Kinetic Hydrate Inhibitors for Natural

Gas Fields: Rational Design and

Experimental Development
Authors: Rashed M. Al-Eisa, Dr. Mohamed S. Elanany, Dr. Khalid A. Al-Majnouni, Ali A. Al-Jabran,
Hassan A. Al-Ajwad, Dr. Ibrahim A. Abba and Dr. Abdullah R. Al-Malki

ABSTRACT
The formation of gas hydrates is a major nuisance to the oil
and gas industry, causing pipelines to plug, gas flow disrup-
tions and safety issues. This phenomenon occurs in natural gas
when the temperature and pressure of the flowing gas falls be-
low the hydrate equilibrium region, leading to the formation
of ice-like gas hydrates. Chemical inhibitors are commonly
used to mitigate hydrate formation through injection in the
natural gas pipelines system. Kinetic hydrate inhibitors (KHIs),
a type of this chemical inhibitor, have received attention recently
due to their environmental tolerance and low operating cost.
Several KHIs have been developed and used in several gas fields
around the world; however, KHIs for gas fields rich in hydrogen
sulfide (H2S) and carbon dioxide (CO2) that are flowing under
high sub-cooling temperature need to be developed.
In this study, we present a rational design and an experimen-
tal approach to develop novel KHIs for gas fields with high
sub-cooling temperatures, with structure I (sI) gas hydrates
present and with a high concentration of H2S and CO2. The
present methodology consists of carrying out performance test-
ing, computational molecular modeling and physicochemical
characterization of polymeric materials. The performances of
commercial KHIs, ready-made polymers and new synthesized
polymers were evaluated using a rocking cell (RC-5) instrument.
Hydrogen bonding between the polymers and water surrogates
was measured using attenuated total reflectance Fourier trans-
form infrared spectroscopy (ATR-FTIR), and the results revealed
a direct correlation between inhibition performance and hy-
drogen bond strength. Additionally, the presence of an amide
group in the polymeric inhibitors was found to be essential for
delaying hydrate formation, because it disrupts the local or-
ganization of water clusters around guest gas molecules.
Computational molecular modeling using a density functional
theory (DFT) method was also carried out to calculate hydro-
gen bonding interaction energies between polymeric inhibitors
and water, and to link the molecular characteristics to actual
performance. Based on this approach, we were able to develop
a novel class of polymeric materials and KHI formulations that
provides protection against gas hydrates at and beyond sub-
cooling temperature levels of 4 °C and 5.6 °C with simulated
natural gas compositions. These KHIs could effectively prevent
the formation of gas hydrates and maintain pipeline integrity
for various gas fields while greatly lowering total costs of off-
shore gas field production.
INTRODUCTION
Clathrate hydrates are ice-like solids formed in the presence of
water, a hydrate guest molecule, e.g., methane, ethane,
propane or carbon dioxide (CO2), and the right combination of
temperature and pressure1. The crystal structure of hydrate
connects water molecules and the host molecule through hydro-
gen bonding to form a 3D network that enclathrates apolar
guest molecules in cages. The hydrate structure is stabilized by
the presence of a weak van der Waals interaction between the
guest molecules and the water molecules. There are three
known gas hydrate structures, namely, structure I (sI), structure
II (sII) and structure H (sH), Fig. 1. The most abundant hydrate
structures are the two cubic forms, which are hydrate sI and sII.
The third structure, sH, is rarely seen outside the laboratory2.
Hydrate formation is favored at a lower temperature and
higher pressure3. The temperature of the hydrate formation in-
creases with increasing pressure; sometimes hydrates can form
at ambient conditions. In fact, they can form at temperatures
higher than 35 °C if the pressure reaches above 1,000 bar1.
Figure 2 illustrates the typical three-phase thermodynamic dia-
gram of natural gas hydrates. It shows the hydrate zone, hydrate
risk zone and hydrate free zone. Each zone’s characterization
Fig. 1. Structures of the gas hydrates sI, sII and sH, presented along with the cages
used to build the structures and common guest molecules enclathrated into the
hydrates2.

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Fig. 2. Three-phase equilibrium curve for typical natural gas hydrates4.
depends on the stability of the hydrate nuclei. The hydrate
zone is the most interesting and the one of immediate concern
because in this region of the thermodynamic diagram, the hy-
drates are thermodynamically stable and could form instanta-
neously4.
Hydrates are a nuisance to the oil and gas industry because
they deposit on pipe walls and accumulate as large plugs, Fig.
3, blocking pipelines and eventually stopping production. The
process of removing hydrates after their formation in subsea
production/transmission lines can be very time-consuming and
costly, while also posing safety concerns. Not only does hy-
drate formation impede subsea production, but it can also
cause substantial losses to onshore production facilities and
equipment. Prevention of hydrate formation is a must to main-
tain high capacity gas production safely5.
Several methods are used to prevent hydrate formation, in-
cluding dehydration, chemical inhibitors, and pressure and
temperature control. These methods are not suitable for all
process schemes, as in the case of gas production from off-
shore wells. Hydrate inhibition based on chemical inhibitors is
considered to be the most efficient. These chemicals are cate-
gorized as thermodynamic or kinetic inhibitors. Thermodynamic
Fig. 3. Hydrate plug formation in a subsea hydrocarbon pipeline; picture from
Petrobras (Brazil).
inhibitors, such as methanol and monoethylene glycol, are
used to alter the thermodynamic conditions, i.e., pressure and
temperature, at which the hydrates are formed. For thermody-
namic inhibitors to be effective, they have to be injected at up
to 60% of the weight of water, which leads to annual costs of
$500 million for the oil and gas industry to prevent hydrate
formation with treatments like methanol injection. These injec-
tions are also inconvenient and hazardous due to their chemi-
cal toxicity6.
The alternative approach, and the focus of this article,
meets the industry’s requirements for kinetic hydrate inhibi-
tion1-3. This approach can lead to substantial cost savings
because of the small amount of the inhibitor required for injec-
tion — < 1% of the weight of water. It can help to maintain
effective pumping and storage capabilities, and can lead to the
design of smaller production facilities. The kinetic control ap-
proach, using what are known as low dose hydrate inhibitors,
features either kinetic hydrate inhibitors (KHIs), which delay
the nucleation and crystal growth of hydrates, or anti-agglom-
erants (AAs), which do not stop the nucleation, but instead
prevent the agglomeration. In both cases, hydrates can form if
enough time is allowed because the hydrate’s formation re-
mains thermodynamically feasible5.
Two types of KHIs have been developed and commercial-
ized in recent years. The first one is a water-soluble polymeric
material that has a tendency to form hydrogen bonding with
the water, thereby preventing hydrate formation1. Typical ex-
amples of polymeric KHIs are based on homopolymers or
copolymers of cyclic amide (lactam), such as polyvinyl capro-
lactam and polyvinylpyrrolidone, or of other amides, such as
polyethyloxazoline and N-methyl-N-vinylacetamide. The sec-
ond type is a non-polymeric material, such as tetrapentylam-
monium bromide and butoxy-ethanol. Even though the latter
performs poorly as a KHI because of their weak interaction
with the hydrate surface, they are very effective as synergists1.
The field of KHIs is not a new field. The first patent for
KHIs dates back to 1994. The discovery of the first and second
generations of KHIs was purely based on trial and error. This
approach is no longer followed, and a fundamental under-
standing of the inhibition mechanism and polymer properties
is essential to designing the next-generation KHIs. The mecha-
nism of KHI action is believed to be two steps: The disturbing
of a water molecule’s local organization, and the KHI’s strong
adsorption to the hydrate surface6. The KHI adsorbs to the hy-
drate clusters or surfaces, as schematically shown in Fig. 4, to
delay the nucleation or the crystal growth for a period of time,
which must be longer than the residence time of free water in
the mixture. The adsorption occurs through hydrogen bonding
and weak van der Waals interactions. The adsorbed polymer
changes the diffusive-sorptional exchange at the inhibitor-
water interface, which ideally results in decreasing the crystal
growth rate and coagulation. For polymeric KHIs to be effec-
tive, they must be very water soluble, and they should not
hydrolyze to any insoluble compounds in the system. They
SAUDI ARAMCO JOURNAL OF TECHNOLOGY FALL 2015
Fig. 4. Schematic presentation of kinetic hydrate inhibition through the KHI Fig. 5. Synthetic natural gas clathrate three-phase (hydrate-liquid-vapor) equilibrium
polymers’ adsorption to the hydrate surface through the hydrogen bonding line. In blue, the intersection of lines 2 and 3 illustrates the sub-cooling temperature
interaction with the methane hydrate cages. of 10 °C where the natural gas clathrate hydrates are stable.

should have a strong adsorption affinity to the hydrate surface,
and they must be compatible with other added chemicals in
the pipelines, such as corrosion inhibitors6.
Designing new KHIs is necessary today to overcome issues
like specific gas stream compositions, changing production
conditions, compatibility with corrosion inhibitors and espe-
cially the high severity of conditions in natural gas fields,
namely a high concentration of hydrogen sulfide (H2S) and
CO2, and a high sub-cooling temperature. In this article, we
followed an experimental approach to develop next-generation
KHI materials for such high severity conditions. Our approach
began with an evaluation of commercial and new synthesized
KHIs in the rocking cell (RC-5) instrument. We then con-
ducted physical and chemical characterizations of the poly-
mers, using attenuated total reflectance Fourier transform
infrared (ATR-FTIR) spectroscopy, to understand the interac-
tions between the polymers and the water. Finally, we modeled
the interactions between the polymers and water molecules to
develop the structure property relationships needed to create
next-generation KHIs.
formation, the target KHI should work at sub-cooling temper-
atures of 5 °C to 10.5 °C. The sub-cooling temperature is the
difference between the operating temperature and the three-
phase equilibrium temperature at a defined pressure, as illus-
trated by the blue line labeled 2 in Fig. 5.
Figure 6 shows the RC-5 used to test the formation of natu-
ral gas clathrate hydrate from the synthetic gas. The RC-5
consists of five Hastelloy cells capable of operating under high-
pressure (maximum 200 bar) and sour gas conditions. The
Hastelloy cells are immersed in one temperature controlled
bath containing ethylene glycol and water. The RC-5 enables
formation of natural gas clathrate hydrate under simulated op-
erating conditions to test KHI effectiveness. Data acquisition is
completed with software to enable measurement of the pres-
sure and temperature with time for hydrate formation in each
of the Hastelloy cells.

EXPERIMENTAL

Rocking Cell (RC-5)

During winter months, operating conditions are suitable for

hydrate formation, which raises possible safety and opera-
tional concerns. Figure 5 shows the natural gas clathrate three-
phase (hydrate-liquid-vapor) equilibrium line for the synthetic
natural gas, with high concentrations of H2S and CO2, which
was used in this study. This synthetic gas forms sI gas hy-
drates. When operating at temperatures lower and pressures
higher than those of the curving three-phase equilibrium line,
natural gas clathrates are thermodynamically stable. Fig. 6. RC-5 equipment for evaluating polymers as KHI at simulated operating
conditions.
To protect gas pipelines and the wellhead against hydrate
 In a typical run, each of the Hastelloy cells is charged with
10 ml of aqueous polymers (3 wt%) and pressurized with syn-
thetic gas to a range of 142 bar to 147 bar at 21 °C. After the
reactant composition is fixed, the RC-5 temperature is pro-
grammed to change in three stages, Table 1. Each of the tem-
peratures is selected to fall in a stable natural gas clathrate
hydrate region. The three-phase equilibrium point, calculated
with the HYSYS program, was 19 °C at 150 bar. For screening
purposes, the new synthesized polymers were investigated at a
pressure of 70 bar and with similar sub-cooling temperatures
of 4 °C, 5.6 °C and 10.5 °C.
ATR-FTIR Characterization
A Varian 660-IR Spectrometer with a Specac Golden Gate
ATR was used for the ATR-FTIR analysis. Spectra comprised
an average of 128 scans measured from 4,000 cm-1 to 700 cm-1
with a resolution of 4 cm-1. All analyses were performed at
ambient temperature. A 0.1 g dry sample of polymer was ana-
lyzed first in the ATR-FTIR. Then 10 µl of heavy water (D2O)
was added to the polymer sample and the spectra were
recorded. The reason for using D2O instead of ordinary water
is because the latter’s bending peak would obscure the region
of the amide peak in the ATR-FTIR spectra.
Computational Modeling
to the calculated interaction energy, total energy of the KHI
monomer and total energy of water, respectively.
RESULTS AND DISCUSSION
Performance of Commercial KHI and Ready-Made Polymeric
Inhibitors
Figure 7 shows the performance results of PAC-AA1 and
PEOx, along with brine water, i.e., the control, and a commer-
cial KHI. These polymers were chosen for investigation be-
cause they are relatively good kinetic inhibitors of clathrate
hydrates and have high solubility in water; still, both polymers
underperformed compared to the commercial KHI. The PEOx
performed better than the PAC-AA as a KHI, delaying the
hydrate nucleation at a sub-cooling temperature of 4 °C for
nearly 6,000 minutes. After nucleation, however, hydrate
growth was very rapid (see the slope). PAC-AA did not im-
prove on the induction time to nucleation, and a low rate of
hydrate growth was observed, where the curve for PAC-AA
reaches a steady-state after the curve. At a sub-cooling temper-
ature of 12 °C, a large amount of hydrate was formed in the
presence of PAC-AA — even more than in the brine water.
This clearly indicated that at this temperature, PAC-AA pro-
moted formation of natural gas clathrate hydrates. Both PAC-
AA and PEOx have amide groups. In PEOx, the amide group
1 The PAC-AA used was switched from the acid form to the sodium salt form.

Geometry optimizations and energy calculations for water and

the KHI monomer structures polyethyloxazoline (PEOx) and
polyacrylamide-co-acrylic acid (PAC-AA) were performed us-
ing a density functional theory (DFT) based method and the
DMol3 program with the Materials Studio software package
MS 6.1, based on a generalized gradient approximation level
using the Hamprecht, Cohen, Tozer and Handy exchange and
correlation functional7, 8. The double numerical basis set with
polarization functions was used in all calculations carried out
in this study. A water molecule was placed initially at a similar
o
distance (~1.70 A) from the KHI monomer carbonyl groups.
Geometry optimization and energy calculations were carried
out in the vacuum, vac, and in the aqueous media, aq, using a
conductor-like screening model (COSMO)9. The low level of
theory, i.e., semi-empirical method, was sometimes used to re-
fine the initial geometry of a structure before starting higher
level DFT calculations, to ensure a global minimum was
reached. The interaction energy, EInt, is calculated as EInt =
Fig. 7. Performance evaluation of commercial KHIs, including PEOx and PAC-AA.
E(mono-H2O) − [Emono + EH2O], where EInt, Emono and EH2O refers

Stage Start Temp (°C) Average Ramp (°C/min) Sub-cooling (°C/min) Duration (min)

S-1 21 0.1 5 7,000

S-2 14 0.1 7 7,000 to 8,500

S-3 12 0.08 12 8,500 to 11,000

Table 1. Temperature program to form natural gas clathrate hydrate in the RC-5
is part of the polymer chain, whereas in the PAC-AA group,
the amide group is one of the pendant groups of the copoly-
mer, as can be observed in Fig. 8.

Characterization of Hydrogen Bonding Interactions

Hydrogen bonds are an attractive interaction between mole-

cules with electron deficient hydrogen, i.e. hydrogen bond
donors, and molecules with high electron density, i.e., hydro-
gen bond acceptors. The atoms that are usually involved in hy-
drogen bond interactions are N, F and O. In principle, when
the hydrogen bondings (X-H … Y) form, significant charges
are transferred to the proton-acceptor, Y, from the donor, X-H,
resulting in weakening and elongation of the X-H bond. In
consequence, it decreases the X-H vibration frequency com-
pared to the normal bond measured by infrared spectroscopy.
The shift of bond frequency to a lower frequency, or energy, is
called a red shift, and in the opposite case, the shift of bond
frequency to a higher frequency is called a blue shift10. The
shift in frequency is correlated with the strength of the hydro-
gen bonding, and so is the hydrate inhibition. The hydrogen
bonding interactions play an important role in hydrate inhibi-
tion using KHIs. To measure the polymer-hydrate surrogate
molecule, i.e., D2O interactions, ATR-FTIR was employed.
First, the analysis was done for both neat and hydrated
samples of PAC-AA and PEOx. The spectra, Fig. 9a, show five
major ATR-FTIR bands assigned to the polymer of PAC-AA.
The bands are attributed to both the amide group and the
acrylic acid group, so specific interpretation is challenging.
Features consistent with the carbonyl stretching are at 1,662
cm-1 and 1,548 cm-1. The carbonyl band at 1,662 cm-1 red
shifted when the polymer was hydrated, but the band at 1,548 Fig. 9. ATR-FTIR spectra of (a) PAC-AA, and (b) PEOx in dry (red) and hydrated
cm-1 also broadened, so a specific shift could not be measured with D2O states (black) samples.
accurately8. Because of the limitation of the ATR-FTIR spec-
troscopy, the computational modeling had to be used to
investigate the interactions of the PAC-AA with water. The Modeling the Interactions between the KHI Monomers of
ATR-FTIR spectra of PEOx could be more accurately analyzed PEOx, PAC-AA and Water
because PEOx is not a copolymer like PAC-AA. The major
ATR-FTIR band of PEOx is attributed to the amide group at To investigate potential polymers that could be used as KHIs, a
1,620 cm-1. The red shift of the amide group was noticed also simple model of a monomer — containing the corresponding
for PEOx from 1,620 cm-1 to 1,603 cm-1. The intensity of the functional group — was created, and the hydrogen bonding in-
amide peak increased, but the broadness did not change. This teraction energies were calculated, as well as other important
shift indicates the presence of hydrogen bonding between molecular characteristics, i.e., bond length, frequency and
PEOx and D2O. atomic charges.
Figure 10a shows the geometrically optimized ethyl oxazo-
line monomer with the amide functional group, where nitro-
gen is in the backbone of the PEOx polymer. The minimum
energy structure due to the hydrogen bonding interaction be-
tween the ethyl oxazoline monomer and water is shown in Fig.
10b. Similarly, the geometrically optimized acrylamide-co-
acrylic acid monomer is shown in Fig. 10c with the character-
istic amide and carboxylic acid functional groups. Figure 10d
illustrates the hydrogen bonding interaction between water and
Fig. 8. (a) PEOx, and (b) PAC-AA where R is either OH or NH2.
the acrylamide-co-acrylic acid monomer through the carbonyl,

FALL 2015 SAUDI ARAMCO JOURNAL OF TECHNOLOGY


Fig. 10. (a) Geometrically optimized structures for ethyl oxazoline monomer, (b)
ethyl oxazoline with H2O, (c) acrylamide-co-acrylic acid monomer, and (d)
acrylamide-co-acrylic acid with H2O. Hydrogen, carbon, nitrogen and oxygen
appear in white, gray, blue and red color, respectively.
C=O, in the amide functional group. Table 2 is a summarization
of the calculation results, including geometrical and atomic
parameters.
To calculate hydrogen bonding interaction energy, a water
molecule, H2O, was optimized in the same way as the KHI
monomers. Geometrical parameters, namely H-O and ∠H-O-
H, agreed well with the experimental data. The total energy,
EH2O, was calculated in vacuum and aqueous phases. Results
are indicated in Table 2, where 1 Ha = 2625.5 kJ/mol.
Table 2 also indicates that the calculated hydrogen bonding
interaction energy for the PEOx monomer, -11.82 kJ/mol, is
greater than that for the PAC-AA monomer, -10.14 kJ/mol.
Therefore, a better hydrate inhibition is expected by PEOx.
This better PEOx performance is also reflected in other geo-
metrical and atomic parameters. In more detail, the hydrogen
bond distance, H-O-H…O=C, for the optimized PEOx…H2O
PEOx
Parameter
vac
qO (e) -0.484
C=O (Å) 1.238
oC=O (amide) cm-1 1664
H-O-H…O=C (Å) – 1.938
Total energy (Ha) -366.592998
EInter (kJ/mol)
Table 2. Calculated structural and atomic parameters of PEOx and PAC-AA monomers in the vacuum and aqueous phases as well as their hydrogen bonding interaction
energies
structures of 1.938 Å, Fig. 10b and Table 2, is slightly shorter
and stronger than that for the PAC-AA...H2O structures of
1.989 Å, Fig. 10d and Table 2, which agrees with the calcu-
lated interaction energy order.
Structural changes for the PEOx and PAC-AA monomers,
when optimized in vacuum and aqueous phases, were obtained
to correlate the physiochemical properties and KHI perform-
ance. For example, the C=O bond length of the PEOx
monomer increases slightly in the aqueous phase to 1.253 Å
when compared to the vacuum phase increase to 1.238 Å, due
to hydrogen bonding. A similar trend was observed in the case
of the PAC-AA monomer; the C=O bond length in the aqueous
phase is 1.248 Å as compared with 1.237 Å in the vacuum
phase. In the next stage, the oxygen atomic charge in the car-
bonyl C=O group of benchmark KHI polymers, PEOx and
PAC-AA, was calculated as previously presented in Table 2.
The negative atomic charge of the aqueous PEOx monomer,
-0.580e, is slightly larger than that in vacuum, -0.484e, due to
hydrogen bonding. Similarly, the negative atomic charge of the
aqueous PAC-AA monomer, -0.559e, is slightly larger than
that in vacuum, -0.480e. As a result of the calculated oxygen
atomic charge on the PEOx monomer, i.e., -0.580e, and on the
PAC-AA monomer, i.e., -0.559e, in the aqueous phases, it is
concluded that PEOx has stronger hydrogen bond interactions,
which agrees with the calculated interaction energies.
Linking computational modeling calculations with experi-
mental results is crucial to present a reliable fundamental un-
derstanding of KHI performance, and ultimately, lead to the
rational design of novel KHIs. For achieving this, the asym-
metric stretching frequency of C=O bonds in the amide func-
tional group of PEOx and PAC-AA monomers was calculated
PEOx monomer, Δ72 cm-1, is larger than that for PAC-AA
in vacuum and aqueous phases. The calculated red shift for the
monomer, Δ26 cm-1. This finding agrees well with the stronger
interactions of water with the PEOx than with the PAC-AA,
which leads to the conclusion that PEOx has better inhibition
efficiency than PAC-AA, as was measured by the RC-5. The
computational modeling also enables accurate analysis of the
FTIR data when the experimental FTIR is complicated by the
PAC-AA
aq vac aq
-0.58 -0.48 -0.559
1.253 1.237 1.248
1592 1680 1654
– 1.989
-366.604541 -554.024719 -554.046043
-11.82 -10.14
SAUDI ARAMCO JOURNAL OF TECHNOLOGY FALL 2015
presence of overlapping carbonyl groups.
A further step toward the rational design of potential KHI
polymers is to investigate the effect of additional functional
groups on the parent amide group in an oxazoline monomer,
namely, the ether, fluoride, ethyl and imide functional groups.
The calculated hydrogen bonding interaction energies followed
this order: imide, -21.0 kJ/mol, > ether, -10.9 kJ/mol, > ethyl,
-10.1 kJ/mol, > fluoride, -8.1 kJ/mol. It can be deduced that
the hydrogen bond strength is influenced by the added func-
tional groups, increasing with electron donating groups like
imide and ether, and decreasing with electron withdrawing
groups like fluoride. The hydrogen bond strength is also re-
flected by the shorter hydrogen bond distance; 1.394 Å in the
case of imide as compared to 2.025 Å for fluoride. Based on
this approach, molecular computational modeling can be used
to either optimize current synthesized KHI or propose new
formulated KHIs.
Performance of Novel Synthesized KHIs
By considering the previous results, 12 new synthesized poly-
mers were evaluated as KHIs in the RC-5, Fig. 11. P-9 and
P-12 yielded less hydrate — compared to the control — by
inhibiting hydrate growth at the sub-cooling level of 4 °C and
5.6 °C, respectively. At the same time, no nucleation inhibition
was measured. At the sub-cooling temperature of 10.5 °C, P-9
promoted the growth of hydrates. Also very important to an
understanding of the fundamentals is that the P-9 polymer
stabilized the hydrate, as can be seen from Fig. 11. When the
system was heated to temperatures where hydrate is thermo-
dynamically unstable, a kinetic aspect of the hydrate-polymer
interaction led to stable hydrate. P-7 performed exceptionally
in comparison to other polymers, as can also be seen in Fig.
11. Even in the presence of this polymer, however, hydrate
Fig. 11. Representative curves from evaluating the 12 new polymers in the RC-5.
FALL 2015 SAUDI ARAMCO JOURNAL OF TECHNOLOGY
growth was promoted at the sub-cooling temperature of 10.5
°C. The promotion of hydrate growth is also observed at lower
system pressures compared to the control, e.g., see P-7 and P-9
in Fig. 11. Among the other 12 polymers, P-12 was also inter-
esting because it extended the induction time to 7½ hours and
promoted hydrate growth at a sub-cooling temperature of 10.5
°C. P-8 performed similarly to P-7, suggesting another polymer
has been discovered to be a KHI. The other polymers behaved
similarly to P-11: not inhibiting the hydrate nucleation but
changing the hydrate growth properties. The mechanisms of
these hydrate-polymer interactions are now being investigated
with computational modeling and structural characterization,
as was presented here for the PAC-AA and PEOx systems.
CONCLUSIONS
The issue of gas hydrates occurring in natural gas fields at high
sub-cooling temperatures has triggered the need for a reliable
way to mitigate such a problem. Many challenges are associ-
ated with this type of field that prevents hydrate inhibition,
such as sI hydrate formation and a high concentration of H2S.
As a result, we have developed a comprehensive approach
based on experimental and computational methods to mitigate
this issue by developing a novel class of KHIs.
Our approach consists of KHI performance testing, compu-
tational molecular modeling and acquiring an understanding
of fundamentals through physiochemical characterization of
polymers and model components. The performance testing
was conducted on ready-made polymers, commercial KHIs
and new synthesized polymers. The amide functional group
was found to be an essential chemical group in any KHI,
where the carbonyl group forms hydrogen bonding with the
hydrate surface to delay the enclathration process. The study
of polymer-water hydrogen bonding interactions revealed that
the interaction of PAC-AA and PEOx with water is consistent
with their inhibition performance. Computational molecular
modeling calculations of hydrogen bonding interaction energies
and carbonyl bond frequencies agree with the experimental
results. The calculated molecular characteristics, i.e., atomic
charges and bond distances, were consistent with the perform-
ance of PEOx and PAC-AA. Therefore, molecular modeling is
a very useful approach for describing KHIs at the atomic scale.
Linking of the atomic scale properties to the macro scale per-
formance has led to a crucial understanding of KHI mechanisms.
Our findings have helped us to develop two novel polymeric
KHIs. These new KHIs inhibited the gas hydrates of synthetic
natural gas with high concentrations of H2S and CO2 at and
beyond sub-cooling temperatures of 4 °C and 5.6 °C.
ACKNOWLEDGMENTS
The authors would like to thank Saudi Aramco for permission
to publish this article. Special thanks go to R&DC manage-
ment for their support and encouragement. The authors would
like to thank Dr. Ashrof Ali from the Chemistry Department at
King Fahd University of Petroleum and Minerals for synthesiz-
ing the new KHI polymers, and Dr. Mohammed Al-Daous for
the fruitful discussions.
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BIOGRAPHIES
Rashed M. Al-Eisa is a Scientist in the
Chemicals Research Division of Saudi
Aramco’s Research & Development
Center (R&DC). He joined Saudi
Aramco in 2010 after he finished his
degree as a member of the College
Degree Program for Non-Employees
(CDPNE). Rashid started working with the Advanced
Analysis Unit in the online group specializing in analyzer
and sensor technologies. Rashid then joined the innovative
chemicals sub-team under the Chemicals Research Division
where he focused on the kinetic hydrate inhibitors project.
His areas of interest include polymer science, water-soluble
polymers, and catalyst synthesis and characterization.
Rashed received his B.S. degree in Chemistry from
Aston University, Birmingham, U.K., and his M.S. degree in
Polymer Science from the University of North Carolina at
Wilmington, Wilmington, NC.
He is a member of the American Chemical Society
(ACS) and the International Society of Automation (ISA).
Dr. Mohamed S. Elanany is a Science
Specialist with the Chemicals Research
Division of Saudi Aramco’s Research
& Development Center (R&DC). He
is part of a team focused on the
development of in-house gas hydrate
inhibitors. Mohamed is an expert in
computational molecular modeling, advanced materials
development and characterization.
He has published more than 30 international journal
articles and two patents, and he has presented his research
results at many international conferences.
Mohamed received his B.S. and M.S. degrees in Physical
Chemistry from Egypt. In 2004, he received his Ph.D.
degree in Materials Chemistry from the Graduate School of
Engineering, Tohoku University, Japan. Mohamed gained
further postdoctoral experience in advanced materials and
molecular modeling at the University of Namur, Belgium,
before joining Saudi Aramco in 2007.
SAUDI ARAMCO JOURNAL OF TECHNOLOGY FALL 2015
 Dr. Khalid A. Al-Majnouni is the
leader of the innovative chemicals sub-
team under the Chemicals Research
Division of Saudi Aramco’s Research
& Development Center (R&DC). His
experience includes working at the
Jiddah Refinery for more than two
years as a Process Engineer in crude distillation and
naphtha reforming, and with fluid catalytic cracking (FCC)
units.
In 1994, Khalid joined Saudi Aramco’s College Degree
Program for Non-Employees (CDPNE) and received his
B.S. degree in Chemical Engineering from King Fahd
University of Petroleum and Minerals (KFUPM), Dhahran,
Saudi Arabia. Then, in 2005, he received his M.S. degree in
Chemical Engineering from the Colorado School of Mines,
Golden, CO. In 2011, Khalid received his Ph.D. degree in
Chemical Engineering from the University of Delaware,
Newark, DE.
Ali A. Al-Jabran is a Senior Digital
System Technician currently working
in the Materials Performance Unit of
the Technical Services Division of
Saudi Aramco’s Research &
Development Center (R&DC). He
joined Saudi Aramco in July 1983 as a
trainee in the Industrial Training Center (ITC) and
completed the program in 1985.
Ali is specialized in high-pressure high temperature
(HPHT) operations and specifically in flow accelerated
corrosion, electrochemistry and the process control of
HPHT equipment. He has also been involved in developing
new competencies in corrosion testing.
Ali completed six months of specialized training with
C&C Technologies, Houston, TX.
Hassan A. Al-Ajwad is a Science
Specialist working with the Materials
Performance Unit of the Technical
Services Division at Saudi Aramco’s
Research & Development Center
(R&DC). His focus areas in research
and technical service include high-
pressure high temperature (HPHT) corrosion simulation,
flow accelerated corrosion, oil field chemicals performance
and design of sophisticated laboratory systems. Over the
past few years, Hassan has led the R&DC efforts for in-
house development of world-class capabilities in the areas
of HPHT corrosion testing and flow corrosion simulation
and measurement systems.
He received his B.S. degree in Industrial Chemistry from
King Fahd University of Petroleum and Minerals (KFUPM),
Dhahran, Saudi Arabia.
FALL 2015 SAUDI ARAMCO JOURNAL OF TECHNOLOGY
Dr. Ibrahim A. Abba is Chief
Technologist of the Chemicals
Research Division at Saudi Aramco’s
Research & Development Center
(R&DC). Prior to joining Saudi
Aramco, he taught in academia and
worked for chemical companies, both
in the Middle East and in North America. Ibrahim is
currently responsible for directing technology development
efforts spanning the catalytic and thermal cracking of
unconventional feeds to valorization of low value streams
to high value chemicals.
He received his M.S. degree in Chemical Engineering
from King Fahd University of Petroleum and Minerals
(KFUPM), Dhahran, Saudi Arabia, and his Ph.D. degree in
Chemical Engineering from the University of British
Columbia, Vancouver, British Columbia, Canada.
Ibrahim has authored/coauthored over 40 articles and
patents.
Dr. Abdullah R. Al-Malki is a
Research Science Consultant with the
Chemicals Research Division of Saudi
Aramco’s Research & Development
Center (R&DC). He has 25 years of
experience in crude oil and fuels
characterization, processing, quality
and specifications. Abdullah joined Saudi Aramco in 1988
after graduation and has spent most of his career with
R&DC, although he has had several assignments working
at the Ras Tanura refinery and in the Oil Supply Planning
and Scheduling (OSPAS) Department.
Abdullah received his B.S. degree in Chemistry from
King Abdulaziz University, Jiddah, Saudi Arabia, and M.S.
and Ph.D. degrees in Chemistry from King Fahd University
of Petroleum and Minerals (KFUPM), Dhahran, Saudi
Arabia.