscopic evidence of the hydrocarbons in water after hydrate dissociation, not
residual structure is absent in this experiment. The necessarily by remaining clathrate structure in the
different results from THF and GC experiments may aqueous phase.
be explained as follows. The fact that residual viscosity was not observed after
In GC hydrate experiment, after hydrate dissociation, THF dissociation but an overall structural change
a large amount of hydrocarbons have to get out of the around THF was indicated by NMR results may be
liquid phase because the concentrations of hydrocarbon caused by two reasons. First, strong mixing by the steel
gases in the hydrate phase are much higher than their ball inside the sample tube may have already made
equilibrium concentrations in liquid water under the THF-D2O microscopically homogeneous even before
same condition. The hydrocarbon gases resulting from hydrate formation and destroyed any possible residual
hydrate dissociation can come out of liquid phase by structure as soon as the hydrate melted. Second, even
diffusion or by forming bubbles. Since the diffusion though CTHRC can reproduce the residual viscosity
coefficients of hydrocarbons in water are very small, it phenomenon for the GC hydrate experiment, it may not
is much more efficient for gases to escape as bubbles. be sensitive enough to detect the structural change after
However, from visual observation, few bubbles formed THF hydrate dissociation. In any case, rocking-cell types
during GC hydrate dissociation under constant pres- of apparatus30 may not be appropriate tools to measure
sure. Therefore, gases come out of water mainly by residual structure.
diffusion, which makes this process very time consum-
ing. During the time frame of viscosity measurements, 4. Conclusions
liquid water could be still highly supersaturated with
hydrocarbon gases. This would cause higher than NMR and CTHRC techniques were used to investi-
normal apparent water viscosity.41 THF does not have gate the formation and dissociation mechanisms of THF
the above problem because its concentration in the hydrate. In NMR experiments, T1 of THF in D2O was
liquid phase is the same as that in the hydrate phase measured as the sample was cooled from room temper-
7378 Ind. Eng. Chem. Res., Vol. 44, No. 19, 2005

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