Dissociation of Gas Hydrate in Porous Sediments

Mohamed Iqbal Pallipurath* Research Scholar, Cryogenic Engineering Centre, Indian Institute of Technology Kharagpur, W. Bengal, India Abstract
Gas Hydrates have significant implications for future energy supply and global climate. A simulator for methane hydrate formation and dissociation in porous media is developed for designing and interpreting laboratory and field hydrate experiments. The kinetics of hydrate formation or dissociation is considered using the KimBishnoi model. Heat transfer involved in formation or dissociation of hydrates are included in the governing equations, which are discretized with finite volume difference method and are solved in Explicit, semi-implicit and fully implicit manner. The software simulator is used to study the formation and the dissociation of hydrates in laboratory-scale samples. Various boundary conditions can be plugged in to the simulator which has a user friendly interface. Property variations are also considered, and can similarly be set before simulation starts. 3D plots of Temperature, Time and space are obtained after simulation is complete. The data generated during simulation can be stored and recalled as and when necessary.

Nomenclature
A Surface area of pore C Specific heat of component k Thermal Conductivity of component K Hydrate generation/dissociation rate Constant Mass rate of component m S Component saturation T Temperature v Velocity of component

Greek

Sediment Porosity Relative Permeability of component Density of component

Subscripts
0 Intrinsic e Equilibrium value g Gas h Hydrate m Mean Value s Skeleton w Water

Superscripts
i Refers to temporal position i

Introduction
The modelling of hydrate formation and dissociation concerns a great number of petroleum and geophysical applications such as Deep offshore Extraction For companies in charge of the drilling of new wells in deep and ultra deep offshore environments, the plugging of annulars by hydrate formation in drilling muds is an important issue. Extreme conditions encountered at these depths require an adaptation of the

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drilling muds. The range of temperature (down to - 1C) and pressure (up to 400 bars) favor the formation of gas hydrates. The water contained in the drilling muds traps the gas molecules coming from the reservoirs. The plugging of the lines as well as the annular may cause interruption of the drilling operation and even destruction of the rig equipment. Flow assurance The production, processing and distribution of gas is a high pressure operation. Under pressure, pipelines can be plugged with gas hydrate in the form of ice. Today every oil and gas company has a flow assurance department responsible for detecting and predicting the formation of gas hydrates in the pipelines and the processing equipment. Natural Gas Hydrates. More and more countries are interested in the investigation of gas hydrates trapped in marine sediments and in permafrost. Gas hydrates occur abundantly in nature, both in artic regions and in marine sediments. Methane trapped in marine sediments as a hydrate represents a huge carbon reservoir. The worldwide amounts of carbon bound in gas hydrates is conservatively estimated at twice the total amount of carbon to be found in all known fossil fuels on earth. Methane hydrate is stable in ocean floor sediments at water depths greater than 300m. Storage and Transportation of Natural Gas. One way of reducing the cost of natural gas transport is to carry it as natural gas hydrates (NGH). The gas hydrate process reduces the volume of natural gas by about 169 times and stores the hydrates within a range of potential temperatures and associated pressures. Such transportation and storage are easier and safer than liquefied natural gas (LNG) handling. But more has to be known about the formation of gas hydrates to optimize the industrial process, and particularly their stability and conditions of safety during transportation and storage. Global warming The stability of gas hydrates and their effect on global warming may become an issue and needs to be investigated. Depending on the stability of the gas hydrates, a 1 or 2C increase in the temperature of the ocean might possibly cause the release of methane into the atmosphere with all the ensuing impacts on climate changes. CO2 ocean sequestration CO2 ocean sequestration is one method being explored to control the build-up of CO2 in the atmosphere. The formation of a CO2 hydrate from fossil fuel CO2 disposal with a solid hydrate as the sequestered form is evaluated. The success of the option of pumping liquid CO2 into the oceans depends above all on the chemical stability of the CO2 hydrate. Cold energy storage As gas hydrates show high latent heat during formation and dissociation, they are considered very interesting materials for cold energy storage. Desalination Gas hydrate technology can be used to produce fresh water. Using an appropriate gas, water molecules go into a hydrate phase during hydrate formation from salt water, while minerals dissolve in the water concentrate. For all the researchers working on the above mentioned topics, it is absolutely vital to have as much information as possible on gas hydrate formation / dissociation such as: - thermodynamic properties - kinetics data of any type of mixture (even including solid particles) These applications motivated the development of a simulator. The aim of the modelling is to simulate experiments and to test different kinetic laws for formation and dissociation. These simulations take into account the thermal effect, i.e. the temperature variation due to the heat of phase transitions: exothermic formation and endothermic dissociation. This model can be equivalently used in order to quantify the dynamic behaviour of hydrate fields and possible gas recovery. During hydrate dissociation, methane concentration in hydrate corresponds to about 170 gas volumes per water volume in standard conditions. The quantity of methane given by hydrate dissociation is much higher that the methane quantity dissolved in water, when temperature and pressure conditions are those corresponding in hydrate accumulations.

Modeling equations
Consider a hydrate bed at a uniform temperature T0 at time t=0, heated from the top as shown in Figure-1. The hydrate dissociates into gas and water during time t>0.

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Figure -1 For the control volume of thickness x, applying mass balance for gas,

g ( g S g ) = (vg g ) + m t x

(1.1)

For water,

w ( w S w ) = (vw w ) + m t x h ( h Sh ) = m t

(1.2)

And for hydrate,

(1.3) (1.4) (1.5)

The source/sink terms i.e.; mg, mw, and mh are related by (Yousif et-al 1991)

h = m g +m w m
Mg

mg = mh

Nh M w + M g

Nh being the hydration number (usually six for pure methane hydrate and 6.5 for natural gas hydrates), and Mw and Mg the moles of water and gas respectively. The local gas generation/depletion rate caused by hydrate dissociation or growth can be obtained by the Kim-Bishnoi model (Kim et al 1987) and the Englezos model (Englezos et al 1987) (1.6) mg = KA( Pe P) Where Pe is the hydrate equilibrium pressure, A is pore surface area and the rate constant K is obtained by an Arrhenius type relation

K = K 0 e E / RT
Where K0 is the intrinsic decomposition constant Equations (1.1), (1.2) and (1.3) are coupled with Darcys law viz.;

(1.7)

vg =

g g vw = w w

P x
P x

(1.8) (1.9)

Rewriting (1.1), (1.2) and (1.3) by incorporating equations (1.8) and (1.9)

g P g ( g S g ) = ( g )+m t x g x P w ( w S w ) = ( w w )+m t x w x

(1.10) (1.11)

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 h ( h Sh ) = m t
From (1.4) mass balance may be written as

(1.12)

P P [( h Sh ) + ( g S g ) + ( w S w )] = ( g g ) + ( w w ) t x g x x w x
[(1 ) s Cs T + Sh h ChT + S w w CwT + S g g C g T ] t T = ( km ) [ ( w hw vw + g hg vg )] + G h x x x km = Sh kh + S w kw + (1 Sh S w )k g + (1 )ks
S g + Sw + Sh = 1

(1.13)

Energy Balance for the control volume,

(1.14)

Where km is the mean thermal conductivity of the sediment + hydrate + water + gas Given by, (1.15) (1.16) And,

Numerical simulation
The packed bed / hydrate layer of thickness L is at the hydrate equilibrium temperature T0. For time t > 0 heat is supplied at a constant rate of q W/m2 to the hydrate layer causing dissociation. We will consider a one dimensional heat transfer across the hydrate layer, with variation in properties along the direction of heat flow. So the thermal conductivity k is varying along x direction.

Figure -2. Control Volume For simplicity we will take xm 1 = xm +1 = x (Figure -2) Integration of (1.14) is done over the control volume, over the time interval t to t+ t , to obtain a relation for Tm where subscript m denotes the spatial position in the grid. Details of the Discretisation are in the appendix. The resulting equation is,

g P 2 P w T T C C C = + + + c w g 1 x x x x 2 2 2 T k T P P + km 2 + m 2 + G h x x x x x x T A t

(2.1)

This may now be discretized by using the forward difference for first order differentials and the central difference for second order differentials as,

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i i i i i i i g g i i w w i i i T T P P i i i P n+1 2P n +P n1 + Cw n+1 n + Cg n+1 n n+1 n A = Tm c Tn C1 + n 2 x x x n n n x t i +1 n i n

+ km
n

i m+1

2T + T x
i m 2

i m1

i +1 i km km T i T i i i Pi Pi + n n n+1 n n+1 n n+1 n x x x x

(2.2)

i Pni+1 2Pni + Pni1 G + h x2 n i n

The discretized equation will be applied to nodes m=1, 2, , M-1; M being the total number of nodes. At nodes n=0 and n=M, we have to apply boundary conditions, k Discretising, T0 = T1 +
i i

qx T i i at n = 0 And = 0 at x = L, t > 0 So, TM = TM 1 at n = M at any k0 x

T = q at x=0, t>0 x

instant i

Results
Results of the simulation are plotted as surfaces with the 3 coordinates of space, time and temperature. The explicit solution gave the following surface.

Figure 3 Temperature surface for initial temperature of 0 oC, insulated far boundary, Implicit Model.

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Figure 4 Temperature Vs Time and Thickness of hydrate for initial temperature of 0 oC, with insulated far boundary, Implicit Model

Conclusion
The simulation scheme has the advantage of allowing prior input of various boundary conditions. It is also possible to run the simulation in explicit, semi-implicit and fully implicit modes and compare the results side by side. Data generated during a simulation run can be stored and later instantly displayed numerically or graphically without having to run the simulation again. Data sets are identified by date and time to simplify retrieval from the database. The simulation accounts for one dimensional heat transfer alone. Whereas this may be a good approximation in laboratory experiments, a multidimensional heat transfer model has to be incorporated in later work to account for the oceanic sedimentary hydrate dissociation. Mass transfer and diffusion are simplistically treated in the current model and needs to be rigorously expressed in the next generation of simulation.

References
[1] Clarke, M., Bishnoi, P.R., 2000. Determination of the intrinsic rate constant of ethane gas hydrate decomposition. Chemical Engineering Science 55, 48694883. [2] Clarke, M., Bishnoi, P.R., 2001. Determination of the activation energy and intrinsic rate constant of methane gas hydrate decomposition. The Canadian Journal of Chemical Engineering 79, 143147. [3] Englezos, P., Kalogerakis, N., Dholabhai, P.D., Bishnoi, P.R., 1987a. Kinetics of formation of methane and ethane gas hydrates. Chemical Engineering Science 42, 26472658. [4] Englezos, P., Kalogerakis, N., Dholabhai, P.D., Bishnoi, P.R., 1987b. Kinetics of gas hydrate formation from mixtures of methane and ethane. Chemical Engineering Science 42, 26592666. [5] E.D. Sloan, Clathrate Hydrates of Natural Gases, second ed., Marcel Dekker, New York, 1998. [6] Patankar S. V. Numerical Heat Transfer and Fluid Flow. Taylor & Francis, 1980 [7] George G. Tsypkin. Mathematical Models Of Gas Hydrates Dissociation In Porous Media

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