Subsidence of Dissociating Gas Hydrate

Mohamed Iqbal Pallipurath*

Abstract
Thermal dissociation of hydrated sediment by a pumped hot fluid is modeled. A radial heat flow from the hot pipe is assumed. The coordinate system is cylindrical. Three components (hydrate, gas (methane) and water) and three phases (hydrate, gas, and aqueous-phase) are considered in the simulator. The intrinsic kinetics of hydrate formation or dissociation is considered using the KimBishnoi model. Mass transport, including two-phase flow, molecular diffusions and 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 an explicit manner. The strength deterioration of the hydrate bed as a result of dissociation is investigated with a geomechanical model. The way in which dissociation affects the bed strength is determined by plugging in the porosity and saturation change as a result of dissociation into the sediment collapse equations. A mechanism to measure the pore pressure changes occurring due to dissociation is developed. The rate of collapse as dissociation proceeds is determined and the model thus enables the definition of a safety envelope for gas hydrate drilling.

It must be pointed out here that the effect of dissociation on the material strength of the hydrate bed has not been the topic of any work so far. This important aspect of recovery of natural gas from hydrated sediments will be our main investigation in this work. 2.1 State of the art Considerable work has gone into exploring Natural Gas hydrate in the last 30 years. Analytical and numerical models of diverse convolution have been developed to simulate hydrate dissociation both considering the kinetics of hydrate dissociation [1] and without that consideration [2]. While several workers have included heat transfer by conduction and convection and the flow (of the gas only, or gaseous and aqueous phases) in their models others have ignored these processes. Yousif et al. [1] developed a 1D model for the kinetics of hydrate dissociation in porous media due to depressurization using the KimBishnoi scheme for the rate of gas generation. The model solved continuity equations for each of the 3 phases (gas, liquid and hydrates) and used relations between the saturations of the phases and the rates of mass transfer of the phases. Darcy's Law was used to model the flow of water and gas separately. Porosity and permeability were updated as dissociation took place. Heat transfer was not considered and the dissociation was considered isothermal. Heat transfer was considered in a numerical model by Masuda et al. (2002). Numerical Study 3.1 Introduction Thermal dissociation of hydrated sediment by a pumped hot fluid is modeled. A radial heat flow from the hot pipe is assumed. The coordinate system is cylindrical. Three components (hydrate, gas (methane) and water) and three phases (hydrate, gas, and aqueous-phase) are considered in the simulator. The intrinsic kinetics of hydrate formation or dissociation is considered using the KimBishnoi model. Mass transport, including two-phase flow, molecular diffusions and heat transfer involved in formation or dissociation of hydrates are included in the governing equations, which are discretized with

1.1 INTRODUCTION Gas hydrates are crystalline compounds formed when gas molecules are trapped by water molecules, which form a cage like structure around the gas molecule. Hydrate formation is favoured at low temperatures and moderate to high pressures [1]. Knowledge about the strength of the marine sediment 'soils', in which these concentrated hydrate deposits are likely to occur, is vital to the eventual economic exploitation of hydrated sediments. The high porosity fine-grained sediments that host variable amounts of hydrate throughout the HSZ are nowhere as strong as conventional geological traps and reservoirs. Geotechnical studies have established that the strength and elastic properties of hydrates are similar to ice, while the morphology and strength of hydrated sediments are similar to those of permafrost [2]. Mechanical Engineering Department, T. K. M. College of Engineering, Kollam, Kerala 691005 India.*Author for corresponding. Email: mohamediqbalp@gmail.com

finite volume difference method and are solved in an explicit manner.

(1.4) Where g is the gas component, existing as free gas (G) or dissolved in water (A), h is the hydrate component present only in the hydrate phase (H).

3.4 Kinetics
The kinetics of dissociation is given by the relation (1.5) (mol/m3.s) is the formation rate of gas; k Where 2 (mol/m .Pa.s) is the kinetic constant of hydrate formation or dissociation; As (m2/m3) is the reaction surface area; f (Pa) is the fugacity of gas under the local temperature and pressure and feq is the fugacity of gas at the equilibrium pressure at the local temperature. Local gas pressure p and gas-water-hydrate equilibrium pressure pe is used to approximate f and fe, respectively, as in the work by Yousif et al. (1991) [1]. Thermodynamic equilibrium relationship between pe and temperature, T, is given by Sloan (1998) [2]. (1.6) The kinetics of hydrate formation and dissociation, written as the consumption rate of gas, is described by Eq. (1.5). The consumption rate of water and hydrate can be determined from Eq. (1.4) (1.7) (1.8) The kinetic constant k is in the form of an Arrheniustype equation [1]. (1.9) Where k0 is the intrinsic kinetic constant; is the

Figure 1 Top view and side view of hydrated sediment.

3.3 Mass balance

The mass balance equations for gas flow through the porous medium can be written as (1.1) And for water flow (1.2)

The conservation equation of the solid hydrate is given as: (1.3) Where is the porosity of the hydrated sediment, is the density, is the Darcy velocity, (mol/m3.s) represents the local mass rate produced by hydrate decomposition per unit volume. The kinetic rate r is multiplied with the corresponding molecular weight to convert the unit from mol/m3 s to kg/m3 s. The subscripts refer to gas, water and hydrate. S is the saturation. In Eq. (1.3) (mol/m3s) represents the local rate of

activation energy and R is the gas constant (8.314 J/mol.K). For SI hydrate in a bulk phase system without salt, k0 = 3.6104 mol/m2 Pa s, and =

9752.73 K, as measured by Clarke and Bishnoi (2001) [3]. We assume that the kinetic constant of hydrate formation to be a constant, and its default value takes the average of the results measured by Englezos et al. (1987a) [4], which is 0.58751011 mol/m2 Pa s. The reaction surface area As in Eq. (1.9) for porous media system is given by Yousif et al. (1991) as referred to in literature [1] as follows.

hydrate dissociated per unit volume. The generation rates of gas and water are dictated by stoichiometry of the hydrate. The transition between gas, water and hydrates can be represented as a chemical reaction

(1.10) Where is the effective porosity and K is the (1.15)

permeability of sediment. The effective porosity is defined as the volume fraction occupied by fluid phases (gas and aqueous-phase), i.e., (1.11) Where is the total porosity including the pore volume occupied by both fluid phases (g and w) and hydrate phase (h); Sg and Sw are the saturations of gas and aqueous-phase, respectively. For the phase saturations, the following equation must hold: (1.12) The density of solid phase , is assumed to be is set (1.16)

In Eqs. (1.18) and (1.19), the residual aqueous phase saturation and gas phase saturation, Swr and Sgr, are based on the pore volume occupied by fluid phases (namely effective pore volume). Note that, Swr and Sgr, are based on the total pore volume (occupied by fluid phases and hydrates) and the ratio or

constant. In the present work, the value of

to be 0.91 g/ml [2]. The convection of fluid phases (g and w) during hydrate formation and dissociation is usually slow, and thus can be considered by applying Darcys law to multiphase flow [5] which gives us the velocities of gaseous and aqueous phases in Eqs. (1.1) and (1.2) (1.13) Where vj is the Darcy velocity of phase j (j =g,w); is the absolute permeability tensor; krj , and pj are, respectively, the relative permeability, the viscosity and the pressure of phase j; is the gravitational acceleration. We use the power-law model proposed by Civan (2001) [6] to evaluate the local absolute permeability. (1.14) Where K is the scalar value of local absolute permeability; K0 is the reference absolute permeability; is the effective porosity as defined by Eq. (1.13); is the reference porosity, which is normally chosen as the total porosity ; is a parameter that determines the decreasing rate of absolute permeability with . This work uses = 0.5 from an assessment of the data from literature [5]. The relative permeabilities of gas and aqueous phases would be given by a Corey model [5]:

denotes the effective pore volume-based saturation. In this work, a value of 0.2 for Swr and 0 for Sgr, are assumed. Corey models are commonly used models, but are not applicable to all porous media. They should be used only if they match experimental measurements for any specific medium. The Aqueous phase viscosity, (cp), is assumed to be constant. The gas phase viscosity, (cp), as a function of temperature and density is given by (Selim and Sloan, 1989) [2]:

(1.17)

3.5 Energy Balance

Heat is transferred through convection conduction. The energy balance equation is and

(1.18) And,

(1.19) Where Cvj is the specific heat at constant volume of phase j, Cpj is the specific heat at constant pressure of phase j; subscript r stands for rock (sediment skeleton); subscript j refers to phases G, A or H. is the throttling Here, Cpj is the heat capacity and coefficient for the jth phase, respectively. is the effective thermal conductivity of the sediment given by [5] (1.20) The enthalpy change due to the hydrate reaction has been incorporated into Eq. (1.18) through the evaluation of CvhT, and the adiabatic effect and JouleThompson throttling effect of gas phase are considered by incorporation of the pressure effect on gas phase internal energy CvgT and enthalpy CphT [5]. The source term qe in Eq. (1.18) is essentially determined by the dissociation heat absorption. (1.21) Where is the enthalpy change in hydrate decomposition. The process of hydrate decomposition is an endothermic phase change process. The latent heat of hydrate dissociation above quadruple point is given as (Selim and Sloan, 1989) [2]: (1.22) Combining the Eqs. (1.18) and (1.19) we get

(1.26) (1.27) Tester (1997) [7] uses Van Der Waals equation to calculate throttling effect caused by the expansion of the gas phase. The throttling coefficient for gas is given by: (1.28) Initial conditions are as follows: (1.29) The following boundary conditions are imposed:

(1.30)

3.6 Collapse of sediment bed

Fine grained sea-floor sediments subjected to compressive vertical load, either from increased overburden or (in the case of hydrate dissociation in hydrated sediment) by sudden lowering of sediment strength, will compress over time. Analysis of such settlements is usually accomplished through onedimensional analysis of three consecutive phases: (a) Immediate settlement also called plastic deformation (non time dependent); (b) primary compression or consolidation (compression that is time dependent because of hydrodynamic effects on pore water being squeezed out of the pore spaces); and (c) secondary compression (time-dependent compressions resulting from relative particle compressions, bending or reorientations) [7]. Dissociation of hydrate causes the voids, earlier filled by solid hydrate, to become filled with gas and water. This causes a drastic reduction in the structural strength of the sediment. This is because now, the load is borne by the empty sediment skeleton. Literature informs us that the drop in structural strength (in terms of shear stress of sediment) is nearly 50%. [7]

(1.23) The following specific heat data are used (Selim and Sloan, 1989) [7}: (1.24) (1.25)

The compression of sediment due to primary compression or consolidation , can be calculated from the following equation. [7]

Where = net flux of water through the sediment element vw = water flow rate across a unit area of the element in z-direction (this is direction specific whereas the differential format above gives the overall value of flux.) dr, dz, d = infinitesimal dimensions in the radial, axial and angular-directions respectively [7]. = formation rate of water in kg.m-3.s-1 is related to terms of the energy equation by Eqn. (1.5)

(1.31) Where, H is the layer thickness, e0 the initial void the shear stress ratio, Cc the compression index, change and the effective overburden pressure. In case secondary compression is considered then the secondary compression is assumed to start once the primary compression had reached completion, which for practical purposes is taken as Degree of Consolidation U = 95%. The amount of secondary compression at any given time t, subsequent to the completion time of primary compression, (t0), is determined from the following equation.

(1.32) Where is the coefficient of secondary

compression. The values of layer thickness H, and the void ratio e, are determined at the completion of primary compression. Having written the energy balance equations, we now need to consider the mass balance equations for both the mobile products i.e. water and gas because these are required to compute the pore pressures of both water and gas, which are in turn, essential to determine the rate of subsidence of the sediment. Here the bed instability caused by the dissociation will impact the thermal balance equations through the change in the values of overall thermal conductivity of the sediment. Figure-2 Unsteady-state gas and water flow during consolidation. (J is the preferred notation for Ficks relation whereas v is customary for Darcys Eqn.). is the angular thickness of the sediment element Expressing the net flux of water per unit volume of the sediment and rearranging Eq. (2.1) yields (2.2) Where V0 = initial total volume of the sediment element = net flux of water per unit volume of the sediment. Substituting Darcys law for the flow rate of water vw into Eq. (2.2) gives

3.8 Water phase partial differential equation

This is the first of the two mass balance equations, necessary for the model of bed collapse during dissociation which will in turn give the pore pressures and subsequently the rate of collapse. Consider a differential element of sediment with gas and water flow during consolidation (Fig.-2). The net flux of water through the element is computed from the volume of water entering and leaving the element within a period of time:

(2.3) Where kw = coefficient of permeability with respect

(2.1)

to water

hw = hydraulic head (i.e., gravitational plus pore water pressure head) = z = elevation pw = pore-water pressures = density of water g = gravitational acceleration = hydraulic head gradient in the ydirection = weight density of water Rearranging Eq. (2.3) gives (2.4) Let us substitute for hw in Eq. (2.4)

= coefficient of water volume change with respect to a change in matric suction, during K0-loading. = gauge pore-gas pressure (kPa) The flux of water per unit volume of the sediment can be obtained by differentiating the water phase constitutive relation [Eq. (2.7)] with respect to time: (2.8) Both equations for flux of water [i.e., Eqs. (2.6) and (2.8)] can now be equated to give a partial differential equation for the water phase: ,

(2.9)

Rearranging Eq. (2.9) gives (2.5) (2.10)

Equation (2.10) is a general form of the partial differential equation for the water phase. This can be rearranged as follows (2.6) (2.11) The water phase constitutive relation defines the water volume change in a sediment element caused by changes in the net normal stress, and the matric suction . [7] (2.7) See appendix for physics of matric suction and significance of each term Where dVw/V0 = change in volume of water in the sediment element with respect to the initial volume of the element Vw = volume of water in the element = coefficient of water volume change with respect to a change in net normal stress, , for K0-loading (Please see Appendix 2 = coefficient of consolidation with respect to the water phase i.e., cg = gravity term constant (i.e., ) The inclusion of the gravitational component of the hydraulic head in the above derivation results in the last term of Eq. (2.11) [i.e., ]. If the gravity term is neglected and the coefficient of permeability kw does not vary significantly with space in the z direction (i.e., is negligible), a simplified form of the differential water flow equation can be written:

Where Cw = interactive constant associated with the water phase partial differential equation, i.e.,

for an explanation of K0-loading)

gas transmissivity variation with space is negligible (2.12) (i.e., is negligible), Eq. (3.15) can be

3.9 Gas phase partial differential equation

The gas phase is compressible and flows in response to a gas pressure gradient. Therefore the flow of gas through a referential element of sediment is computed in terms of the mass rate of gas flow, Ja. The net mass rate of gas flow across the element is obtained as the difference of the mass rates of gas entering and leaving the element within a period of time.

simplified: (3.2) Where The term contains production rate of gas and is thus connected to the energy equation Results and Discussions Table -1 List of models created Model Sediment Thermal Fluid Hydrate No. Subsidence Transport Flow Dissociation 1 Yes No No No 2 Yes Yes No No 3 Yes Yes No Yes 4 Yes Yes Yes No 5 Yes Yes Yes Yes A number of different cases were studied as shown in table 1. Sediment with and without flow of gas and water and with and without hydrate dissociation were studied. The model 5 considers both flow and dissociation. The factor which had the most significant effect on the shape of the curve was the porosity of the hydrated sediment bed. Increasing porosity led to drastic steepness of the initial portion of the curve and also increased the final temperature achieved. The model was found to be very sensitive to the porosity variation. This phenomenon may be attributed to the increased hydrate mass in the pores when porosity increases. So that at higher porosities more of hydrate is dissociated per unit volume of sediment.

(3.1) Where dMa = change of gas mass in the sediment element for a specific time, dt = net mass rate of gas flowing through the sediment element Ja = mass rate of gas flowing across a unit area of the sediment. = mass rate of formation of gas in kg.m-3.s-1 is related to terms of the energy equation by Eqn. (1.5) By steps similar to those we used in deriving equation (2.12) we can arrive at the gas phase partial differential equation

(3.2) Where Ca = interactive constant associated with the gas phase partial differential equation, i.e.,

= coefficient of consolidation with respect to the gas phase, i.e.,

The coefficient of transmission,

, is a function of Fig-3 Temperature of sediment along radial direction at different times (Model 5)

matric suction which can vary in the y-direction. The transmissivity variation of the gas phase is taken into account by the last term in Eq. (3.15). However if the

Fig-4 Sediment subsidence with time at different depths (Model 5)

in the sediment at various instants. The subsidence model considers water and gas flow velocity and mass balance. Consolidation model employs matric suction and constitutive relations for pore water and pore gas pressures are incorporated. The instantaneous values for rate of production of gas and water are obtained from the thermal dissociation model. These values are incorporated in the pore pressure relations to obtain pore pressure. Pore pressures at instants in turn give us the subsidence rate. A compression subsidence formulation models bed collapse during dissociation of the hydrate. The subsidence model is validated by data on marine sediment subsidence from literature [8]. The temperature and pore pressure data is validated from a similar model from literature [8]. The model will enable the safety of gas hydrate drilling to be ascertained before actual drilling by plugging in the sediment properties, rate of heating, temperature of drilling/heating fluid and obtaining the rate of collapse. The optimum temperature of fluid can be found which will enable safe drilling in that particular sediment. References [1] Yousif. M. H, Abass. H. H., Selim. M. S. and Sloan. E. D., Experimental and Theoretical Investigation of Methane Gas Hydrate Dissociation in Porous Media. SPE Res. Eng., 69-76, 1991 [2] Selim, M. S. and Sloan, E. D.: 1989, Heat and mass transfer during the dissociation of hydrate in porous media, AIChE J. 35, 10491052. [3] Javanmardi J., Nasrifar Kh., Najibi S.H., Moshfeghian M. Economic evaluation of natural gas hydrate as an alternative for natural gas transportation Applied Thermal Engineering, Volume 25, Issues 1112, August 2005, Pages 1708-1723 [4] Goel N. In situ methane hydrate dissociation with carbon dioxide sequestration: Current knowledge and issues. Journal of Petroleum Science and Engineering 51 (2006) 169184 [5] Yuehong Bi, Tingwei Guo, Liang Zhang, Hua Zhang and Lingen Chen Experimental study on cool release process of gas-hydrate with additives. Energy and Buildings Volume 41, Issue 1, January 2009, Pages 120-124 [6] Civan, F.C., 2001. Scale effect on porosity and permeability: kinetics, model and correlation. A.I.Ch.E. Journal 47 (2), 271287. [7] Tester, J. W.: 1997, Thermodynamics and Its Applications, 3rd ed., Prentice Hall, New Jersey. [8] Reem Freij-Ayoub et al., A wellbore stability model for hydrate bearing sediments, Journal of Petroleum Science and Engineering (2006), doi:10.1016/j.petrol.2005.10.011

Fig-5 Temperature and Pore Pressure profiles for dissociating hydrated sediment used for model validation.[8]. (Compare with Fig-6)

Fig-6 Model compared with actual settlement data [8]. Void ratio of 1.5, compression index 0.2, shearstress change of 1 kPa and effective overburden pressure of 10 kPa Conclusion Heat transfer in the hydrated sediment bed is modeled. A parametric study was conducted to ascertain the influence of three variables on the temperature time curve and temperature distribution