Kinetics of Gas Hydrate

 Nucleation
 Growth
 Growth Prevention and Enhancement
 Dissociation
 9.6

Dissolution
Reactor Pressure (bar) 9.4

9.2

Nucleation
and Decomposition
9.0 Growth

8.8

270 272 274 276 278 280 282

Gas-Liquid Interface Temperature (K)

Fig. Temperature and pressure trace for formation and decomposition of ethane hydrates
Nucleation
 Hydrate Nucleation is the process, during which
small hydrate crystals (nuclei) grow and disperse in
an attempt to achieve critical size for continued
growth.
 Nucleation step is a microscopic phenomena
involving tens to thousands of molecules (Mullin.
1993).
 The current hypotheses for hydrate nucleation are
based upon the better-known phenomena of water
freezing, the dissolution of hydrocarbons in water,
and computer simulation of both phenomena.
 Nucleation is a statistically probable process.
Mechanism for nucleation of water to
Ice
 Two models of water exist
 “Iceberg” model proposed “ water as an

equilibrium mixture of short-lived hydrogen-

bonded clusters, together with a non-
hydrogen-bonded dense phase.
 A second model and currently the most

favored model, is based on the liquid water

“hydrogen-bonded network”.
Solubility of Natural gas in water
 Methane solubility in water is very less.
 Methane solubility in water depends on

pressure and temperature of the system.

 Also depends on the presence of extraneous

materials in water, like salt and suspended

solids.
 Types of Nucleation
 Basically nucleation is of two types
 1) Homogeneous nucleation
 2) Heterogeneous nucleation
 Homogeneous nucleation:Homogeneous

nucleation (HON) is rarely encountered in the

real world.
 Homogeneous nucleation is a solidification process occurring
in the absence of impurities. It involves many more molecules
than could collide simultaneously, so a sequence of
bimolecular collisions of an autocatalytic nature is more
probable.
 That is, there is a sequential formation of clusters (embryos)
within the supercooled liquid of increasing cluster size ( A2 =
cluster containing two molecules, A3 = cluster containing three
molecules, etc.), until the critical ncluster size, An is reached.
 The critical cluster size (also called critical nucleus) is the
cluster size that must be reached before nuclei/clusters can
grow spontaneously.
 A+A↔A2
 A2 +A↔A3
 ………………
 An-1+ A ↔An (Critical Cluster)
 Such a phenomena may be interpreted by the
excess Gibbs free energy (∆G) between a
small solid particle of solute and the solute in
solution. ∆G is equal to the sum of the
surface excess free energy ∆Gs and the
volume excess free energy ∆Gv.
 ∆G= ∆Gs + ∆Gv

 Where is the free energy per unit volume and δ is the

interfacial tension. ∆Gs and ∆Gv. are of opposite sign and
are function of r, radius of solid particle.
 The maximum value of ∆G and the critical
radius are obtained by differentiating the
above equation and setting the result to zero
to obtain
 r =-2δ/∆gv
c crit
 And ∆Gcrit =4πδ rc2/3
 Below the critical radius a new crystal may
either grow or re-dissolve. The critical radius
represents the minimum size, above which a
nucleus will only grow.
 Heterogeneous Nucleation

 Heterogeneous nucleation occurs in the presence of a

foreign body or surface, at supercoolings lower than
that required for homogeneous nucleation.
 The angle of contact (θ) between the hydrate crystal
and a surface is related to Φ, a fraction which
multiples the value of ∆Gcrit in homogeneous
nucleation to obtain a smaller value ∆G’crit for
heterogeneous nucleation, by the relation.
∆G’crit= Φ ∆Gcrit
Φ=[(2+cosθ)(1-cosθ)2]/4
When the angle of contact θ=180° then ∆G’crit= ∆Gcrit
 And when θ=0° then ∆G’crit= 0
Temperature pressure trace of hydrate formation and
dissociation
Conceptual Kinetic Model
 All modern pictures and models of hydrate crystal growth
include mass transfer from the bulk phase to the hydrate.
Noyes and Whitney (1897) proposed that the change in the
rate of crystal growth (dm/dt) was controlled by diffusion
from the bulk concentration to the crystal interface, which
can be represented as:

dm
 K d A(C  C eq )......... ...1
dt

 where C and Ceq are the solution concentration in the

supersaturated solution and at equilibrium respectively. A
is the crystal area and Kd is the coefficient of mass transfer.
Conceptual model of mass transfer from gas phase to crystal surface (Sloan, 1998)
 Berthoud (1912) and Valeton (1924) modified
the concept to include two steps: (1) diffusion
to the interface and (2) reaction at the
interface (Fig. 3a). Now the diffusion step can
be represented by modifying the driving force
in the previous equation for the solute
concentration at the crystal-solution
interface, Ci, this is:
dm
 K d A(C  Ci ).......2
dt
 The second reaction step for incorporation of
the substance into the crystal at the interface
can be written as :
dm
 K r A(C i  C eq )..... 3
dt
 where Kr is a rate constant for the surface reaction.
Since the interfacial concentration (Ci) is difficult to
measure, the above two equations are combined by
eliminating dm
Ci to obtain:
 K '' A(C  C eq )......4
dt

 where the overall transfer coefficient is expressed in

terms of the coefficients for diffusion Kd and reaction Kr
1 1 1
as : ''
  ......5
K dK rK

 Some modifications are often made to the basic Eq. (4)

(Sloan, 1998):
 The crystal growth rate (dm/dt) is represented as the
rate of gas consumption,
 The concentrations (C) are replaced with fugacities.
Modified conceptual model of mass transfer from gas phase to crystal surface