DIPLOMA THESIS

SURFACE PHENOMENA IN GAS HYDRATE SYSTEMS

MOHAMMED MAMUN AZAD
STUDENT NUMBER 677698




________________________________________________________________________

Institutt for petroleumsteknologi og anvendt geofysikk
Department of petroleum engineering and applied geoscience

Norwegian university of science and technology (NTNU),
Trondheim
June 2006



NTNU
Norges teknisk-naturvitenskapelige Fakultet for ingenirvitenskap og teknologi
universitet Faculty of Engineering and Technology
Studieprogram i Geofag og petroleumsteknologi
Study Programme in Earth Sciences and Petroleum Engineering



Institutt for petroleumsteknologi og anvendt geofysikk
Department of Petroleum Engineering and Applied Geophysics

HOVEDOPPGAVEN/DIPLOMA THESIS/MASTER OF SCIENCE THESIS


Kandidatens navn/ The candidates name: MOHAMMED MAMUN AZAD.

Oppgavens tittel, norsk/Title of Thesis, Norwegian:

Oppgavens tittel, engelsk/Title of Thesis, English: Surface phenomena in gas hydrate systems.

Utfyllende tekst/Extended text:

This report presents experiments, observations and analysis of wetting tendency of different kinds
of oil samples on hydrate layers. The observations were carried out visually by using a digital
camera. This report also covers design and building of the cell where the experiments were to be
performed. The ultimate purpose of the experiments was to know the tendency of oils to form
hydrate plugs which may impede the flow.

Studieretning/Area of specialization: Petroleum Engineering
Fagomrde/Combination of subjects: Production


Tidsrom/Time interval:


Faglrer/Teacher

SKJEMAET TAS INN SOM SIDE 1 I HOVEDOPPGAVEN/PLEASE USE THIS FORM AS PAGE 1 IN
THE THESIS


Original: Student
Kopi: Fakultet
Kopi: Institutt

Abstract

Surface phenomena in gas hydrate systems are important for understanding the behaviour
of multiphase flow in pipelines, particularly regarding the tendency for oils to form
hydrate plugs which may impede the flow. It is important to gather more data on these
phenomena. Not many works have so far been done upon the surface phenomenon of gas
hydrates. In this work, a cell was designed and built based on the some new ideas and
sketches and then it was tested for the purpose of low pressure testing of gas hydrate,
water, oil surface phenomena, especially wetting angles. The tests were planned with
visual observations and measurements in the cell to determine wetting angles between a
hydrate surface and droplets of varying compositions of oil samples. During the entire
span of the experiments, the operating pressures were kept at laboratory conditions.
Tetrahydrofurane (THF) was used to form hydrates at the laboratory conditions. Different
oil samples such as Exxsol d80 (which is a condensate-like refined oil), Paladio crude oil
(from West Africa real oil straight from the well), and King crude oil from the Gulf of
Mexico as well as an unknown sample of a light oil from Norsk Hydro were used in order
to try to observe their wetting angles with hydrate layers. Then the experiments and
observations were compared with previous works. In addition to performing and
reporting on a brief literature study of the subject, a description of the equipment and
related experiments in detail is provided.
i


Acknowledgement
I would like to send my gratitude and appreciations to all who helped me in one way or
another to facilitate my Thesis. Special thanks to my supervisor Prof. Jon Steinar
Gudmundsson of Department of Petroleum Engineering and Applied Geophysics at
NTNU for his time dedication to assist me in various part of this study. I am also grateful
to him for his patience, co-operation and excellent supervision throughout this work.

I would specially like to thank Roar Larsen for contributing with the idea, feedback and
theoretical frameworks which had given me the foundation when executing this work. He
was always willing to answer my questions. I also appreciate his enthusiasm, patience
and encouragement.

I also wish to thank Mr. Helge Johansen and Knut Glas of the Refrigeration Lab. at
NTNU, Glshaugen for setting the cooling unit and building hydrate cell for me. I am
grateful to them for their willingness in repairing the problems with the cooling unit and
hydrate cell. I am grateful to Mr. Anwar Hossain Bhuiyan (PHD student) who offered me
tremendous supports during the formatting stage of the thesis.

I wish to thank NORAD for giving me the scholarship award and an opportunity to study
here in Norway.

I do remember my mother for her moral support. I specially appreciate my wife Sadia
Akter for providing me excellent support and encouragement during the entire period of
pursuing the thesis. Last but not least thanks to my friends and class-mates who helped
me in making numerous improvements not only to its wording but to its technical
contents.
ii

Nomenclature

A : Area.
Atm. : Atmosphere.
ID : Inner Diameter.
HCFC : Hydrochloroflourocarbon.
PMMA : Polymethyl methacrylate.
S : Second.
THF : Tetrahydrofuran.
: Surface tension.
A : Work.
A : Net minimum surface free energies.

: Surface tension of phase .

: Surface tension of phase .

: Surface tension between phases and .

SV
: Surface tension of phase between solid and vapor phases.

SL
: Surface tension of phase between solid and liquid phases.

LV
: Surface tension of phase between liquid and vapor phases.
: Angle of contact.

A
: Advancing contacting angles.

R
: Receding contact angles.
iii

Table of contents

Abstract............................................................................................................................... i
Acknowledgement ............................................................................................................. ii
Nomenclature ................................................................................................................... iii
Table of contents .............................................................................................................. iv
Table of Figures................................................................................................................ vi

1 Background .................................................................................................................... 1
1.1 Introduction........................................................................................................................... 1
1.2 Objective ............................................................................................................................... 1
1.3 Methodology......................................................................................................................... 2
1.4 Block Diagram...................................................................................................................... 2

2 Literature Review.......................................................................................................... 4
2.1 Introduction to Clathrate Hydrates........................................................................................ 4
2.2 The History of Gas Hydrates................................................................................................. 4
2.3 Basics of Hydrates ................................................................................................................ 7
2.4 Structures of Natural Gas Hydrates....................................................................................... 7
2.5 Gas Hydrate Formation......................................................................................................... 9
2.6 Kinetics and Morphology of Gas Hydrates......................................................................... 10
2.7 Fundamental Phase Equilibrium for Natural Gas Hydrates ................................................ 12
2.8 Hydrate Properties............................................................................................................... 14
2.9 Chemicals for Gas Hydrate Control .................................................................................... 15
2.9.1 Thermodynamic Inhibitors .......................................................................................... 15
2.9.2 Kinetic Inhibitors (KI) ................................................................................................. 16
2.9.3 Anti-Agglomerants (AA)............................................................................................. 17
2.10 Background of Colloids .................................................................................................... 20
2.11 The Classical Interface Model .......................................................................................... 21
2.12 Wetting Mechanism: Liquid on Solid............................................................................... 22
2.13 Static Contact Angles........................................................................................................ 23
2.14 Works of Hirata and Mori (1998) ..................................................................................... 24
2.14.1 Experiments ............................................................................................................... 24
2.14.2 Results and Discussion of Hirata and Moris Experiment......................................... 26

3 Set-up and Procedure of Experiment......................................................................... 28
3.1 Introduction......................................................................................................................... 28
3.2 Hydrate Cell ........................................................................................................................ 28
3.3 Leakage and Performance Tests.......................................................................................... 29
3.4 List of chemicals and samples............................................................................................. 30
3.5 Preparation of THF Solution............................................................................................... 31
3.6 Procedure of Experiment..................................................................................................... 31

4 Observations and Results............................................................................................ 33
4.1 Some Important Observations............................................................................................. 33
4.2 Results................................................................................................................................. 34

iv

5 Discussion...................................................................................................................... 37
5.1 Discussion of problems encountered and solutions ............................................................ 37
5.2 Discussion of Results .......................................................................................................... 38
5.3 Comparison with previous works of Hirata and Mori (1998)............................................. 40

6 Conclusion and Recommendation for Future Works .............................................. 41
6.1 Conclusion .......................................................................................................................... 41
6.2 Recommendations for future works .................................................................................... 42

References:....................................................................................................................... 43

APPENDICES ................................................................................................................. 45

v

Table of Figures

Figure 1.1 Block Diagram................................................................................................... 3
Figure 2.1 Schematic of Gas Hydrate Knowledge.............................................................. 6
Figure 2.3 Autocatalytic reaction mechanisms for hydrate formation ............................. 10
Figure 2.4 Cavities in gas clathrate hydrates .................................................................... 10
Figure 2.5 Hydrate Phase Diagram................................................................................... 12
Figure 2.6 Hydrate formation regions for C1 to C4 paraffins .......................................... 13
Figure 2.7 Equilibrium curve for methane hydrate and mixture hydrate ......................... 14
Figure 2.8 Monomer Units for Kinetic Inhibitor Polymers .............................................. 16
Figure 2.9 Interaction of a pendent alkylamide group of a kinetic inhibitor .................... 17
Figure 2.10 Structure of quaternary anti-agglomerants .................................................... 18
Figure 2.11 Hydrate Control Methods Tree...................................................................... 20
Figure 2.12 Interface between phase and phase ......................................................... 21
Figure 2.13 Equilibrium of a non-spreading drop on a planar solid................................. 22
Figure 2.14 Sessile bubble with axial symmetry on a solid surface ................................. 24
Figure 2.15 THF hydrate partly immersed in liquid phases ............................................. 25
Figure 2.16 Video graphic pictures................................................................................... 27
vi

1 Background

1.1 Introduction
Since the beginning of the 20
th
century, the production of natural gas has encountered
difficulties with the plugging of piping by the deposition of crystals, first thought to be
ice crystals. These crystals are in fact hydrates of natural gas which can appear far above
the temperature at which ice is formed. They are inclusion compounds which result from
the combination of water with some of the components of natural gas, and primarily
methane. The oil and gas industry is facing increasing costs in inhibiting gas hydrate
formation due to the development of offshore gas reservoirs. Recent international
estimates of the cost of the conventional inhibitor, methanol, alone are in excess of $150
million/year. Gas hydrates are likely to form in subsea flowlines unless the water is
removed down to the lowest dew point encountered, highly effective insulation is in
place, or inhibitors are used (Paez and Blok, 2001). Since complete stripping of water
from condensates and/or natural gas is prohibitively expensive, and effective insulation is
beyond current economic limits, the most effective solution includes the use of low
dosage hydrate inhibitors- Kinetic inhibitors and Anti-agglomerants. The understanding
of wetting phenomena, specially the wetting angles of kinetic inhibitors onto the hydrate
layers is very important.
1.2 Objective
The wetting phenomena of gas hydrates in oil or water are still not well known. One of
the most important properties of wetting phenomena is wetting or contact angle between
the hydrate phase and water or oil phase. In this thesis my main objective was to find the
contact angles between hydrate and oils of different types and compositions by doing
some tests. And, finally compare the observations and result with the previous works.
The tests would be carried out with visual observations and measurements in the cell to
determine wetting angles between the hydrate surface and droplets of varying
1

compositions. For this reason, a cell was to be designed and built at first using some
available sketches and ideas.
1.3 Methodology
This thesis was based on some observations of experiments with hydrates and oil in a
certain cell, which was at first designed and built with the help of some existing concepts
and sketches. Designing and building of the cell to meet the experimental requirements
were the important tasks of the thesis. Once the cell found ready, it should be connected
with a cooling unit and then its performance and leakage tests should be conducted by
using water.

Then hydrates were to be prepared in that cell in order to find the surface angles between
hydrate layer and oil layer. But the most favourable conditions for the formation of gas
hydrates are very high pressure or low temperature which is quite difficult to maintain in
laboratories. So, a mixture of tetrahydrofurane (21% vol) and water was used to form
hydrate because this mixture could form hydrates at atmospheric pressure and 4.4C.

96% (wt) of ethanol was circulated into the cell for cooling the THF solution below its
hydrate equilibrium temperature of 4.4C. Hydrates would presumably be formed at the
wall between the coolant and THF solution. Then the droplets of the oil to be tested were
allowed to be deposited upon the hydrate layer by using a syringe and a narrow needle.
Then the pictures of the contact surfaces were taken by a digital camera and sketches
were drawn to make visual observations and measurements of wetting angles between a
hydrate surface and droplets of oil of different compositions.
1.4 Block Diagram
The entire tasks and procedures planned to be performed in this thesis are given in the
following block diagram.
2

Literature
Studies
Design
Existing concepts
& ideas
Available
sketches
Building
Cell
ready
P
e
r
f
o
r
m
a
n
c
e

&

l
e
a
k
a
g
e

t
e
s
t
THF solution
preparation
Hydrate
preparation
Addition
of oil
droplets
O
b
s
e
r
v
a
t
i
o
n

Taking
pictures
Drawing
sketches
Discussion
Conclusion

Figure 1.1 Block Diagram
3


2 Literature Review

2.1 Introduction to Clathrate Hydrates
Clathrate hydrates are ice-like crystalline solid solutions each composed of hydrogen-
bonded water molecules (host molecules) and guest molecules of some other species.
Each guest molecule is enclosed, without the aid of any chemical bonding, in a cavity
created by the water molecules. Because water molecules account for a major proportion
in any clathrate hydrate, it is likely that the surfaces of clathrate hydrate phases are
hydrophilic, i.e. well wettable with liquid water (Hirata and Mori, 1993).
2.2 The History of Gas Hydrates
Revealing the truth in the history of development of any considerable scientific idea
usually turns out to be very complicated. Early scientists frequently would not pay proper
attention to a natural phenomenon he had revealed, especially if the discoverer had no use
for his contemporaries. The majority of scientific discoveries result from the absorbed
work of some creative individuals searching and constantly filling in the blank spaces in
science (Makogon, 1997).

The boundary between 18
th
and 19
th
centuries was a time when developing industry
acutely needed science, when every new discovery had a profound impact on the pace of
civilized developments and the hopes of the society were pinned to physics and
chemistry. It was then that gas hydrates, solid molecular compounds of water with gas,
were discovered. It is well known today there are vast natural gas hydrate accumulations
on Earth, however the first hydrates were synthesized in-vitro. Most specialists believe
that gas hydrates were first obtained in 1810 in the laboratory of Sir Humphrey Davy,
who cooled an aqueous solution saturated with chlorine gas below 9C to yield a
crystal/ice-like material. However, analysis of the preceding works allowed us to obtain
evidence of hydrate retrieval more than 30 years prior to H. Davy. The great English
philosopher and naturalist Joseph Priestley happened to obtain hydrate of sulphur dioxide
4

(SO
2
) both from its water solution and from its gaseous phase and ice. The results of the
experiments were reported in his three volume work Versuche und Beobachtungen uber
vershiedene Gattungen der Luft (Makogon Y. F., 1997).

In the beginning of the 20
th
century, oil and gas became important in the world of energy
balance. During the 1920s large gas pipelines were constructed and put into operation in
the United States. Gas was supplied under pressure through these pipes from the gas
fields to the consumption centres. Solid plugs complicated the transportation of gas
during autumn and spring periods. Plugs were misinterpreted to form from water
remaining in the pipelines after construction and hydraulic pressurizing. This estimate led
to a deadlock in solving the problem. However, an important conclusion was made by the
American chemist E. G. Hammerschmidt in 1934. Not ice but hydrate plugs were
responsible for gas transport complications in the pipeline sections.

The history of studies on natural gas hydrates had been presented in numerous articles,
scientific reports and addresses. A great number of patents have been taken out based on
the investigations in hydrate properties. Today two major directions have formed in the
problem: technogenic and natural gas hydrates. Both these directions are based on the
results of fundamental research of the genesis and properties of gas hydrates. Figure 2.1
presents a principal schematic of the major directions of studying gas hydrates (Makogon,
1997).
5


Figure 2.1 Schematic of Gas Hydrate Knowledge (Makogon, 1997)
6


2.3 Basics of Hydrates
Hydrates are solid crystalline metastable compounds whose properties and stability
depend on the values of pressure and temperature. Clathrate hydrates designate a
particular class of crystalline solid compounds.

Now-a-days, clathrate hydrates are increasingly involved in various technological aspects
of energy utilization by human beings. Examples include the prediction and prevention of
plugging due to hydrate formation in the pipelines for transporting natural gas including
water vapour, the formation and storage of clathrate hydrates as cool storage media for
residential air conditioning, and the ocean disposal of liquefied carbon dioxide, a green-
house effect gas, separated at fossil-fuel-fired power plants. The formation of a clathrate
hydrate includes a variety of physical, chemical and/or physicochemical processes. When
the guest species and liquid water are sparingly soluble in each other and hence the
formation of clathrate hydrate is inherently limited to the macroscopic interface between
the two fluid phases, the water/guest reaction at the interface, the diffusive transport of
water and/or the guest across the interface, and the diffusive transport of the heat of
hydrate formation away from the interface are considered to be the processes possibly
controlling the hydrate formation while the hydrate is spread over no more than a
considerable proportion of the interfacial area. If the liquid water is not saturated with the
guest species, the hydrate once formed may continuously decompose, releasing the
molecules of the guest species which will be dissolved into the water, causing a mass
transfer process. As the hydrate phase grows so as to spread over a significant proportion
of the interface or even cover the entire interface, the further growth of the hydrate phase
must depend on the penetration of water and/or the guest species across the very hydrate
phase to maintain the mutual contact. This penetration process has been little investigated
so far, and it is not well understood (Sugaya and Mori, 1995).
2.4 Structures of Natural Gas Hydrates
Gas hydrates are a large subgroup of clathrate hydrates forming mostly under high
pressure or/and low temperatures. Hydrates of natural gases prevail in deep-sea sediments
7

and permafrost, and could play an important role in the formation of the planetary
nebulae (Lovanob et. al., 2005).

All common natural gas hydrates seem to belong to the three crystal structures, cubic
structure (s), cubic structure (s), or hexagonal structure H (sH) shown in figure 2.2.
Structure is formed with molecules smaller than 6 , such as methane, ethane, carbon
dioxide, and hydrogen sulphide. Nitrogen and smaller molecules (d<4.2 ) are
exceptions and form structure as single guests. Somewhat larger (6 <d<7 ) single
guest molecules such as propane or iso-butane will form structure . Still larger
molecules (7 <d<9 ) such as iso-pentane or neohexane can form structure H when
accompanied by smaller molecules such as methane, hydrogen sulphide, or nitrogen
(Sloan, 1997).



Figure 2.2 Structures of Clathrate Hydrates (Makogon, 1997)

In these structures, the water molecules form polyhedra. The pentagonal dodecahedron,
designed by the notation 5
12
, is a basic building block of hydrate structures. It is not
possible to fill space entirely with dodecahedra. Because of to this restriction
dodecahedra are necessarily associated with other types of polyhedron to form the
structure of the hydrates. Structure I is composed of two small cavities formed by a
8

dodecahedron and six large cavities formed by a tetradecahedron with twelve pentagonal
faces and two hexagonal faces referenced as 5
12
6
2
(Figure 2.2). Structure II is composed
of sixteen small cavities (5
12
) and eight large cavities, formed by a hexadecahedron with
twelve pentagonal faces and four hexagonal faces. Each of these polyhedra forms a cavity
which can contain a molecule of natural gas components with which it forms a hydrate.
Methane fits into the small cavities (5
12
) of structures I and II, and in the large cavities
(5
12
6
2
) of structure I. Nitrogen, propane and isobutene form structure-II hydrates. In the
pure state, methane, ethane, carbon dioxide and hydrogen sulfide form structure-I
hydrates. However, since propane and isobutene molecules can enter only the large
cavities of structure II, a natural gas containing propane and isobutane generally forms
structure-II hydrates. Normal butane does not form hydrates as a pure component.
Hydrate formation can occur when normal butane is mixed with other components (Rojey
et al., 1994; Sloan, 1997). The structure H was determined through diffraction and NMR
studies. In this structure, the 5
12
dodecahedra coexist with 4
3
5
6
6
3
dodecahedra as well as
5
12
6
8
polyhedra, with twelve pentagonal faces and eight hexagonal faces, forming large
cavities. The small cavities are stabilized by molecules like Xe, H
2
S and CH
4
, and the
large cavities by hydrocarbons with much higher molecular weights such as adamantine
and methylcyclohexane. The role that structure-H hydrates may play in natural gas
production is still unclear. However, it has been proven that hydrocarbon molecules
commonly found in condensates or oils, together with methane, can form this new
hydrate structure, under pressure and temperature conditions easily encountered in
production and transport facilities (Ryba, 2005).
2.5 Gas Hydrate Formation
Kinetics of hydrate formation is still a current research topic and it is discussed
elaborately in the next section. Since this process is not well understood, several theories
have been developed explaining the mechanisms of hydrate formation. Lederhos et al.
(1996) proposed that gas hydrates form in an autocatalytic reaction mechanism, when
water molecules cluster around natural gas molecules in structures similar to the ones
shown in Figure 2.3.
9


Figure 2.3 Autocatalytic reaction mechanisms for hydrate formation (Lederhos et al., 1996)

This attraction between neighbouring guest molecules is termed hydrophobic bonding,
which can be described as an attraction between the apolar molecules inside the clusters
(B). Large and small clusters forming structures I and II are termed labiles because
they are easy to break down, but relatively long-lived. Labiles can dissipate, or grow to
become hydrate unit cells forming what are known as metastable nuclei (C). Then,
growth can continue until crystals are stable, indicating the onset of secondary nucleation
(D). This process is illustrated in Figure 2.4.


Figure 2.4 Three cavities in gas clathrate hydrates: (a) 5
12
, (b) 5
12
6
2
, (c) 5
12
6
4
(Paez et al., 2001)

2.6 Kinetics and Morphology of Gas Hydrates
Many articles have been published concerning the processes of gas hydrate formation.
The researchers became well aware from the experiments that at the beginning of hydrate
formation the temperature can vary widely, at one and the same pressure. As a result of
experimental studies it was determined that the process of hydrate formation starts at the
free gas water surface:
a. on a free contact surface of liquid water-gas or liquid water-liquid gas,
b. on the surface of the water drop-water film that condensed in a gas volume,
10

c. on the surface of gas bubbles that separate out within a water volume,
d. on the interface of the condensed gas drops-dispersed condensed gas, as the
condensed gas evaporates within a volume of free gas saturated with water vapours,
e. on the water-metal interface where the absorption of the molecules of gas dissolved
in the water takes place,

After the formation of critical size nuclei, a hydrate film forms around them and blocks
the free interface. After the hydrate film formation over the whole gas-water interface,
the surface-contact process becomes a diffusive one, when the molecules which form
hydrate on the sorptional surface of the growing crystal through defects in the formed
hydrate film. Sorptional surface can be on the free surface of growing crystal (massive
hydrate crystals) and at the base of the growing crystals (whiskery crystals). Molecules of
water and gas diffuse to the sorptional surface both from a volume of gas and from a
volume of water through the hydrate film at the gas-water interface. During the formation
of whiskery crystals, hydrate forming molecules go to the sorption surface on the surface
of growing whiskery crystals by means of tunnel diffusion. Tunnels are formed at the
vessel-growing hydrate interface. During tunnel diffusion the size of the diffusion
channels are much smaller than during the sorption by an open surface of a growing
crystal. Massive crystals grow more often in a volume of gas. Whiskery crystals grow
both in a volume of gas and a bulk of water. Gel-like crystals are formed at certain
conditions in bulk of water, whose nature will be studied further. In redistribution of mass
and volume of crystals a change occurs in P-T conditions- possibly changes in crystals
also occur. Crystals may sublimate in a volume of gas, dissolve in a volume of water, and
form new forms of crystals.

Unfortunately, the mechanism of nucleation and growth of hydrate crystals in static
conditions and in fluid flow is unknown at this time. Previous models for hydrate kinetics
that are quantified have normally been limited to the regime of steady crystal growth.
Kinetics of hydrate formation was viewed only from the aspect of hydrate accumulation,
depending on the degree of flow super cooling and turbulence. These are only the
external factors of hydrate formation. The kinetics of hydrate dissociation was studied
11

very little. Morphology of hydrate crystals has hardly been studied at all, although it
allows us to discover the crystals nucleation and growth. The modern theory of hydrate
formation processes can not answer many fundamental questions (Makogon, 1997).
2.7 Fundamental Phase Equilibrium for Natural Gas Hydrates
The phase equilibria of natural gas hydrates represents the most important set of
properties which differ from those to ice. In contrast to kinetic phenomena, hydrate phase
equilibrium is well-defined and determines a boundary to the kinetic problem (Sloan,
1997). Figure 2.5 shows the main features of the phase diagram when a hydrate is formed
with a pure hydrocarbon.

Figure 2.5 Hydrate Phase Diagram (Rojey et al., 1997)

In this figure, curve 1 represents the vapour pressure of the hydrocarbon. Curve 2, 2, 2
delimits the hydrate formation region. The slope change at LQP corresponds to the water-
ice phase change. At point LQP (low quadruple point), the gaseous hydrocarbon, liquid
water, ice and hydrate phases coexist. The slope change at HQP corresponds to the phase
change of the hydrocarbon. At point HQP (high quadruple point), the liquid hydrocarbon,
vapour hydrocarbon, liquid water and hydrate phases coexist. For hydrates to be formed,
12

the presence of liquid water has traditionally been considered necessary (Katz et al.,
1959).


Figure 2.6 Hydrate formation regions for C1 to C4 paraffins (Katz and Lee, 1990)

However, Sloan (1997) indicates that this is not an absolute prerequisite. If the
thermodynamic conditions necessary for hydrate formation are satisfied, the absence of
liquid water introduces a limitation of a kinetic order, making hydrate formation unlikely
but not impossible, especially if nucleation seeds are present. In general, hydrate
formation is favoured by the presence of fine particles acting as crystallization seeds,
such as hydrate microcrystals and solid particles (dust, corrosion products). It is also
favoured by factors that tend to influence flow turbulence, such as a high flow velocity,
pressure pulsation and any type of agitation. To remove the hydrates formed, it is
normally sufficient to establish temperature and pressure conditions lying outside the
formation region. However, the disappearance of hydrate crystals may take relatively
long time, and may be difficult to achieve. Hydrates remaining outside equilibrium for
periods of several days have been observed in the laboratory and in depressurized
13

collecting systems. Microscopic crystals generally persist for long periods after the
hydrates have disappeared visually (Rojey et al., 1997). Figure 2.6 shows the hydrate
formation ranges for methane, ethane, propane and butanes determined from the data
presented by Katz and Lee (1990).
2.8 Hydrate Properties
Natural gas hydrate contains about 180 Sm
3
of gas per m
3
of hydrate and can be used to
store and transport natural gas. The hydrate needs to be refrigeration to a temperature in
the range -20C to -10C to be stable at near atmospheric pressure. The pressure suitable
for making hydrates (formation pressure) will be in the range 60-90 bar, depending on
temperature. Natural gas hydrate formed at equilibrium conditions contains about 15%
wt. gas and 85% wt. water. The exact pressure-temperature conditions for hydrate
formation and decomposition are governed by thermodynamic equilibrium. Equilibrium
curves for methane hydrate and a mixture hydrate (93% mol methane, 5% mol ethane and
3% mol propane) are shown in figure 2.7. Methane hydrate needs higher pressure to form
than mixture hydrate; similarly, methane hydrate decomposes into gas and water at
higher pressure than mixture hydrate. The heat of natural gas hydrate formation is about
410 KJ/Kg compared to 333.5KJ/Kg for ice. The higher heat of formation of hydrate is
due to the inclusion of gas molecules in the ice-like hydrate structure. It follows that
considerable heat must be removed before natural gas hydrate forms. In industrial
processes, the hydrate heat of formation must be removed in heat-exchange equipment.

Figure 2.7 Equilibrium curve for methane hydrate and mixture hydrate (Gudmundsson et. Al., 2000)

14

When heat is removed, hydrate will also be formed, provided the pressure is above the
equilibrium line. This is one of the major challenges in designing commercial NGH
processes. The high heat of NGH formation contributes also its stability at atmospheric
pressure. NGH particles at temperature in the range -20C to -10C and atmospheric
pressure will be below the equilibrium line. Given enough time, the refrigerated particles
will decompose into gas and water. However, hydrate particles refrigerated -20 C to -10
C and stored in large-volume tanks will be surrounded by other hydrate particles. If the
large-volume tanks are insulated, there will be no or limited heat flow from the outside.
The refrigerated hydrate particle will therefore not receive the heat needed to melt
(Gudmundsson et. al., 2000).
2.9 Chemicals for Gas Hydrate Control

Gas hydrate formation can cause problems in several areas of the gas and oil industry
including drilling operations (particularly in deep water), production and process, well
workovers, and injection pressure support operations where gas and water come into
contact.

There are three basic ways in which chemicals can be applied to prevent gas hydrates
from plugging pipes and flowlines. They are categorised as follows:
2.9.1 Thermodynamic Inhibitors

These chemicals change the bulk thermodynamic properties of the fluid system, thereby
shifting the equilibrium conditions for hydrate formation to lower temperatures. Thus
they can be used to prevent hydrate formation and also melt existing hydrate deposits.
They are added at high concentrations, often 10-50% based on the water phase to shift the
chemical potential of a system for hydrate formation to lower temperature at a given
pressure or higher pressure at a given temperature. They are also called anti-freezes and
by far the most common chemical class used to prevent hydrate formation and remove
hydrate plugs. The most commonly used classes of thermodynamic inhibitors are
alcohols, glycols and salts (Kelland, 2000).
15

2.9.2 Kinetic Inhibitors (KI)

These chemicals delay hydrate nucleation (slow crystal growth) for long enough periods
to allow the fluids to be transported or operations to be carried out without hydrate
formation. They are added at less than 1 wt.%.

The key ingredients in kinetic inhibitors are water-soluble polymers or copolymers with
pendent alkylamide groups. Polyoxyalkylenediamines have also been used. A variety of
polymer classes have been investigated but to date the only polymer classes in
commercial use are based on vinyl pyrrolidone or N-methyl-N-venyl acetamide. Other
classes of polymers which have been shown to have significant performance as KIs
include amide derivatives of maleic anhydride (now commercially available), and
alkylacrylamides (Figure 2.8).


Figure 2.8 Monomer Units for Kinetic Inhibitor Polymers: Vinyl Pyrolidone (top left) and
Vinylcaprolactam (top right), Isobutylamine Derivative of Maleic Anhydride (bottom left), Acryloyl
Pyrrolidine (bottom middle) and isopropylacrylamide (bottom right) (Kelland, 2000)

There are two proposed theories on the mechanism of inhibition by kinetic inhibitors. The
first is related to the perturbation of the water by the inhibitor preventing hydrate
embryos from reaching the thermodynamically stable critical nuclear size. The second
theory states that interaction of the inhibitor with the hydrate embryos delays (prevents)
their growth to the critical nuclear size. This second theory has evidence both from
experimental and molecular modelling studies to suggest that it accounts for at least part
of the inhibition mechanism. For example, kinetic inhibitors have been shown
16

conclusively to adsorb to tetrahydrofurane hydrate crystal surfaces, which are Structure
type. Secondly, molecular modelling indicates that the alkylamide side chains of kinetic
inhibitors interact strongly with the cavitous surface of hydrates. The pendent alkylamide
groups can interact in two ways with the hydrate surface. Firstly, the alkyl group
penetrate an open cavity, and then the amide group hydrogen-bonds to the hydrate
surface via the carbonyl group locking the alkylamide to the surface (Figure 2.9).


Figure 2.9 Crude illustration of the interaction of a pendent alkylamide group of a kinetic inhibitor
polymer with a cavity of a gas hydrate (Kelland, 2000)

2.9.3 Anti-Agglomerants (AA)

Anti-agglomerants prevent the deposition and agglomeration of hydrates by forming
slurry of hydrate particles which can be transported in the remaining fluid comprising
mostly liquid hydrocarbon. They are surfactants and are added at less than 1 wt. % based
on the water phase. The need for a liquid hydrocarbon phase restricts their use to oil and
gas condensate fields. There are two methods by which a surfactant can function as an
anti-agglomerant. Firstly, the surfactant interacts via its polar headgroup with the hydrate
surface affecting the crystal growth process. In addition, the hydrophobic tail of the
molecule oil-wets the hydrate particles preventing their agglomeration and dispersing
them in the liquid hydrocarbon phase. Secondly, the surfactant forms a tight water-in-oil
emulsion with the produced fluids. Hydrate formation occurs within the water droplets
and is confined to the droplets. This prevents hydrate agglomeration and produces a
dispersion of hydrate particles. The surfactant has no significant interaction with the
hydrate crystal surface. These products are also known as hydrate dispersant additives.
Products that function by the first mechanism were first developed by Shell. The best
17

performing anti-agglomerants are quaternary ammonium surfactants in which the
ammonium headgroup has two or three butyl or pentyl groups attached to the quaternary
nitrogen. The surfactant can be twin-tailed or mono-tailed (Figure 2.10).


Figure 2.10 Structure of quaternary anti-agglomerants; R is a long alkyl chain, R
1
is H, or methyl,
and R2 is butyl or pentyl (Kelland, 2000)

Besides inhibiting the hydrate crystal growth, the quaternary anti-agglomerants function
in the following ways:
Keep the walls of the pipeline oil-wet, hindering hydrate formation and
deposition at the walls (act as weak corrosion inhibitors).
Concentrate at the water-hydrocarbon interface, where hydrate formation is
most pronounced, and thereby raise the local concentration of ions to freezing
point depressing levels.
Modify the structure of the water near the water-hydrocarbon interface in such
a way as to hinder the formation of hydrate crystals.
Impede further access of water molecules to the hydrate crystal after
attachment to the hydrate crystal.
Prevent agglomeration of hydrate crystals by making their surface
hydrophobic.

The second anti-agglomerant mechanism, involving emulsion technology, was developed
by IFP. One product has been field trialled twice in Argentina with varying success. The
active emulsifier is a complicated mixture of polymerised fatty amides and fatty asters.
Since this technology does not rely on slowing the growth rate of hydrate formation, but
only confining it to the emulsified water droplets, it has the potential to work at any
18

subcooling. For all anti-agglomerant products, one must consider the transportability of
the hydrate slurry. The hydrate particles must be kept transportable and not deposit or
build up at any point in the line. Most applications will be restricted to a water-cut of
maximum 30-40%, since above this value the slurry rheology changes significantly
which may cause flow problems and unwanted pressure drop in the line. Anti-
agglomerants must be compatible with other production chemicals as well as with
sealants and other pipeline materials. The products should not cause any process upsets
such as emulsion separation problems and discharge water quality. Finally, the products
must also be compatible with downstream processing facilities such the condensate
stabiliser equipment, i. e. they must degrade at a suitable rate at the system temperature
(often 150-200C). Some crude oils contain components which act as anti-agglomerants.
By understanding the conditions under which these oils are able to prevent hydrate
plugging, it should be possible to avoid the use of artificial hydrate inhibitors in some
applications (Kelland, 2000).

Kinetic inhibitors and anti-agglomerants are collectively known as low dosage hydrate
inhibitors or LDHIs. LDHIs have only recently been applied in the field but offer
significant cost savings and other benefits compared to non-chemical hydrate methods or
the more traditional thermodynamic inhibitors. In addition to the above methods, a fourth
chemical method is possible, so-called heat-generating chemicals. However, their use
seems more applicable to melting existing hydrate deposits rather than preventing hydrate
formation and deposition (Kelland, 2000).

Different types of hydrate control methods are shown in a Hydrate Control Methods
tree upon a ground of Sound Engineering Practice/design in Figure 2.11.
19


Figure 2.11 Hydrate Control Methods Tree (Gjertsen, 2000)

2.10 Background of Colloids
The concepts and the name of colloid are credited to Thomas Graham (1861). His two
criteria were: (a) restricted diffusivity (colloids being held back by a membrane), (b)
optical turbidity (light scattering). Both indicate the presence of particles much larger
than ordinary molecules such as sucrose. Nowadays it is clear that the former typify
dispersions of optically sub-microscopic particles, while the latter consist of stable
solutions of very large molecules. The first class is now referred to as lyophobic
colloids (i.e. disliking their environment, and hence potentially unstable) and the second
as lyophilic (liking and spontaneously soluble in their liquid). Colloids seemed not to
20

fit the standard laws of the classical physical chemists, and were simply disregarded by
many of them. Qualitative ideas about electrical charges on colloidal particle were
around long before 1930. However, calculating the repulsion forces between particles as
a function of the distance between them is not a simple matter of applying Coulombs
law. A start on the problem was made around 1938. By then it was realized that all
colloidal particles have an influence on the liquid around them. Lyophobic particles,
when charged, exert an effect on the ionic environment; lyophilic particles interact with
their solvent medium in the same way as sucrose does. Already in the 1920s the great
classical colloid chemist H. Freundlich realized that the key to colloid science was to be
found in the special phenomenon associated with surfaces (most of the information in this
section is taken from Laskowski and Ralston, 1992).
2.11 The Classical Interface Model
Phase
Phase
i
Phase
Phase
i

Figure 2.12 Interface between phase and phase

An interface is boundary between two phases (such as Gas/Liquid, Liquid/Solid, L
1
/L
2
; in
Figure 2.12). To the eye it appears perfectly sharp. The very fact that the phases do not
intermingle shows that there is a drastic difference in the molecular environment on the
opposite sides. The difference may lie in the packing (as for a solid at its m. p.) or
molecular kind (as for oil/water). Long before it became possible to analyze
intermolecular forces at interfaces, valuable understanding was achieved through the
dynamic approach- a method which, within limits, is still valid and useful. Capillary
phenomena indicate that a force is required to extend a liquid meniscus the classical
model of surface tension. Experiment shows that the tension () does not change with
21

extension of area (A) and does not depend on the size or form of the liquid surface, but
does depend on the substance.

It follows that at constant temperature and pressure, an interface of area A and tension
requires work A to form it and this work must somehow be stored by the molecules. It is
recoverable and is therefore surface free energy. For pure liquids the surface free energy
per unit area (measured in mJm
-2
) in numerically equal to its surface tension (mNm
-1
).
All the phenomena of capillarity can be perfectly explained surface tension model,
provided that the system is macroscopic. The model is not valid for exceedingly small
bodies (Laskowski and Ralston, 1992).
2.12 Wetting Mechanism: Liquid on Solid
Spreading or retraction of a liquid over a solid depends on the principle of surface tension
of that liquid. Here, firstly,

and

can not be identified with measurable tensions, but
must be read as surface free energies. Secondly, the problem is simplified only if the
solid surface can be assumed to be ideally smooth and uniform in molecular nature; if it
is not, there may be barriers to the movement of a meniscus. Thirdly, the liquid is
assumed to be both pure and a non-solvent for the solid. As with liquid substrates, three
types of behaviors may be found with different materials. There may be complete
spreading, as with water on perfectly clean glass. Or there may be non-spreading, the
liquid shrinking into one drop (e. g. mercury on glass, water on paraffin wax). Or there
may be initial spreading, followed by liberation of droplets with an invisible monolayer
between them- as happens with certain polar oils on metals or polar solids.



Figure 2.13 Equilibrium of a non-spreading drop on a planar solid (Laskowski and Ralston, 1992)

22

In an ideal system of the kind defined above, a retracting drop shrinks in area until it
reaches an equilibrium form. Its perimeter can be seen to meet the solid at a certain angle,
the angle of contact, , measured in the liquid phase at the 3-phase line (Figure 2.13). The
equilibrium angle corresponds again to the net minimum of surface free energies, A,
for which Thomas Young in 1805 gave the equation named after him, namely:

SV
=
SL
+
LV
cos
Where, the subscripts S, L and V stand for solid, liquid and vapour phases, respectively.
As before, the values must be those for mutually equilibrated phases. The form of the
bulk of the drop is governed by the minimum of surface plus gravitational energy,
unaffected by (Laskowski and Ralston, 1992).
2.13 Static Contact Angles
A bubble or a droplet minimizes its free energy by adopting a spherical shape in the
absence of gravity. When the bubble or droplet contacts either a solid or a liquid substrate
it will still minimize its free energy. Essentially the sum:

LV
A
LV
+
SV
A
SV
+
SL
A
SL
, must be minimized where is a surface on interfacial tension,
A is an area and the subscripts LV, SV and SL denote the respective interfaces between
the liquid, vapor and solid phases. If, say, a drop is placed on a solid surface it may
spread to form a thin liquid film or it may remain as a discrete droplet. In the first
instance the behavior may be described as complete wetting whilst the latter corresponds
to partial wetting. Similar behavior is exhibited by a bubble contacting a substrate. There
will certainly be some interaction between the fluid and the solid substrate upon which it
rests, even if this is due only to Van der Waals forces. Some type of surface interaction,
such as adsorption or ionization of surface groups is likely in many cases.
23



Figure 2.14 Sessile bubble with axial symmetry on a solid surface immersed in a liquid in a constant
temperature chamber (Laskowski and Ralston, 1992)

As shown in figure 2.14, the contact angle is the angle contained between planes tangent
to the surfaces of the solid and the liquid at the Wetting perimeter. In the example shown,
is measured through the vapor phase. The wetting perimeter is frequently referred to as
the three-phase line of contact (tplc) but really is a small zone where the three phases
merge. One needs to distinguish, in practice, between situations where the fluid is tending
to advance over or retreat from the surface in question. The limiting static angles
determined for these two cases correspond to the advancing (
A
) and receding (
R
)
contact angles. In general,
A

R
(Laskowski and Ralston, 1992).
2.14 Works of Hirata and Mori (1998)
Hirata and Mori used a simple experimental technique in order to observe the
axysymmetric menisci formed on vertically-oriented cylindrical rods of a polycrystalline
clathrate hydrate. They observed the menisci formed with water/fluorocarbon, air/water
and air/fluorocarbon pairs so that they could evaluate, though rather roughly, how water
and a fluorocarbon wet, in a macroscopic sense, clathrate hydrate surfaces when they are
displacing, or displaced by, the fluorocarbon or air.
2.14.1 Experiments

An aqueous THF solution adjusted at the theoretical composition of THF hydrate
(THF.17H
2
O) into vertically held 12 mm ID silicon rubber tubes each stoppered at its
both ends with rubber plugs and axially pierced by a 2 mm diameter stainless steel rod.
24

These tubes charged with the THF solution were kept in a refrigerator till the solution
was totally solidified. The tubes were then cleaved carefully so that the cylindrical THF
hydrate rods (12 mm in diameter and typically some ten centimeters long, each holding a
steel rod on its axis) could be taken out. The steel rod was to serve as a weight to enable a
gravity dependent immersion of the hydrate rod. Then each hydrate rod was vertically
hung in a low temperature chamber by thread which was connected to a fine motor-
driven screw-gear mechanism. Manipulating this mechanism, the hydrate rod could be
pulled up or down at a prescribed speed. A 300 cm3 glass beaker (72 mm ID) holding
HCFC-123 and water or HCFC-123 only or a 100x100x100 mm rectangular vessel made
of transparent PMMA [polymethyl methacrylate] plates holding water only was placed,
together with a rectangular PMMA-made water bath, in the chamber such that the hydrate
rod was immersed partly in the liquid (or liquids) or contained in the beaker or the
PMMA vessel, crossing the water/HCFC-123, air/water or air/HCFC-123 interface
(Figure 2.15).


Figure 2.15 THF hydrate partly immersed in liquid phases contained in a water-jacketed test vessel
(Hirata and Mori, 1998)

Some portion of the inside beaker wall including the water/HCFC-123 interface level was
covered with a thin, semitransparent Teflon film to modify the shape of the meniscus
formed on the wall in such a way that it no longer interfered with the meniscus formed on
25

the hydrate rod. A thin vinyl chloride sheet, instead of a Teflon film, was attached onto
the inside wall of the PMMA vessel to almost vanish the water meniscus on the wall. The
temperatures of the test liquids as well as the ambient air temperature were kept below
the critical dissociation temperature of THF hydrate, 4.1C. It is well known that the
macroscopic contact angle measurement through a liquid phase partly wetting a solid
surface inherently depends on the direction and the speed of liquid-to-solid relative
motion. Therefore every experiment was so operated that it could continuously be
observed with the aid of a video camera, the geometry of a liquid/liquid or air/ liquid
interface while a hydrate rod was pulled down across the interface at a constant speed as
low as .06 mm/s, or pulled up at the same speed. The contact angle of the denser liquid
observed on the hydrate rod being pulled down should approximate the advancing contact
angle, while that observed on the rod being pulled up should approximate the receding
contact angle.
2.14.2 Results and Discussion of Hirata and Moris Experiment

Figure 2.16 summarizes typical video-graphic pictures obtained with three kinds of
interfaces each advancing or receding on a THF hydrate rod as the result of its
descending or ascending motion. The temperature was held almost constant during each
run but slightly different from run to run; the liquid temperatures measured in the runs in
which the pictures shown in figure 2.15 were obtained fell in the range 1.0-2.1C. Since
the hydrate rods were kept at an even lower temperature before use, it was likely that
there was a weak spatial temperature variation inside the test vessel in each experimental
run. Nevertheless, no evidence was found for even a minute thermocapillary or free-
convection motion inside the vessel and hence assumed that any temperature variation
possibly present in that experimental system little affected the wetting behavior of present
interest.

26



Figure 2.16 Video graphic pictures (a) water/HCFC-123, (b) air/water, and (c) air/HCFC-123
deformed by THF hydrate rods in vertical motion across the interfaces (Hirata and Mori, 1998)

In the first two pairs of pictures, (a) and (b), given in figure 2.16, it was readily noted that
liquid water had small contact angles, whether it was faced with a fluorocarbon liquid or
air, on the surface of a hydrate phase. This fact indicated that THF hydrate and
presumably clathrate hydrates in general had highly hydrophilic surfaces. On the other
hand, the last pair of pictures, (c), suggested that in the absence of any liquid water, even
hydrophobic liquids may contact the hydrate surfaces at small contact angles. In their
work, the quantitative evaluation of the on-hydrate contact angles based on the
observations was abandoned. This was because the surfaces of hydrate-rod samples were
not highly smooth and hence the location of the three-phase contact line on each video
image could not be specified with a sufficient accuracy. Nevertheless, the present study
has provided with some fundamental knowledge of liquid wetting on hydrate surfaces.
27

3 Set-up and Procedure of Experiment
3.1 Introduction
Different from the works of Hirata and Mori (1998), where they used hydrate rods, I tried
with a cell (Figure 3.1) designed and built for conducting the experiment of hydrates.
Then I should be able to compare the observations and findings from these two methods.
For safety and avoiding hazards, I should at first make some leakage and performance
tests of the cell. Then, I should make solution of THF and water to make hydrate with
proper safety measures. The procedures of THF solution preparation with necessary
safety measures and experiments are given in the next sections in details.
3.2 Hydrate Cell
The cell (Figure 3.1) was an almost cube-shaped box with 15 cm. x 15 cm. base-area and
10 cm. height. There was a horizontal partition at 3 cm. below the top. This partition
completely isolated the upper chamber from the lower chamber. The cell and the partition
are made of PMMA. The upper chamber was used for coolant circulation and THF
solution was kept inside the lower chamber. For filling THF solution into the lower
chamber, there was a hole at the bottom of the THF chamber. Normally this hole was
closed but can be opened while filling or emptying was required.

28



Figure 3.1 Hydrate Experiment Cell

There were two lines into the upper chamber, one for coolant inlet while the other for
coolant outlet. These were connected to a cooling unit which circulates 96% pure ethyl
alcohol across the cell. There was a temperature controlling system at the cooling unit,
which helped to control the circulation temperature. A hydrate layer is normally formed
at the top of the THF chamber (lower chamber), where the temperature is achieved as low
as the coolant temperature. There was no insulation or cooling of the rest of the cell
ensuring that it would have ambient temperature at the bottom. So it would give a finite
layer of hydrate without filling the entire chamber. Oil droplet was then allowed to
deposit underneath the hydrate layer by the use of an inverted needle and syringe. Once
the oil droplet contacts the hydrate layer, the contact angle could be observed by taking
pictures. From the observations, contact angles could be measured as a function of crude
oil composition, temperature etc.
3.3 Leakage and Performance Tests
Once the hydrate cell was found ready for conducting our specific experiment, it was
necessary to carry out certain leakage and performance tests in order to be sure if there
29

was any leakage in the joints or partitions of the cell and if it functioned well along with
the cooling unit. At first the bottom chamber was filled completely with water for few
hours. If no leakage was found around the cell then the circulation of coolant was started
at a very low temperature (say -9C). If the cooling unit functioned properly then one
would be able to find a layer of ice at the top of water phase in the bottom chamber after
some time (Figure 3.2). There would be no pressure test because the experiment would be
carried out at atmospheric conditions.


Figure 3.2 Performance test of hydrate cell

3.4 List of chemicals and samples
The following chemicals and samples were used in the experiments:
Tetrahydrofuran (for hydrate preparation),
Water,
Ethyl Alcohol (for circulation of coolant),
Exxsol d80 which is a condensate-like refined oil (Sample-1),
30

King crude oil from the Gulf of Mexico (Sample-2),
Paladio crude oil from West Africa real oil straight from the well (Sample-
3),
Unidentified light oil from Norsk Hydro which is light condensate-like refined
oil (Sample-4).
3.5 Preparation of THF Solution
To mix a solution which would form hydrates, I should do the following:
In a mixing container, I poured in carefully 19% by weight THF and 81%
by weight water; this is the same as 21% by volume THF and 79% by
volume water.
I mixed the solution properly, by gentle stirring.
I poured the mixture into the cell carefully using a funnel to avoid spilling.
I used gloves and glasses for protection and tried to avoid breathing the
fumes.
I closed the cell carefully, making sure that it was completely full.
I should not pour the remaining extra solution back into the THF bottle. I
covered it well (with plastic, to avoid evaporation) and saved for future
use.
3.6 Procedure of Experiment
At first I filled the bottom chamber completely with 21% (volume) of THF
in water.
I connected the inlet and outlet lines of the upper chamber with cooling
unit.
Then I started circulation of coolant at -9C. Although the hydrate
formation temperature for this mixture is 4.4C, I set the circulation
temperature at -9C just to get the hydrate layer quickly.
After circulating for few hours, layer of hydrate was formed. But it was
not a regular shaped layer. The hydrate layer was extremely rough and
irregular.
31

A sample of oil was taken into the syringe.
Very little (1 or 2 droplets) amount of the sample oil was deposited
underneath the hydrate layer with the help of the syringe.
The oil droplet went just below the hydrate layer and the contact surfaces
between the hydrate layer and oil droplet were observed.
To make better observation, I took some pictures and drew sketches.
Then I attempted to measure the contact angle.
I repeated the experiments with other samples.
Variation of contact angles for different kinds of samples was observed.
32


4 Observations and Results
4.1 Some Important Observations
The cell designed and built by me, passed the performance and leakage tests
satisfactorily. The cooler performed very well and could cool down the water inside the
cell satisfactorily. During performance test, a thin layer of ice was noticed over the water
level after circulating the coolant across the cell. The thickness of ice remained constant
when equilibrium (thermally) was achieved (as shown in figure 4.1).


Alcohol
T
h
i
c
k
n
e
s
s

o
f

i
c
e

Water
Figure 4.1 Observation of Performance test

Gel-like white hydrate was produced at the top of THF chamber from THF and water
mixture at very low (-9C) temperature. After that the THF chamber of the cell gradually
became opaque. So the hydrate layer was not seen clearly. But its existence was observed
by injecting coloured water. The hydrate layer was existing above the coloured water
phase (Figure 4.2). Here the cell was vertically rotated by 180 to bring the THF chamber
up.

33

Hydrate Level


Figure 4.2 Existence of hydrate level
Coloured Water
Alcohol

Among the four samples, Exxsol d80 (Sample-1) was almost transparent. Nothing
was observed when droplets of this sample were deposited underneath the hydrate
layer with the help of the syringe. But satisfactory observations were possible for the
other samples. All of them showed wetting angles although all the angles were not
clear but some ideas were possible to find out. Pictures of these observations are
given in Appendix A-6.
4.2 Results
The cell for hydrate experiment was built successfully. The dimensions of
the cell are given in figure 3.1. It was made of transparent polymethyl
methacrylate (PMMA) plates and the plates were fitted with each-other by
glue. A partition of PMMA plate inside the cell was also fitted by using
glue. The roof plate was fitted with several bolts. Then it passed the
performance and leakage tests satisfactorily. The cell functioned well
during the experiments only except some problems which were
manageable. These are discussed in details in chapter-5.
During the experiment gel-like hydrate was formed. As per available
literatures, it was structure-II hydrate.
The transparent and light Exxsol d80 (sample-1) did not give any good
result, because it was mixed into the THF chamber immediately after
being injected by the syringe. From figure 4.3, the angle was assumed to
34

be some 10. But this value was extremely rough because the wetting was
not clear and the droplets were mixed into the THF solution very quickly.

Figure 4.3 Wetting angle of Exxsol d80
King Crude Oil (Sample-2) showed a clear angle of 100 with completely
non-wetting tendency with the hydrate phase. The picture of this
experiment is shown in figure 4.4.

Figure 4.4 Wetting angle of King Crude Oil

In the next experiment, Paladio Crude Oil (Sample-3) produced an angle
of 45 with partially wetting with the hydrate phase (shown in figure 4.5).
35


Figure 4.5 Wetting angle of Paladio Crude Oil
The last sample of unidentified light oil from Norsk Hydro (Sample-4)
showed slightly different result than Exxsol d80. It roughly showed an
angle of some 29 (figure 4.6) with a tendency of mixing into the THF
solution.

Figure 4.6 Wetting angle of light oil from Norsk Hydro
36

5 Discussion

5.1 Discussion of problems encountered and solutions
Sometimes the alcohol level inside the cooling unit went down and
circulation of coolant was stopped giving an alarm. In these
circumstances, some alcohol was added (make up) into the alcohol
chamber of the cooling unit to start it again.

The quality of THF deteriorated while conducting the experiments. As a
result, the THF chamber became completely cloudy, and nothing inside
the chamber could be seen clearly (Figure A-5, Appendix A-6). It was thus
impossible to observe the wetting angles of the oil samples. The THF
chamber was washed with warm water, alcohol and at last with soap but it
was not as clear as at the early stages of experiments. And this not due to
the cell itself, as the same clouding was observed in glass containers. Due
to scarcity of THF, it was not possible to change the THF. A new solution
of THF was prepared and the previous solution was replaced by the new
solution. But it showed the similar behavior. The replaced solution was
stored safely in jars covered with plastic (Figure A-6, Appendix A-6).
Then the injecting needle was cut short such as the droplets of sample oil
contact the hydrate layer somewhere very close to the wall of the cell. This
time it was possible to see the droplets and take pictures.

While carrying out the experiments, some leakages at the partition inside
the cell were gradually being noticed. Then the leakages were repaired
with glue and the cell was filled with alcohol. It was observed for 24 hours
and no leakage was found. Whenever the experiment was started with
THF solution, it was leaking again at the partition. Then it was suspected
that the glues were poisoned by the low quality THF. Another possible
reason was that the glue might have been affected by the velocity of
37

alcohol circulation which was not encountered when the cell was filled up
with alcohol remaining stationary (figure 5.1).
Alcohol
Molecule
Glue
Alcohol
Molecule
Glue

Figure 5.1 Attack of alcohol molecules on the surface of glue

Figure 5.1 shows an idea of one possible reason of damage of glue due to
attack of high velocity alcohol molecules upon the surface of glue.
For the ease of observation and measurement of angles, the hydrate surfaces
were assumed to be plane but in reality these were very rough (figures A-1, A-
2, A-3 & A-4 in Appendix A-6).
The hydrate surface was assumed to be in equilibrium with the surroundings
(i. e. no more hydrate will be formed under those conditions) when the oil
samples were injected into the chamber although it was very difficult to notice
the equilibrium. It was not very unrealistic to run the circulation for several
hours at much lower temperature than the hydrate formation temperature of
the solution (4.4C at 1 atm. Pressure) and to assume that the surface to be in
equilibrium with the surroundings.
5.2 Discussion of Results
According to Hove (1998), a wetting surface is not a precise description. It can be
divided into the categories complete, partial and no wetting. The difference will be
due to the composition of wetting liquid and contact angles between the liquid and
38

hydrate surface. The liquid droplets may have different configurations on a hydrate
surface. On a plane surface they may be like anyone in figure 5.2. If the contact angle
between the droplet and the surface is higher than 90 as shown in figure 5.2 (a), the
surface is not wetted. If it is lower than 90 as in figure 5.2 (b), the surface will be
partially wetted. If the contact angle is close to zero like figure 5.2 (c), the surface is
completely wetted.


Figure 5.2 Wetting on hydrate surface

If figure 5.2 and figure 4.2 are compared then it can be clearly noticed that the
wetting angle for Exxsol d80 (sample-1) was close to zero (10). So sample-1 had a
tendency of wetting the hydrate surface.

King Crude Oil (sample-2) in figure 4.4 was clearly showing same wetting nature as
figure 5.2 (a). In figure 5.2 (a), the wetting angle was higher than 90 and for King
Crude Oil the angle was found 100. So it had no wetting tendency with the hydrate
layer.

Paladio Crude Oil had tendency of partial wetting with the hydrate layer because its
wetting angle was found 45 from figure 4.5, i. e. the wetting angle was <90 which
was same as figure 5.2 (b).

An unidentified light oil from Norsk Hydro (sample-4) showed wetting angle of 29
(figure 4.6). Its wetting angle was in between that of Exxsol d80 and Paladio Crude
Oil. So it had more wetting tendency than Paladio Crude Oil but less than Exxsol d80.
39


5.3 Comparison with previous works of Hirata and Mori (1998)
In Hirata and Moris experiment, a hydrate rod was pulled down pulled up at the
same speed (figure 2.16). The geometry of liquid/liquid or air/liquid interface was
observed with aid of a video camera. From the observations it was readily noted that
liquid water had small contact angles which indicated that clathrate hydrates in
general have highly hydrophilic surfaces.

Hirata and Mori (1998) abandoned to quantitatively evaluate the on-hydrate contact
angles based on observations because the surfaces of the hydrate rod samples were
not highly smooth and hence they could not specify the location of the three phase
contact line on each video image with a sufficient accuracy. However their study
could provide some important fundamental knowledge of liquid wetting on hydrate
surfaces.

I did not have any arrangement for observing wetting characteristics of water upon
clathrate hydrate surfaces. The excellent idea of Hirata and Moris experiment was
that they could observe the wetting angles of different substances in different phases
at the same time. But the problem was it had been very difficult to find the wetting
angle from their experiment. Since both the hydrate layer and THF solution were
stationary in our experiment, it was easier to observe and measure the wetting angles.

Hirata and Mori used extra pure grade THF (99.0 wt % certified purity) supplied
from Junsei Chemical Co. Ltd., Tokyo while I used 99.8% pure THF from Merck
KGaA, 64271, Dramstadt, Germany (properties are given in Appendix A-1). They
used de-ionized and distilled water but I used fresh tap water. In my case, the THF
was showing some inexplicable clouding features, which the manufacturer was
unable to explain. As a result, they could not form very good hydrates. For obtaining
better observation and quantitative data, a considerable refinement of experimental
techniques and higher quality chemicals are required.
40


6 Conclusion and Recommendation for Future Works
6.1 Conclusion
Hydrate wettability is found to be a governing parameter for hydrate morphology and
hence, the hydrate plugging tendency. The wettability of clathrate hydrates is
significantly altered on addition of chemical additives at low concentrations.
Moreover the chemical effect is crucially dependent upon crude oil composition and
same additive may give different effects on different crude oils. Study of wetting
phenomenon/wetting angle of crude oil with clathrate hydrates is now-a-days very
important issue because it determines the complete, partial or non-wetting tendency
of crude oils upon clathrate hydrates.

In order to study the wetting phenomena, a simple cell was designed and built where
the experiment would be carried out. 21% (wt) of THF solution was used for hydrate
preparation. It starts forming hydrate at 4.4C. 96% pure ethyl alcohol was circulated
to cool the THF solution down to -9C so that hydrate could form quickly. An
achievement of equilibrium of hydrate phase with THF phase was assumed.
Structure-II type hydrate was supposed to form.

Four different kinds of oil samples were studied in the experiments. Each sample was
injected underneath the hydrate layer by droplets with the help of a syringe. Then
their wetting angles with hydrate surface were observed. An attempt was made to
measure wetting angles of the samples on the basis of visual observation and
photographs taken during the experiments. It was not an easy task to observe the
wetting angles at the hydrate surface because the surface was not theoretically smooth
and on the other hand it was a soft gel-like layer. The experiment could only give an
idea of wetting characteristics of crude oil with clathrate hydrates.

The observations showed a higher wetting tendency if the angles between oil droplet
and hydrate surface were lower than 90 (Paladio Crude Oil and the unidentified oil
41

from Norsk Hydro). This is called partial wetting. If the angle approached towards
zero then the surface would be called completely wetted (Exxsol d80). The surface
would be considered no or little wetted if the angle was more than 90 (King Crude
Oil). It was found from the work of Hiland and others (2005) that wetting is
dependent on crude oil composition and the generation of oil wet hydrates could be
correlated to low hydrate plugging tendencies at realistic conditions. If the findings of
Hiland and others work and that of my work are compared, then it comes out that
Exxsol d80 will have the lowest hydrate plugging tendency and King Crude Oil will
be more likely to form hydrate plugs. Paladio Crude oil and the unidentified oil from
Norsk Hydro will show an intermediate tendency of forming hydrate plugs i. e. more
plugging tendency than Exxsol d80 but less than King Crude Oil.
6.2 Recommendations for future works
Very little have so far been studied and reported on surface phenomena of gas
hydrates. More experiments should be carried out with varieties of samples of oil in
order to understand the phenomena. Different structures of hydrates should also be
studied. Refinements of experimental techniques are required for obtaining
quantitative data with higher level of accuracy.

The quality of observation could be improved by introducing better kind of hydrate
i.e. hard and smooth hydrate levels where wetting takes place. Special care is needed
for preparing hydrate. Very high quality THF and pure distilled water should be used
for preparing hydrates in future. And also glass cell needed (as the walls of PMMA
cell got cloudy and the glue disintegrated) with rubber sealings instead of glue. For
continuous monitoring of experiments, both video and still cameras can be introduced
in future.

The mechanisms of gas hydrate formation and inhibition are still not well understood.
More researches should be conducted to understand the mechanisms of formation and
inhibition of gas hydrates.
42


References:
Andersson V., Mork M and Gudmundsson J. S., 2000, Hydrater for Lagring og
Transport av Naturgass in Hydrateroljeindustriens usynlige problembarn,
TEKNA course compendium, NTNU, January, P2, P10.

Binks B. P., 2002, Particles as surfactants similarities and differences in Current
Opinion in Colloid & Interface Science, Volume 7, PP 21-41.

Gjertsen L. H., 2000, Hva koster en plugg in Hydrateroljeindustriens usynlige
problembarn, TEKNA course compendium, NTNU, January, P10.

Hirata A. and Mori Y. H., 1998, How liquids It clathrate hydrates: some
macroscopic observations, Chemical Engineering Science, Volume 53, No. 14, PP
2641-2643.

Hove A. M., 1998, Transport of Hydrates in Multiphase Pipelines, Unpublished
Diploma Thesis, Department of Refrigeration and Air Conditioning, NTNU, PP 5-8.

Hiland S., Askvik K. M., Fotland P., Alagic E., Barth T., Fadnes F., 2005,
Wettability of Freon hydrates in crude oil/brine emulsions in Journal of Colloid
and Interface Science, Volume 287, Issue 1, PP 217-225.

Hiland S., Borgund A. E., Barth T., Fotland P. and Askvik K. M. 2005, Wettability
of Freon hydrates in crude oil/brine emulsions: The effects of chemical additives,
Proceedings of the 5
th
International Conference on Gas Hydrates, Trondheim,
Norway, June 13-16, PP 1151-1161.

Kalli C. J. And Cowie D., 1990, Hydrates: Towards the Complete Solution, SPE
20958, PP 147-150.

Katz D. L., Cornell D., Kobayashi R., Poettmann F. H., Vary J. A., Elenbass J. R.,
Iinaug, C. F., 1959, Handbook of Natural Gas Engineering, McGraw Hill Book
Co., PP 775-777.

Katz D. L., Lee R. L., 1990, Natural Gas Engineering- Production and Storage,
McGraw Hill Publishing Co., PP 197-230.

Kelland M., 2000, Hindering av hydratproblemer- Kjemiske metoder in Hydrater
oljeindustriens usynlige problembarn, TEKNA course compendium, NTNU,
January, PP 1-13.

Laskowski J. S. and Ralston J., 1992, Colloid Chemistry in Mineral Processing,
Elsevier Science Publisher B. V., PP 2-8, 173-223.

Lederhos J. P., Long J. P., Sum A., Christiansen R. L. And Sloan E. D. Jr., 1996,
Effective Kinetic Inhibitors for Natural Gas Hydrates, Chemical Engineering
Science, Volume 51, No. 8, PP 1221-1222.
43


Lobanov M. V., Lokshin K. A. and Zhao Y., 2005, Multiple cage occupancy and
crystal structure variations in natural gas clathrate hydrates, Proceedings of the Fifth
International Conference on Gas Hydrates, Volume 2, Structure and Physical
Properties, PP. 1-4.

Lken K. P., 1989,Hydrate Kinetics in Fluid Flow, Unpublished Diploma Thesis,
Department of Chemical Engineering, NTNU, PP 2-5.

Makogon Y. F., 1997, Hydrates of Hydrocarbons, 1
st
edition, Pennwell Publishing
Company, PP 1-8.

Paez J. E., Blok R., Vaziri H. and Islam M. R., 2001, Problems in Hydrates:
Mechanisms and Elimination Methods, SPE 67322, PP 1-9.

http://physchem.ox.ac.uk/MSDS/TE/tetrahydrofuran.html (June 05, 2006)

Rojey A., Jaffret C., Cornot-Gandolphe S., Durand B., Jullian S. and Valais M.,
1997, Natural Gas Production processing and Transport, Editions Technip, PP
202-217.

Ryba A., 2005, Reduction in emissions and energy use at makowice natural gas
dehydration facility, Unpublished Diploma Thesis, Dep. of Petroleum Engineering
and Petroleum Geoscience, NTNU, PP. 6-9.

Sloan E. D. Jr., 1997, Clathrate Hydrates of Natural Gases, 2
nd
edition, Marcel
Dekker, Inc., P-12, PP. 26-62.

Sugaya M., Mori Y. H., 1996, Behavior of Clathrate Hydrate Formation at the
Boundary of Liquid Water and a Fluorocarbon in Liquid or Vapor State, Chemical
Engineering Science, Vol. 51, No. 13, PP. 3505-3517.
44


APPENDICES
45

Appendix A-1


Table A-1: Table of Specification of THF

Full Name Tetrahydrofuran
Purity (GC) 99.8%.
Identity Appearance Conforms Clear.
Colour 10 Hazen.
Specific Gravity (20C/20C) 0.885-0.895.
Acidity 0.0003 meq/g.
Peroxide (as H
2
O
2
) 0.005%.
Al (Aluminium) 0.00005%.
B (Boron) 0.000002%.
Ba (Barium) 0.00001%.
Ca (Calcium) 0.00005%.
Cd (Cadnium) 0.000005%.
Co (Cobalt) 0.000002%.
Cr (Cromium) 0.000002%.
Cu (Copper) 0.000002%.
Fe (Iron) 0.00001%.
Mg (Magnesium) 0.000002%.
Ni (Nickel) 0.000002%.
Pb (Lead) 0.00001%.
Sn (Tin) 0.00001%.
Zn (Zinc) 0.00001%.
Evaporation Residue 0.0005%.
Water 0.03%.
Stabilized With 2,6-Di-tertbutyl-4-methylphenol.
Produced by Merck KGaA,
64271 Dramstadt, Germany.

46


Appendix A-2

Safety (MSDS) data for tetrahydrofurane
(http://physchem.ox.ac.uk/MSDS/TE/tetrahydrofuran.html, June 05, 2006)




General

Synonyms: THF, 1,4-epoxybutane, butylene oxide, cyclotetramethylene oxide,
oxacyclopentane, diethylene oxide, oxolane, furanidine, hydrofuran, agrisynth
THF
Molecular formula: C
4
H
8
O
CAS No: 109-99-9
EC No: 203-726-8
EC Index No: 603-025-00-0

Physical data

Appearance: colourless liquid with ether-like odours
Melting point: -108 C
Boiling point: 66 C
Vapour density: 2.5
Vapour pressure: 129 mm Hg at 20 C
Specific gravity: 0.89
Flash point: -14 C
Explosion limits: 1.5% - 12%
Autoignition temperature: 610 F

47

Stability

Stable. Incompatible with halogens, strong oxidizing agents, strong reducing
agents, strong bases, oxygen. May generate explosive peroxides in storage if in
contact with air. Highly flammable. Store at room temperature under nitrogen.
Hazardous polymerisation may occur. Light sensitive. May contain 2,6-di-
tertbutyl-4-methylphenol (BHT) as a stabiliser.

Toxicology

May be harmful by inhalation, ingestion or skin absorption. Skin contact may
cause dermatitis. Long-term exposure may lead to kidney or liver damage.
Irritant. May cause narcotic effects. TLV 200 ppm.
Toxicity data
ORL-RAT LD50 2816 mg kg
-1

IHL-RAT LC50 62 mg kg
-1

IPR-RAT LD50 2900 mg kg
-1

IPR-MUS LD50 1900 mg kg
-1

ORL-GPG LD50 2300 mg kg
-1

Risk phrases
R11 R19 R36 R37.
Transport information

UN No 2056. Packing group II. Hazard class 3.0. Transport category 2.

Personal protection

Safety glasses, nitrile gloves. Effective ventilation.
Safety phrases
S16 S29 S33.
48

Appendix A-3
Abbreviations used in Toxicity data


Table-A2: Abbreviations used in Toxicity data

asn Aspergillus nidulans
ast Ascites tumor
bcs Bacillus subtilis
bfa body fluid assay
bmr bone marrow
brd bird (domestic or lab)
bwd wild bird species
chd Child
ckn Chicken
CL Ceiling concentration
clr Chlamydomonas reinhardi
ctl Cattle
cyt cytogenetic analysis
D Day
dck Duck
dlt cominant lethal test
dmg Drosophila melanogaster
dnd DNA damage
dni DNA inhibition
dnr nNA repair
dns Unscheduled DNA synthesis
49

dom domestic animal (goat, sheep)
dpo Drcsophila pseudo-obscura
emb Embryo
esc Escherichia cold
eug Euglena gracilis
eye administration into eye (irritant)
fb Fiber
fbr Fibroblast
frg Frog
gm Gram
gpg Guinea pig
grb Gerbil
grh Grasshopper
H Hour
ham Hamster
hla HeIa cell
hma host-mediated assay
hmi Haemophilus influenzae
hmn Human
hor horse, donkey
I Intermittent
ial Intraaural
IARC International Agency for Research on Cancer
iat Intraarterial
ice Intracerebral
icv Intracervical
50

idr Intradermal
idu Intraduodenal
ihl Inhalation
imm Immersion
imp Implant
ims Intramuscular
inf Infant
ipc Intraplacental
ipl Intrapleural
ipr Intraperitoneal
irn Intrarenal
isp Intraspinal
itr Intratracheal
itt Intratesticular
iu international unit
iut Intrauterine
ivg Intravaginal
ivn Intravenous
kdy Kidney
kg Kilogram
klp Klebsiella pneumoniae
L Liter
LC50 lethal concentration 50 percent kill
LCLo Lowest published lethal concentration
LD50 lethal dose 50 percent kill
LDlo Lowest published lethal dose
51

leu Leukocyte
Liq Liquid
lng Lung
lvr Liver
lym Lymphocyte
M Minute
m3 cubic meter
mam mammal (species unspecified)
man Man
ug microgram
umol Micromole
mg milligram
mky Monkey
mL Milliliter
MLD mild irritation effects
mma Microsomal mutagenicity assay
mmo mutation in microorganisms
mmol Millimole
mmr mammary gland
mnt micronucleus test
MOD moderate irritation effects
mol Mole
mppcf million particles per cubic foot
mrc gene conversion and mitotic recombination
msc mutation in mammalian somatic cells
mul multiple routes
52

mus Mouse
n/a Not available
ng nanogram
nml non-mammalian species
nmol Nanomole
NOAEL No Observed Adverse Effect Level
nsc Neurospora crassa
ocu Ocular
ofs other fish
omi other microorganisms
oms other mutation test systems
oin other insects
open open irritation test
orl Oral
ORM Other Regulated Material (DoT)
oth other cell types
otr oncogenic transformation
ovr Ovary
par Parenteral
pg Pictogram
pgn Pigeon
pic phage inhibition capacity
pig Pig
Pk peak concentration
pmol Picomole
post after birth
53

ppb parts per billion (v/v)
pph parts per hundred (v/v) (percent)
ppm parts per million (v/v)
ppt parts per trillion (v/v)
preg Pregnant
qal Quail
rat Rat
rbt Rabbit
rec Rectal
rns rinsed with water
S Second
sal Salmon
sat Salmonella typhimurium
sce sister chromatic exchange
scu Subcutaneous
SEV Severe irritation effects
skn administration onto skin
sln Sex chromosome loss and nondisjunction
slt specific locus test
slw Silkworm
smc Saccharomyces cerevisiae
spm sperm morphology
spr Sperm
sql Squirrel
srm Serratia marcescens
ssp Schizosaccharomyces pombe
54

STEL short term exposure limit
TC toxic concentration (other than lowest concentration)
TCLo Lowest published toxic concentration
TD toxic dose (other than lowest toxic dose)
TDLo Lowest published toxic dose
tes Testis
TLV Threshold Limit Value
tod Toad
trk Turkey
trn heritable translocation test
TWA time weighted average
Unr Unreported
W Iek
Wmn Woman
Y Year

55

Appendix A-4

Risk Phrases

Chemical data sheets available in many countries now contain codes for certain "risk
phrases", shown as R23, R45 etc. These risk phrase codes have the following meanings:
o R1 Explosive when dry.
o R2 Risk of explosion by shock, friction, fwere or other source of ignition.
o R3 Extreme risk of explosion by shock, friction, fwere or other sources of
ignition.
o R4 Forms very sensitive explosive metallic compounds.
o R5 Heating may cause an explosion.
o R6 Explosive with or without contact with air.
o R7 May cause fwere.
o R8 Contact with combustible material may cause fwere.
o R9 Explosive when mixed with combustible material.
o R10 Flammable.
o R11 Highly flammable.
o R12 Extremely flammable.
o R13 Extremely flammable liquefied gas
o R14 Reacts violently with water.
o R15 Contact with water liberates extremely flammable gases.
o R16 Explosive when mixed with oxidizing substances.
o R17 Spontaneously flammable in air.
o R18 In use may form inflammable/explosive vapour-air mixture.
o R19 May form explosive peroxides.
o R20 Harmful by inhalation.
o R21 Harmful in contact with skin.
o R22 Harmful if swallowed.
o R23 Toxic by inhalation.
o R24 Toxic in contact with skin.
o R25 Toxic if swallowed.
56

o R26 Very toxic by inhalation.
o R27 Very toxic in contact with skin.
o R28 Very toxic if swallowed.
o R29 Contact with water liberates toxic gas.
o R30 Can become highly flammable in use.
o R31 Contact with acids liberates toxic gas.
o R32 Contact with acid liberates very toxic gas.
o R33 Danger of cumulative effects.
o R34 Causes burns.
o R35 Causes severe burns.
o R36 Irritating to eyes.
o R37 Irritating to respiratory system.
o R38 Irritating to skin.
o R39 Danger of very serious irreversible effects.
o R40 Limited evidence of a carcinogenic effect.
o R41 Risk of serious damage to the eyes.
o R42 May cause sensitization by inhalation.
o R43 May cause sensitization by skin contact.
o R44 Risk of explosion if heated under confinement.
o R45 May cause cancer.
o R46 May cause heritable genetic damage.
o R47 May cause birth defects
o R48 Danger of serious damage to health by prolonged exposure.
o R49 May cause cancer by inhalation.
o R50 Very toxic to aquatic organisms.
o R51 Toxic to aquatic organisms.
o R52 Harmful to aquatic organisms.
o R53 May cause long-term adverse effects in the aquatic environment.
o R54 Toxic to flora.
o R55 Toxic to fauna.
o R56 Toxic to soil organisms.
57

o R57 Toxic to bees.
o R58 May cause long-term adverse effects in the environment.
o R59 Dangerous to the ozone layer.
o R60 May impair fertility.
o R61 May cause harm to the unborn child.
o R62 Risk of impawered fertility.
o R63 Possible risk of harm to the unborn child.
o R64 May cause harm to breastfed babies.
o R65 Harmful: may cause lung damage if swallowed.
o R66 Repeated exposure may cause skin dryness or cracking.
o R67 Vapours may cause drowsiness and dizziness.
o R68 Possible risk of irreversible effects.
58


Appendix A-5

EC Safety Phrases

Under EC legislation, data sheets available in the UK now contain codes for certain
"safety phrases", shown as S1, S17 etc. These phrases are also extensively used
elsewhere in the world. Safety phrase codes have the following meanings:
S1 Keep locked up.
S2 Keep out of the reach of children.
S3 Keep in a cool place.
S4 Keep away from living quarters.
S5 Keep contents under ... (there follows the name of a liquid).
S6 Keep under ... (there follows the name of an inert gas).
S7 Keep container tightly closed.
S8 Keep container dry.
S9 Keep container in a well-ventilated place.
S12 Do not keep the container sealed.
S13 Keep away from food, drink and animal foodstuffs.
S14 Keep away from ... (a list of incompatible materials will follow).
S15 Keep away from heat.
S16 Keep away from sources of ignition.
S17 Keep away from combustible material.
S18 Handle and open container with care.
S20 When using, do not eat or drink.
S21 When using do not smoke.
S22 Do not breathe dust.
S23 Do not breathe vapour.
S24 Avoid contact with skin.
59

S25 Avoid contact with eyes.
S26 In case of contact with eyes, rinse immediately with plenty of water and seek
medical advice.
S27 Take off immediately all contaminated clothing.
S28 After contact with skin, wash immediately with plenty of soap-suds.
S29 Do not empty into drains.
S30 Never add water to this product.
S33 Take precautionary measures against static discharges.
S35 This material and its container must be disposed of in a safe way.
S36 Wear suitable protective clothing.
S37 Wear suitable gloves.
S38 In case of insufficient ventilation, Wear suitable respiratory equipment.
S39 Wear eye / face protection.
S40 To clean the floor and all objects contaminated by this material, (there
follows suitable cleaning material).
S41 In case of fire and / or explosion do not breathe fumes.
S42 During fumigation / spraying wear suitable respiratory equipment.
S43 In case of fire use ... (there follows the type of fire-fighting equipment to be
used.)
S45 In case of accident or if you feel unwell, seek medical advice immediately
(show the label whenever possible.)
S46 If swallowed, seek medical advice immediately and show this container or
label.
S47 Keep at temperature not exceeding...
S48 To be kept It with (there follows a material name).
S49 Keep only in the original container.
S50 Do not mix with ...
S51 Use only in Ill ventilated areas.
S52 Not recommended for interior use on large surface areas.
S53 Avoid exposure - obtain special instructions before use.
60

S56 Dispose of this material and its container at hazardous or special waste
collection point.
S57 Use appropriate container to avoid environmental contamination.
S59 Refer to manufacturer / supplier for information on recovery / recycling.
S60 This material and its container must be disposed of as hazardous waste.
S61 Avoid release to the environment. Refer to special instructions / safety data
sheets.
S62 If swallowed, do not induce vomiting; seek medical advice immediately and
show this container or label.

61

Appendix A-6
Time-frame

Table A-3: Time-frame

62

Appendix A-7
Pictures of Experiments


Figure A1: Experiment of Exxsol d80



Figure A2: Experiment of King Crude Oil

63



Figure A3: Experiment of Paladio Crude Oil





Figure A4: Experiment of an unidentified light oil from Norsk Hydro


64



Figure A5: Defective THF solution in the upper chamber



Figure A6: Defective THF solution stored carefully in plastic jars
65

Appendix A-8
Pictures of Hydrates

Figure A-7: Methane hydrate formed on water surface at P = 96 bar, T = 4C (Makogon, 1997)

Figure A-8: Massive methane hydrate formed in the gas sphere at P = 95 bar, T=7C (Makogon,
1997)
66


Figure A-9: Soft massive methane hydrate, formed in the water volume in dynamic situation at P =
107 bar, T = 12C (Makogon, 1997)

Figure A-10: Massive and whiskery crystals of methane hydrate, formed in the gas sphere and water
volume at P = 91.4 bar, T = 3C (Makogon, 1997)
67


Figure A-11: Dimensions of molecules entering hydrate cavities (Rojey et. al. 1997)
68


Figure A-12: Spherical particles at oil/water interface; Oil-wet particles (contact angles >90) will
reside mainly in the oil phase (right), and tend to stabilize water-in-oil emulsions. Water-wet
particles (contact angle <90) reside mainly in the water phase (left), and tend to stabilize oil-in-water
emulsions (Hiland et. al., 2005)
69

Appendix A-9
Hydrate Data
Table A-3: Schematic representation of hydrate types (Makogon, 1997)

Table A-4: Characteristics of hydrate structures I, II and H (Makogon, 1997)

70

Table A-5: Some potential gas hydrate formers in natural and industrial
environments (Makogon, 1997)


71

Table A-6: Structural characteristics of hydrates (Makogon, 1997)

Table A-7: Geometry of cages (Sloan, 1998)


72

Table A-8: Hydrate crystal cell structures (Sloan, 1998)

73


Table A-9: Comparison of properties of ice and sI and sII hydrates (Sloan, 1998)

74