Ph.D. Thesis of Dr. Annie FIDEL-DUFOUR
"Influence d'additifs anti-agglomérants sur l'agrégation et les propriétés de transport des hydrates de méthane cristallisant dans des émulsions eau/dodécane"
defended by A. FIDEL-DUFOUR on June 11th, 2004
Ecole Nationale Superieure des Mines de St-Etienne, France (Order number 338 CD)
It was carried out in the GasHyDyn Center (Archimede Project)
ABSTRACT
The gas hydrates are solid compounds of clathrate type which can be formed
starting from cold water and hydrocarbon gas molecules under pressure. These
conditions are met in certain oil conduits and can lead to a problem of production.
Indeed, the oil effluent which leaves a well of production always contains light
water and hydrocarbon molecules (methane, ethane, propane) suitable form a gas
hydrate. The methane hydrates are not naturally present in the layers of production
because the temperature is too high (until 200°C). On the other hand, the
oil fluid cools at the time of its transport in a control, either because control
is localized in a particularly cold zone, or because control is underwater,
by the contact with cold water. It can then create hydrates being likely to
block the conduits. To prevent their crystallization, the current tendency is
to couple three types of approaches: insulation of the conduits, injection of
additive at the time of the critical phases, reheating of control by hot water
circulation at the time of accidental stopping. This thesis takes part in the
modeling of the flows after formation of hydrates. It is not thus a question
of preventing crystallization but of being interested in rheology of the flow
after formation of crystals. The long-term objective is to identify the origin
of the transportability of the purées of hydrates under the influence
of additives known as "anti-binders". The mechanisms of crystallization
indeed are very often coupled: germination, growth, agglomeration, attrition...
The comprehension of the mechanism of action of an additive is thus a complex
spot, more especially as crystallization is closely related to the physical
system in which it develops. The studies seeking to identify the mechanisms
of crystallization, for then including/understanding the effects of additives
all (or practically) were carried out in closed engines and simple systems (eau/gas)
(Herri (1996), Pic (2000)...). Conversely, tests of validation of additives
were carried out on loops control representing a real flow, therefore complex.
Our work is thus halfway of the two preceding approaches. It is a question of
approaching the geometrical conditions of an oil flow (pilot buckles) while
preserving a simple system (eau/dodécane) with for objective on the long
term identifying the coupling: geometry/crystallization/influence of the additives.
The experimental device (height 12m, width 3m, length 6m) carried out within
the framework of this thesis is a pilot loop of circulation reproducing certain
conditions of the flow of an oil fluid (emulsion water in oil) in a subsea pipe,
i.e. under strong pressure [ 1-10 MPa ] and low temperature [ 0-10°C ].
The various parts of this instrument are:
The serpentine being rolled up on 3 levels
The tube going up is a riser. With the base of this tube is injected methane
in order to reduce the column of fluid to create an effect elevator: gaslift.
The separator located at the top of the riser separate by gravity the gas part,
of the liquid part (water, oil) which goes down again in a tube parallel with
the riser towards the loop of circulation
The system of recompression of gases recovers gases of the separator to reinject
them with the bottom of the riser after increase in the pressure. This experimental
system is composed in fine of two loops circulating on themselves: a loop liquidates
and a loop gas. These two loops share a common section made up of the riser
and separator. This device made it possible to make rheological studies on the
phase only continues (dodecane) according to the pressure of methane and on
emulsions containing various water contents and of additives. Studies concerning
the crystallization of the methane hydrates within the emulsions were carried
out by considering the influence of the water content then that of the content
of additive on the apparent viscosity of dispersions thus formed. We finally
propose a modeling connecting crystallization to the rheological behavior.