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ELSEVIER Fluid Phase Equilibria 117 (1996) 186-192

NATURAL HYDRATE INHIBITING COMPONENTS IN CRUDE OILS.

Finn Hallstein Fadnes.

Norsk Hydro Research Center,

Sandsliveien 90,
N-5049 Sandsli,
Bergen, Norway.

ABSTRACT
Reservoir fluids have been observed to show significant variations in their ability to form hydrate plugs. It is
therefore likely that the different oils contains components that effect their tendency to form plugs.
A procedure for evaluation of the plugging potential and for identifcation and extraction of naturally hydrate
inhibiting components in crude oils is presented. The actual oil is characterized with respect to emulgating
properties, content of polar components (resins and asphaltenes), interfacial tension, hydrate equilibrium,
kinetics and potential of plug formation. The oil is then modified, by extracting the polar components. The
modified oil is characterized, in the same manner as described above.
The extracted polar components are used as a base for secondary extraction and fractionation of surface
active components. Component fractions having high surface activity will be tested as hydrate inhibitors.
The results indicate that it is possible to identify naturally inhibiting components in crude oils having a low
potential of forming hydrate plugs.

INTRODUCTION
Present and future development of North Sea oil reserves presupposes extensive use of sub sea production
solutions. Transport of unprocessed, multiphase well streams at sea bottom temperatures give a high potential
for formation of gas hydrates.
Gas hydrates are non-stochiometric, ice-like crystals formed by low molecular weight hydrocarbons
confined in a framework of water molecules. Depending on the pressure and the composition of the hydrocarbon
fluid, hydrates may be stable at temperatures up to 30 °C. The traditional way to prevent hydrates has been to
inject methanol as a freezing point depressant. The main problem of using methanol is the high cost and
volumes. The volumes required are typically in the order of 30 % of the aqueous phase.
The complexity of the sub sea completion's is continuously increasing. The number of sub sea wellheads
and manifolds in a completion increases, the gas oil ratio and the water cut of the transported fluids show a high
variation and the transport distance increases. These aspects, combined with the enviromental demand of
reducing the contamination of the disposed water, are all factors that may prohibit the use of methanol for
hydrate prevention. There is a cost saving potential of finding alternative, more efficient hydrate inhibitors.
Furthermore, it may be a potential in being capable of accurately defining process conditions where hydrate
inhibition might all together be avoided.
There is presently a high activity in the search for alternative hydrate inhibitors (Sloan et. al. 1994). The
methods for selection of potential candidates are varying, from those based on molecular simulations to those
based on experience and qualified guesses. Promising candidates are then subjects of extensive screening tests.
In the present work a different approach is chosen. Initially the hydrate formation characteristics are
established for a number of crude oils. In this characterization the emulgating properties, the hydrate equilibrium
conditions and the plugging tendency of different oils are determined. The characterization is performed in a

0378-3812/96/$15.00 © 1996 Elsevier Science B.V. All rights reserved

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 F.H. Fadnes / Fluid Phase Equilibria 117(1996) 186-192 187

stirred, high pressure sapphire cell. In the future also a wheel formed flow simulator and a low pressure flow
loop will be used.
Oils having a low potential of forming hydrate plugs, are further characterized, with respect to fluid
properties. The amount of asphaltenes, determined as the C 5 insolubles, and the interracial tension against
formation water are determined. The surface active components of the fluids are extracted and the modified oils
and the extracted components are characterized with respect to hydrate and fluid properties.
In this paper we report results of experiments involving three different oils, one non-emulgating and two
emulgating. The objective of the work is to show that the oils have different hydrate formation characteristics
and that hydrate inhibiting components can be extracted fi'om the emulgating oils.

EXPERIMENTAL SECTION

H i ~ pressure sapphire cell.

The sapphire cell setup is outlined in figure 1.

1) Thermal Cabinet,
2) Sapphire Cell,
3) Piston,
4) Stirrer,
5) Stirrer Motor,
6) Temp.Sensor,
7) Pressure Transducer,
8) Oil Cell,
9) Water Cell,
10)Piston motor,
11)Controllers/Amplifiers,
12)Computer

u I

12
5U !1

Figure 1. Sapphire cell.

The cell is placed in a temperature-controlled air bath in which the temperature can be varied between -40
and +200 °C. The temperature stability is 0.1 °C and the resolution is 0.01°C. The cell has a maximum working
pressure of 500 bara. The cell pressure is maintained by the help of a compressed stuff'mg box. The accuracy of
the pressure measurement is estimated to be within 0.5 bar and the resolution is 0.1 bar. The cell volume is
controlled and varied using a piston directly coupled to a computerized brushless motor. Volumes are read with
a resolution of 0.0001 cm 3. The estimated accuracy is 0.005 cm 3. Maximum cell volume is 100 cm 3.
Stirring is provided by a magnetically coupled stirrer, driven by a computer controlled, variable speed
motor. Maximum speed is 1000 rpm. Rheology changes of the experimental fluids are continuously monitored
by measurement of the effect required to keep the motor running at constant speed.
188 F.H. Fadnes / Fluid Phase Equilibria 117 (1996) 186-:192

Exnerimental nrocedures.
Two different types of hydrate experiments are performed. Both experiments give information on the
appearance and the amount of the hydrates formed. The dynamic experiment is designed to simulate hydrate
formation at flowing conditions. In this experiment hydrate formation is initiated by cooling the system at a
constant rate, 3 - 5 °C/hours, while continuously stirring the cell. After a period of time, allowing for equilibrium
to be established, the system is heated at a rate of 1 - 1.5 °C/hours until the hydrates are completely melted. The
dynamic experiment give information of the hydrate equilibrium temperature and the degree of sub cooling. The
start-up experiment is designed to simulate hydrate formation upon start-up of a previously shut down pipeline.
In this experiment hydrate formation is initiated, at sea-bed conditions, by starting the stirrer. This experiment is
used mainly to evaluate kinetic hydrate inhibitors.
The experiments are performed at isobaric conditions, at 70 bara. Hydrate formation and decomposition are
indicated by deflections in a volume vs. temperature plot (the isobar) and by change in the rheology of the
system (the apparent viscosity).
Characterization of the emulsion properties is performed by visual observations.

Extraction and characterization of active components.

The extraction of surface active components from the oils is performed in to stages, as outlined in figure 2.
The primary extraction is performed using two different methods: 1. By titration with ethane (C~) and 2. By
dilution with n-pentane (n-Cs) followed by a treatment with active silica gel. In the type I primary extraction
100 cm 3 of the oil is added to a 500 cm 3 high pressure piston cell. 400 cm3 C 2 is then added at room temperature
and a pressure of 200 bara. The content of the piston cell is mixed and let~ to equilibrate and fmally filtrated
through a high pressure Millipore filter, pore size 0.2 I,tm. In the type 2 primary extraction 150 cm3 of the oil is
diluted in 1600 cm3 n-C 5 and then added 375 gram silica gel. The mixture is stirred for 24 hours and is then
filtrated.
The soluble fraction from the primary extraction is characterized by measurement of interfacial tension
(IFT) against formation water. A part of this fraction is recombined with a separator gas and the hydrate and
emulgating properties is characterized, as described in the preciding section. The non-soluble fraction is
dissolved in toluene and the IFT is measured.
The secondary extraction of active components will be performed using Sequential Elution Solvent
Chromatography (Homhof et.al. 1988). The surface activity of the eluted fractions will be characterized by IFT
measurements and the fractions having the highest surface activity will be added to a non-emulgating oil for
characterization of hydrate and emulgating properties. The active componets may be further modified to
improve their performance as hydrate inhibitors. The results of the secondary extraction is not presented in this
work.

INITIALOIL

I
SOLUBLE PRECIPITATE

l ACTIVECOMPONENTS[
Figure 2. Extraction of active components.
 F.H. Fadnes / Fluid Phase Equilibria 117 (1996) 186-192 189

IFT measurements.
IFT is measured for the oil samples against synthetic formation water. The measurements are performed
using The Pendant Drop method. In this method a video picture of an oil drop formed in the aqueous phase is
taken. The picture is digitized and fitted to a theoretical function in order to calculate the IFT (Hansen et. al.
1991).

Exoerimental fluids.
The study has been performed using two emulgating oils, A] and A 2 and one non-emulgating oil, B. Oil A~
and A 2 are from the same reservoir but from different structures. Oil A~ was recombined to the reservoir fluid
gas oil ratio (GOR) while oil A 2 was recombined to a higher GOR, as the GOR in a transport pipeline is
expected to show variations. After recombination of the samples, oil A~ was stored somewhat longer than A 2
before it was used in the experiments. It was observed that A~ was the oil having the most distinct emulgating
properties. Some basic properties of the fluids are presented in table 1 and the composition of the fluids are
given in table 2.
The aqueous phase consists of a synthetic formation water, having a salinity of 4,5 %.

Table 1. Some basic properties of the experimentalfluids

Property Oil A~ Oil A2 Oil B
GOR (Sm3/Sm 3) 61 89 302,4
Dens STO (kg/m3) 898 886,3 823,5
Mole weight STO 255 230,8 197,7
Asphaitenes (C5) 1,5 1,4 0,2

Table 2. The composition of the exFerimental~uids.

Component Oil A~ Oil A 2 Oil B
(Mole %)
N2 0,41 0 1,03
CO 2 0,38 1,36 0,78
CI 36,91 39,4 50,16
C2 2,87 4,56 7,17
C3 0,51 1,64 6,71
i-C 4 0,92 1,18 1,28
n-C 4 0,13 0,38 3,61
i-C 5 0,23 0,88 1,21
n-C 5 0,08 0,14 1,79
C6 0,84 1,27 2,27
C7 3,57 3,94 3,51
C8 4,36 5,14 3,38
C9 3,38 3,55 2,17
C10+ 45,44 36,56 14,93
 190 F.H. Fadnes I Fluid Phase Equilibria 117 (1996) 186-192

RESULTS

Figure 3 shows the asphaltene content of the three oils, as a function of the precipitant. In this work the
hydrate and emulgating properties were observed in the high pressure sapphire cell. Examples of dynamic and
start-up experiments are shown in figure 4 and 5. The main results of the characterization are presented in table
3. The results of the IFT measurements ofoil A 2 and B are given in figure 6.

14

12

lO

i,
'~ 4

I I I It
il 3 4 5

Precipitant (Carbon number)

Figure 3. The asphaltene content of the originalal oils.

n
m

I j.- .

:'o ~, A ~...> ,A, ,Ao ,A~ " ,', .. ,. A A o

riME I r / I

Figure 4. Example of dynamic hydrate experiment, Figure 5. Example of start-up hydrate experiment,
Oil A 2. Plugging. Explanations in text. Oil A 2. T=4.5°C. Partial plugging. Explanations
in text.

In figures 4 and 5 label 1 indicates start of hydrate formation, label 2 indicates reheating and start of hydrate
decomposition and, in figure 4, label 3 indicates hydrate equilibrium at 12,3 °C.
 F.H. Fadnes / Fluid Phase Equilibria 117 (1996) 186-192 19 !

Oil A~ and A: were both modified by C 2 titration. The oils, which initially were very dark colored were
observed to be significantly lighter and more transparent after the titration. Only oil A2 was modified by the
silica gel treatment. After the treatment this oil was transparent and light orange colored. A white precipitate was
observed in this oil. The precipitate had a melting point of approximately 30 °C and is suspected to be wax.

Table 3. Main results o~fh~drate and emulsion characterization.

Emulsion stability* Hydrate exluil. Water cut Hydrate apperance
(Minutes) (@ 70 bara) (%)
OIL A t > 30 11,7 45 No plug
OIL A I (C 2 < 1 13 45 Plug
modified)
OIL A s > 10 13,8 50 Partial plug**
OIL A s > 10 13,8 80 No plug
OIL A s (C 2 <1 12,3 50 Plug
modified)
OIL A 2 (C2 <1 12,3 80 No plug
modified)
OIL A s (Silica gel <l 12,2 50 Plug
modified)
OIL A s (Silica gel <1 12,2 80 No plug
modified)
OIL B Immediate 10,7 45 Plug***
* Emulsion stability, given as time required for phase separation.
** Plugged in dynamic experiment. Partial plug in start-up experiment. (Figures 4 and 5).
*** The plugging was in this case qualitatively evaluated to be fare more extensive than in the other
experiments.

I Si ge~ soluble fraction of oil A21

i o . , . ol. ~1 " -~ . ........

•I I Etheme inm°luble fracti°n in t°luenel

500 1000 t,$00 2OOO

Tlnne (s)

Figure 6. IFT measurements of oils ,42 and B.

192 F.H. Fadnes / Fluid Phase Equilibria 117 (1996) 186-192

DISCUSSION

The oils content of asphaltenes seems to correlate well with the emulsion and hydrate forming
characteristics. Oil B, which has a low content of asphaltenes, do not form stable emulsions and plugs are
formed immediately after hydrate formation is initiated. Oil A t and As are from the same field, but from different
structures. There is not significant differences in the measured asphaltene content of these oils but, all the same,
there is still a significant difference in the emulsion and hydrate characteristics. This may be due to the fact that
oil A t was stored, at reservoir temperature and pressure, for nearly a year before it was used in the experiments.
During this period of time it is probable that, at least a fraction of the asphaltenes that would precipitate during
the production test is redissolved. The amount of dissolved asphaltenes can presumably associatedted with the
oils ability to form emulsions.
The IFT measurements show that the surface activity decreases significantly when the heavy ends are
removed. Experiments involving oil A 2 indicates that the tendency of forming plugs increase as the surface
activity decrease. The relation between high IFT's and the plugging potential is, however, still not clear as oil B
seems to have a higher potential to form plugs than the silica gel modified oil A2, even if the IFT of the latter
have the highest value. The modified oil contains wax crystals that might act as nucleating agents, thus
preventing plug formation.
The potential of extracting naturally inhibiting components from oils is most distinctly demonstrated in the
experiments involving oil A t. In this oil the tendency of forming plugs is clearly changed when the heavy end is
removed by titration with C 2. The same picture is indicated in the experiments involving oil A2, but in this case it
is less distinct as this oil initially has a higher potential of forming plugs.
It was observed that the plug formation potential of oil A s was a function of the water cut. No plugs formed
at a water cut of 80%. This is, however, believed to be a system effect. In this work the water cut is defined as
the aqueous phase volume related to the volume of liquid hydrocarbons, both at standard conditions. At water
cut 80% the available amount of hydrate forming components is low compared to the aqueous volume, and a
limited amount of hydrates are formed. When the water cut is decreased to 50%, the aqueous volume is kept
constant while the hydrocarbon volume is increased.

CONCLUSIONS

The main conclusions of this work can be summarized as follows:

- Crude oils have varying potential offorming hydrateplugs.
- The oils content of polar components reflects the potential of emulsion- and hydrate plug formation.
- Non-emulgating oils have a higher potential offorming hydrate plugs.
- Components having an inhibiting effect on hydrateplugformation can be extractedfrom crude oils.

ACKNOWLEDGMENT

The author thanks Norsk Hydro for permission to publish the results and Dr. Robert Orr at Norsk Hydro
Research Center Porsgrunn for performing the silica gel extraction and the IFT measurements.

REFERENCES

Hansen, F. K. and Rodsrud, G. 1991, Surface Tension by Pendant Drop 1. A Fast Standard Instrument Using
Computer Image Analysis, J. Coll. Int. Sci., 141: 1.

Khulbe, K. C., Neale, G. H. and Hornhof, V. 1988, Interracial Tension Behavior and ESR Properties of
Asphaltenes Derived from Heavy Oil, Fuel Processing Technology, 19:61.

Long, J., Lederhos, J., Sum, A., Christiansen, R. and Sloan, E. D. 1994, Kinetic Inhibitors of Natural Gas
Hydrates, Presented at the 73rd Annual GPA Convention in New Orleans, March 7 - 9.