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Abstract
In the last 10 years, there have been a number of studies in modeling of the deposition processes in flowlines. Most of these models: (1)
assume empirical or semi-empirical correlations to predict the pressure drop and temperature profile, (2) ignore the radial convection
flow in the layer composed of the two-phase wax and oil (that is the gel layer), and (3) use Fick’s law to describe the diffusion flux of
species towards the wall by using the chain rule to relate concentration gradient to temperature gradient. In this work, a rigorous math-
ematical model for the prediction of wax deposition in pipelines is presented for laminar flow. The transient deposition of each compo-
nent is calculated from the solution of the coupled momentum, energy and, species balance equations, and a thermodynamic wax
precipitation model at the local level. An enthalpy formulation based on a fixed-grid approach is used to approximate the convection
flow in the gel layer. We do not use the chain rule to relate composition gradient to temperature gradient in Fick’s law to avoid violating
the laws of irreversible thermodynamics. Our diffusion flux expression includes molecular diffusion (concentration gradient is driving
force) and thermal diffusion (temperature gradient is driving force) with appropriate diffusion coefficients. This work also includes
the description of the numerical solution of the governing equations. Numerical results and features of wax deposition as well as model
verification with experimental data are presented in a separate paper.
Ó 2007 Published by Elsevier Ltd.
Nomenclature
to some 60 have high crystallization temperatures and may wax precipitation from crude oils and gas condensate fluids
crystallize even at low concentration in the petroleum fluid for local equilibrium calculations [6]. However, despite
mixture. The crystallites from petroleum fluids are often much progress, the more complicated problem of wax
referred to as waxes; the temperature at which crystalliza- deposition in non-isothermal flowlines is still in an early
tion occurs is referred to as wax-appearance temperature stage of development.
(WAT). There are two main processes that affect the deposition
An understanding of the mechanisms of the wax deposi- of wax in flowlines: (1) heat transfer, and (2) species flow.
tion and modeling of the process is likely to be a key step The heat transfer is mainly from conduction and convec-
towards an optimum design and prevention of the tion. The flux of species by convection and diffusion is
problem. expected to strongly influence the deposition. To the best
There has been an extensive effort in the last decade to of our knowledge, the radial convective velocity in the
develop theoretical models for wax deposition calculations. region containing the deposition for the laminar flow has
In recent years, there has been success in the prediction of been neglected in the past [7–16]. The radial velocity is
R. Banki et al. / International Journal of Heat and Mass Transfer 51 (2008) 3387–3398 3389
expected to be small in comparison to axial velocity, but its fluxes and the study of diffusion effects are major goals of
contribution to species flux in the radial direction may be this work.
comparable to radial diffusion flux (due to non-uniform This paper is organized as follows. First, a detailed
wax deposition, radial convection develops). One objective description of the mathematical model is presented for
of this work is to include the radial convective flux in the the coupled momentum, energy, and mass balances. We
formulation. then provide the thermodynamics of wax-precipitation
Wax deposition is a moving boundary problem and the model followed by presenting the numerical formulation
numerical solution of the balance equations can be a chal- of the governing equations and the algorithm. The work
lenge. A large number of numerical techniques are avail- is ended with a general summary and concluding remarks
able for the solution of a moving boundary problem. emphasizing that concentration gradient and temperature
There are two main approaches. In the transformed-grid gradient may not be related through a chain rule.
approach, the governing differential equations and their
boundary conditions are cast into a generalized curvilinear 2. Domain definition and basic assumptions
coordinate system. The equations can then be solved on a
uniform-rectangular grid, which remains fixed in space We consider a horizontal pipe of length L and inner
and time. In essence, the moving boundary is immobilized. radius R0 (Fig. 1). A multicomponent fluid is injected at
Extra terms in balance equations may be required for one end with a volumetric flow rate Q at temperature,
conservation of mass, momentum, and energy [17]. In the Tin. The pipe wall temperature is set at constant tempera-
fixed-grid approach, which is also known as the ture, Ta where Ta < Tin. The outlet pressure is held
enthalpy–porosity approach [18], a fixed grid is applied constant at p0. We assume single-phase and gel subdomains
directly in real space (that is, the problem domain) and as shown in Fig. 1. The formation of solid wax crystals
the interface conditions are accounted for by the definition creates a gel layer, which consists of a liquid phase and a
of suitable source terms in the governing equations [18–20]. nonmoving solid phase [15]. Studies of distillate fuels
The enthalpy–porosity approach has been successfully and model petroleum fluids reveal that as little as 2%
implemented in many engineering problems that involve of the crystal precipitate is required to gel the fluid
a liquid to solid phase change such as freezing of a pure [15,23,24,27]. When the amount of crystallites increases,
liquid in a thermal cavity and melting of a pure metal the gel hardens. The process is called aging of the gel layer.
[18,21,22]. In this work, we adopt this approach for the first The following assumptions are made in our work:
time in the formulation of wax deposition by treating the
layer with deposition as a pseudo-porous medium. Various (1) Shear dispersion and Brownian diffusion are
authors have shown that the crystallization of paraffins in neglected.
oil leads to the formation of gel with a complex morphol- (2) Gravity is neglected.
ogy. The gelation is due to flocuulation of orthorhombic (3) Diffusions (both thermal and molecular) are
wax crystallites that appear in the solution. Observation neglected in the axial direction.
with cross-polarized microscopy has revealed that the (4) Diffusion is neglected in the solid phase.
crystallites have structures of platelets that overlap and (5) Solid heat capacity and fluid thermal conductivity of
interlock and a network structure of wax crystals are each component are assumed temperature indepen-
formed [15,23,24]. Therefore, the gel behaves as porous dent.
media. In this work the Darcy-type source term is added (6) Laminar flow is assumed.
to the momentum equation to describe the deceleration (7) Multisolid wax precipitation is assumed.
of flow in the gel layer. The energy equation for the multi-
component, two-phase flow is written in terms of the Ta
enthalpy. The relationship between the enthalpy and the
Gel layer
temperature can be described by an equation of state.
To the best of our knowledge, in all the models in the R0
Liquid region
literature the driving force for radial diffusion is first
written in terms of concentration gradient and then
through the chain rule, the temperature gradient is intro-
duced [7–11,13–16,25,26]. In other words, various authors
use the molecular diffusion coefficients with the driving
force represented by temperature gradient. Thermodynam-
ics of irreversible processes offers a different representation r
of diffusion with temperature gradient. In our formulation,
we represent the molecular diffusion (driving force is z
concentration gradient), and thermal diffusion (driving
force is temperature gradient) from thermodynamics of Fig. 1. Computational domain, the geometry of problem is a 2D circular
irreversible processes. Proper representation of diffusion coordinate system.
3390 R. Banki et al. / International Journal of Heat and Mass Transfer 51 (2008) 3387–3398
we find C = 106 m2 for describing flow in the gel layer as The last expression in Eq. (15), which ignores the axial
we will comment in Hoteit et al. [32]. thermal conduction at the outlet, is based on a pseudo-stea-
dy state assumption. The effective thermal conductivity keff
3.2. Energy balance in Eq. (14) can be calculated from the Maxwell correlation
[33]:
The general form of the energy equation for a single ½2k o þ k s 2S s ðk o k s Þ
phase, multicomponent mixture can be written as [28]: k eff ¼ ko: ð16Þ
½2k o þ k s þ S s ðk o k s Þ
!
o X n
DP One may use other models in the calculation of the effective
ci H i ¼ r e þ þ T : rv; ð10Þ
ot i¼1 Dt thermal conductivity of a two-phase mixture [34]. The mo-
lar enthalpy of the oil phase can be calculated from the PR-
where H i is the partial molar enthalpy of component i, and EOS [35]:
DP/Dt is the energetic contribution of the pressure due to
H o ðT ; p; xo Þ ¼ H ðT ; 0; xo Þ þ RT ðZ 1Þ
expansion or compression. The term T is the stress tensor
and T:$v is the energetic contribution of viscous dissipa- T daðT Þ aðT Þ Z þ 2:414B
þ pffiffiffi pffiffiffi ln ;
tion. The term e is the multicomponent energy flux relative 2 2b dT 2 2b Z 2:414B
to fixed coordinates; it is defined as [28]: ð17Þ
X
n
where Z = pvo/RT is the compressibility factor of the oil
ev ci H i þ q: ð11Þ
i¼1
phase and H*(T, 0, xo) is the ideal gas enthalpy of liquid
P mixture at zero pressure, which can be calculated from:
The term v ni¼1 ci H i is the energy flux due to convection. X
n
The term q is given by [28]: H ðT ; 0; xo Þ ¼ xo;i H i ðT ; 0Þ: ð18Þ
i¼1
X
n
q ¼ krT þ J i H i þ qðxÞ ; ð12Þ In Eq. (18), H i ðT ; 0Þ is the ideal gas enthalpy of component
i¼1
i. Passut and Danner [36] provide correlations for ideal gas
whereP k$T is the energy flux due to conduction and the enthalpy of some 90 substances.
n
term i¼1 J i H i represents energy transfer due to diffusion We use the following expression to calculate the
of species. The term q(x) represents the Dufour or diffu- enthalpy of the solid wax:
sion-thermo effect, which is usually negligible. Neglecting X
n
the energetic contributions of the pressure DP/Dt, viscous H s ðT ; p; xs Þ ¼ xs;i H s;i ðT ; pÞ: ð19Þ
i¼1
dissipation
Pn T:$v, and the inter-diffusion of enthalpy
i¼1 J i H i , the energy equation for the single-phase liquid Assuming that pressure has negligible effect on the molar
flow can be written as enthalpy of the solid, and neglecting the effect of tempera-
3392 R. Banki et al. / International Journal of Heat and Mass Transfer 51 (2008) 3387–3398
ture variation on heat capacity of component i in the solid The total molar density c is defined by
state, we can write [35]: X
c¼ S j cj : ð29Þ
H s;i ðT ; pÞ H s;i ðT ; pfi Þ H s;i ðT fi ; pfi Þ þ Cps;i ðT T fi Þ: ð20Þ j¼o;s
From the definition of molar latent heat of component i The overall composition of component i is related to the
(heat of fusion): phase composition of component i by
X
ki ¼ H o;i ðT fi ; pfi Þ H s;i ðT fi ; pfi Þ: ð21Þ czi ¼ S j cj xj;i ; i ¼ 1; . . . ; n: ð30Þ
j¼o;s
Eqs. (19)–(21) are combined to obtain
Using Eq. (30) one can write Eq. (28) as
X
n
H s ðT ; P ; xs Þ ¼ xs;i ½H o;i ðT fi ; pfi Þ ki þ Cps;i ðT T fi Þ: o X
i¼1 ðczi Þ þ r ðS j cj xj;i vj þ S j J j;i Þ ¼ 0; i ¼ 1; . . . ; n:
ot j¼o;s
ð22Þ
ð31Þ
In this work, the terms ki ; H o;i ðT fi ; pfi Þ; and Cps,i are as-
sumed constant; ki can be evaluated as the average value The total molar balance from Eq. (31) can be written as
at T and T fi . oc X
þr ðS j cj xj;i vj Þ ¼ 0; i ¼ 1; . . . ; n: ð32Þ
ot j¼o;s
3.3. Species balance
Eqs. (31) and (32) are subject to the following boundary
The gel layer has structure of platelets that overlap and conditions:
interlock and may contain up to 98% liquid in early time of
deposition [23,24,37]. The gel layer may grow with time. zi ¼ ðzi Þin at z ¼ 0;
Let us consider flow in two-phase in the domain and write ðJ j;i Þr ¼ 0 at r ¼ 0; R0 ; ð33Þ
the mass balance of species i: ozi
¼ 0 at r ¼ 0:
o X X or
ðS j cj;i Þ þ r: ðS j cj;i vj;i Þ ¼ 0; i ¼ 1; . . . ; n; ð23Þ
ot j¼o;s j¼o;s
3.3.1. Diffusion flux
where cj,i and vj,i are the molar density of component i in The molar diffusion flux in a vector form can be written
phase j, and the velocity vector for component i in phase as [38]:
j, respectively. The relation between the bulk velocity, vj
of phase j, molar diffusive flux, Jj,i, and velocity of compo- J ¼ cðDM rx þ DT rT þ DP rpÞ: ð34Þ
nent i in phase j, vj,i is given by M T P
where J, D , D and D are the total diffusion flux vector,
S j cj;i vj;i ¼ S j cj;i vj þ S j J j;i ; i ¼ 1; . . . ; n: ð24Þ molecular diffusion coefficient matrix, thermal diffusion
coefficient vector, and pressure diffusion coefficient vector,
Substitution of Eq. (24) into Eq. (23) yields
respectively. On the right side, the first, second, and third
o X X terms represent molecular diffusion, thermal diffusion,
ðS j cj xj;i Þ þ r ðS j cj xj;i vj þ S j J j;i Þ ¼ 0; i ¼ 1; . . . ; n;
ot j¼o;s j¼o;w and pressure diffusion, respectively. Neglecting the pressure
diffusion, the diffusion flux of component i, i = 1, . . . , n 1,
ð25Þ
in phase j is given by
where cj and xj,i are the molar density of phase j and mole
J j ¼ cj ðDM T
j rxj þ Dj rT Þ: ð35Þ
fraction of component i in phase j. The molar density of
phase j and molar density of component i in phase j are re- where Jj = [Jj,i] and $xj = [$xj,i]; DM M
j ¼ ½Dj;i;k ; k ¼ 1; . . . ;
lated by T T
n 1 and Dj ¼ ½Dj;i are the molecular diffusion coeffi-
cj;i ¼ xj;i cj : ð26Þ cients and the thermal diffusion coefficients in phase j,
respectively. Firoozabadi et al. [38,39] describe the method-
Note that in each phase ology for calculating molecular and thermal diffusion
X
n coefficients. Eq. (35) consists of two terms. The first term
ðJ j;i Þ ¼ 0; j ¼ o; s: ð27Þ on the right side is known as the Fick’s law and the second
i¼1
term is often referred to as the Soret effect. In a multicom-
By summing Eq. (25) for i = 1, . . . , n and using
P ponent mixture such as a petroleum fluid with varying
n
i¼1 xj;i ¼ 1; j ¼ o; s, and Eq. (27), the total molar balance molecular sizes and molecular shapes, in addition to diag-
expression is given by onal molecular diffusion coefficients, cross coefficients may
o X X become important [40].
ðS j cj Þ þ r ðS j cj vj Þ ¼ 0: ð28Þ To the best of our knowledge, in all of the existing
ot j¼o;s j¼o;s models for wax deposition, the diffusion flux in a (pseudo)
R. Banki et al. / International Journal of Heat and Mass Transfer 51 (2008) 3387–3398 3393
" #
binary mixture in the radial direction is written in the fol- X
n
N s;k
lowing form: zi xo;i 1 ¼ 0; i ¼ 1; . . . ; ðn ns Þ; ð40Þ
k¼nns þ1
F
oz1 oz1 oT
J o;1 ¼ cDM
o;1;1 ¼ cDM
o;1;1 : ð36Þ where fo,i(p,T,xo) is the fugacity of component i in the oil
or oT or
phase with composition xo,i, Ns,i is the number of moles
The concentration gradient in the Fick’s law of diffusion is
of component i in the wax phase, F is the total number
subject to constant temperature and pressure and thus the
of moles of the wax components.
expression above is not valid. The appropriate form of the
The fugacities of a pure component i in solid and liquid
diffusion flux without pressure diffusion is given by Eq.
states are related by [33]:
(35).
fs;ipure ðp; T Þ ¼ fo;i
pure
ðp; T Þ exp ½Dli ; ð41Þ
3.4. Solid–liquid equilibria
where Dli ¼ lpure pure f f f
o;i ls;i =RT ¼ Dhi =RT i DCp i =RT i
There are two types of models for wax precipitation cal- T fi =T 1 DCpi =RT fi ln T fi =T :
culations in petroleum fluids; (1) solid solution, and (2) The symbols are defined in the Nomenclature. The
multisolid-phase. The multisolid model can describe the fugacity of pure component i in the liquid state can be
WAT and the amount of precipitation more accurately calculated from the Peng–Robinson equation of state.
than the solid solution model [41,42]. In this work, we per-
form the solid–liquid phase calculations by using the mul- 4. Numerical model
tisolid-phase model by Lira-Galeana et al. [6], where each
precipitated component forms a solid layer, which does The momentum, energy, and species mass balance equa-
not mix with the other solid layers. The model uses a tions and the local wax solid–liquid model are coupled and
two-step procedure for the phase-split calculation: solved with initial and boundary conditions to predict the
pressure, temperature, velocity and composition in the gel
(1) Stability analysis. and liquid regions as well as the wax fraction (i.e., volume
(2) Phase-split calculation. fraction or weight fraction). The 2D computational
domain is discretized into a structured grid of rectangular
3.4.1. Stability analysis elements. A finite-volume based method is used for the spa-
This is a preprocessing step to identify which of the com- tial approximations. Different temporal, spatial and linear-
ponents are precipitating and which are not. A component ization schemes are implemented to solve the governing
i precipitates at a given temperature and pressure if the fol- equations. The scalar unknowns like the pressure, temper-
lowing condition is satisfied [33]: ature, enthalpies, densities, mole fractions and saturation
are approximated over the same control volumes while
fi ðp; T ; zÞ fs;ipure ðp; T Þ P 0; ð37Þ
the velocity is approximated over a different control vol-
where fi(p,T,z) and fs;ipure ðp; T Þ
are the fugacity of compo- ume. The numerical algorithm uses two levels of iterations
nent i with overall composition z, and fugacity of pure so- at each time step. In the inner level, we solve the coupled
lid-component i at pressure p and temperature T, momentum and total mass balance equations to approxi-
respectively. mate the pressure and the velocity field. In the outer level,
we solve the energy equation and the species balance equa-
3.4.2. Phase-split calculation tions to calculate the temperature and the overall composi-
Suppose the stability-analysis provides the condition tion. Once the overall composition, temperature, and
that ns components of the n-component mixture (i.e., the pressure are known, we apply the phase-equilibria model
components (n ns + 1), . . . ,n) precipitate. These compo- to calculate the oil and wax compositions and the wax sat-
nents, therefore, fulfill Eq. (37). uration in the gel layer.
The governing equations for the wax precipitation are Here, we provide the basic numerical methods used to
given by the equilibrium and the material balance equa- solve our system of equations.
tions. For every precipitating component i, the equilibrium
and material balance equations are, respectively, given by 4.1. Solution of the momentum equation
fo;i ðp; T ; xo Þ ¼ fs;ipure ðp; T Þ; i ¼ ðn ns þ 1Þ; . . . ; n; ð38Þ
The momentum equation is solved by using the SIM-
and " # PLER method of Patankar [43]. In this method, a ‘‘stag-
X
n
N s;k N s;i gered” or a displaced grid for the velocity components is
zi xo;i 1 ¼ 0; i ¼ ðn ns þ 1Þ; . . . ; n: used. The velocity components are calculated for the points
k¼nns þ1
F F
that lie on the faces of the control volumes and the pressure
ð39Þ at the main grid points (see Fig. 3). For presentational con-
The material balance equations for the non-precipitating venience, the general discretization of axial and radial
components are momentum equations (combined Eqs. (1) and (5), and
3394 R. Banki et al. / International Journal of Heat and Mass Transfer 51 (2008) 3387–3398
4.3. Solution of the species balance equations 7. Normalize the oil mole fraction xo,i.
8. Check if the convergence criterion kxo xold
o k < TOL is
Neglecting the velocity and diffusion in the solid phase satisfied. If not, set xold
o ¼ xo and repeat steps 2–8.
and using Eq. (31), the species balance can be written as
o The computational speed of each SSI iteration is quite
ðczi Þ þ r ðcvo zi Þ ¼ r ðS o J o;i Þ þ r ðS s cs xs;i vo Þ; fast but generally it requires more iterations than the NR
ot
method. In the NR algorithm, we define the residual func-
i ¼ 1; . . . ; n: ð49Þ
tion gi from (see Eq. (38)),
The finite-volume scheme is also used for the spatial dis- gi ðxo Þ fo;i ðp; T ; xo Þ fs;i ðp; T Þ ¼ 0; i ¼ ðn ns þ 1Þ; . . . ; n:
cretization of the species balance equations. The convec-
tion term in the left-hand side of Eq. (49) is treated ð50Þ
implicitly in time with a first-order upwinding scheme. The composition of the precipitating components is then
The terms on the right-hand side are calculated explicitly. computed by solving:
JDxo ¼ G; ð51Þ
4.4. Solution of the phase-equilibria model
where
The stability analysis can be readily performed by using
ogi
the PR-EOS and the expression of the fugacity of the wax J¼ ; Dxo ¼ ½xi i¼ðnns þ1Þ;...;n ; and G
oxo;j i;j¼ðnns þ1Þ;...;n
phase given in Eq. (41). The phase-split calculation can be
performed efficiently by using the successive-substitution- ¼ ½gi i¼ðnns þ1Þ;...;n :
iteration (SSI) or the NR methods. Here, we provide the
algorithms for the phase-split calculation by both methods. Note that the size of the linear system is equal to the num-
The governing system has (n + ns) equations given by ber of precipitating components. The mole fractions of the
Eqs. (38)–(40) and (n + ns) unknowns, which are the mole oil phase for the precipitating components are then up-
fraction of the oil phase (xo,i; i = 1, . . . , n) and the number dated from
of mole of the precipitated wax components (Ns,i;
xo;i ¼ xold
o;i þ Dxo;i ; i ¼ ðn ns þ 1Þ; . . . ; n: ð52Þ
j = (n ns + 1), . . . , n).
The main steps of the SSI algorithm are as follows: The NR algorithm is similar to SSI algorithm described
above and is implemented by replacing the update of the
1. Guess an initial oil mole fraction xold o . If no information composition of the precipitating components in Eq. (52)
is available, take the oil mole fraction to be the same as by step 3 in the SSI algorithm. The other steps are exactly
the feed mole fraction (i.e., xold
o ¼ z). the same.
2. Calculate the fugacity fo;i ðp; T ; xold
o Þ from the PR-EOS. In all our calculations, even very close to phase
3. Update the oil mole fraction of the precipitating compo- boundaries, the SSI method performed very well. Unlike
nents from (see Eq. (38)): vapor-liquid equilibria calculations, where close to phase
fs;i ðp; T Þ boundaries the SSI algorithm becomes inefficient, there
xo;i ¼ xold
o;i ; i ¼ ðn ns þ 1Þ; . . . ; n: was no convergence problem with the SSI algorithm in
fo;i ðp; T ; xold
o Þ
the entire saturation range in wax precipitation
4. Define Ns from calculations.
X
n
N s;j
Ns ¼ :
j¼nns þ1
F 5. General algorithm
Ns can be calculated by summing Eq. (39) for The main steps of the algorithm for predicting the wax
i = (n ns + 1), . . . ,n, that is, deposition in pipelines are the following:
Zs X o
Ns ¼ ; – Initialize the fluid and pipe parameters.
1 Xo
P P – Iterate over the time step (outer loop).
where X o ¼ ni¼nns þ1 xo;i and Z s ¼ ni¼nns þ1 zi . 1. Update the diffusion coefficients and the fluid
5. Use Eq. (39) to calculate the number of moles of the pre- viscosity.
cipitating components 2. Iterate until convergence (inner loop).
N s;i ¼ zi xo;i ½1 N s ; i ¼ ðn ns þ 1Þ; . . . ; n:
2.1 Solve the momentum and the total mass balance
6. Use Eq. (40) to calculate the oil mole fractions of the equations to approximate the pressure and
non-precipitating components velocity field.
zi 2.2 Solve the energy equation to calculate the
xo;i ¼ ; i ¼ 1; . . . ; ðn ns Þ:
1 Ns temperature.
3396 R. Banki et al. / International Journal of Heat and Mass Transfer 51 (2008) 3387–3398
2.3 Solve the species balance equations to calculate gel layer, the source term increases gradually with a
the overall composition. Carman–Koseny-type function as the solid saturation
2.4 Set cold = c, where c is the overall density. increases. The velocity field is inversely proportional
2.5 Apply the phase-equilibria model to calculate to source function. The increase in the source term
phase compositions, saturation, and oil, wax leads to a decrease in the velocity field. The energy
and overall densities. equation is written in terms of the liquid and solid
2.6 Check the convergence criterion enthalpies.
kcold ck < TOL. If no convergence, repeat
steps 2.1–2.6. A detailed numerical algorithm to solve the mathemati-
– Repeat until the assigned time is reached. cal model is also provided. The momentum equation cou-
pled with the total mass balance equation is solved by the
The fluid viscosity is a function of temperature, pressure SIMPLER method to approximate the pressure and veloc-
and composition. It is calculated from the correlation of ity field. The energy equation is discretized by a finite vol-
Lohrentz et al. [45]. The diffusion coefficients and the vis- ume scheme and linearized by the NR method. The liquid
cosity are updated outside the inner loop for their weak enthalpy is related to temperature using the PR-EOS. A
dependency on the temperature and pressure variation dur- robust algorithm for solid–liquid equilibria is presented.
ing the convergence process of the inner loop. The algorithm uses the SSI method or the NR method.
With the NR method, the size of the linear system is the
6. Summary and concluding remarks number of precipitating components which makes the algo-
rithm very efficient.
A mathematical model for wax deposition in pipelines
for a multicomponent fluid is presented. The model couples
the momentum, energy and species balance equations and Acknowledgements
a multisolid-wax precipitation model. There are two main
features that characterize our model: The funding for this work was provided by the member
companies of the Reservoir Engineering Research Institute
1. We include molecular diffusion and thermal diffusion (RERI). We thank Daniel Rosner and Alana Leahy-Dios
in our formulation. Both affect the flux of species of Yale University for reading the paper and their
towards the pipe wall by diffusion. The driving force comments.
for molecular diffusion is the concentration gradient.
The driving force for thermal diffusion is temperature Appendix A
gradient. These two gradients may not be proportional
in the gel layer. The temperature gradient is expected The energy balance equation (Eq. (46)), in cylindrical
to be high close to the pipe wall. The concentration coordinates, is written as
gradient, because of phase change, is expected to be !
high close to the interface of the single liquid phase o X o 1 o
S j cj H j þ ðJ z Þ þ ðJ r Þ ¼ 0; ðA:1Þ
region and the gel layer. Furthermore the temperature ot j¼o;s oz r or
gradient close to the wall may reach a pseudo steady
state quickly and stay large close to the wall. This where
may not be true for the concentration gradients. All
these aspects may lead to incorrect results by the com- oT
J z ¼ S o co H o vo;z k eff and
monly accepted use of the chain rule to replace con- oz
centration gradient by temperature gradient in the
oT
Fick’s law. In Hoteit et al. [32], the numerical results J r ¼ r S o co H o vo;r k eff :
or
will demonstrate the importance of the use of the
proper diffusion flux expression and the need for con- Let P be a control volume with edges e, w, n and s, and
sistency in diffusion flux expression from irreversible neighboring control volumes E, W, N, and S. Fig. A1 illus-
thermodynamics. With consistent formulation the trates the five point grid cluster at P. For the sake of sim-
model is predictive. plicity, we suppose that the domain is uniformly discretized
2. An enthalpy–porosity approach is used to account for with space steps Dz and Dr along the z- and r-directions,
the flow deceleration in the gel layer where it is mod- respectively (Fig. A1).
eled as a pseudo-porous medium. A Darcy-type Integrating Eq. (A.1) over the control volume P, we get
source term is added to the momentum equations. the semi-discretized equation:
This source term is a function of the porosity (oil sat-
!
uration) in the gel layer. In the single-phase liquid o X
region, this function is set to zero and the velocity S j cj H j DzDr þ J e J w þ J n J s ¼ 0: ðA:2Þ
ot j¼o;s
is calculated from the momentum equation. In the P
R. Banki et al. / International Journal of Heat and Mass Transfer 51 (2008) 3387–3398 3397
J n ¼ Fe n H o;n Dn ðT N T P Þ; J s ¼ Fe s H o;s Ds ðT P T S Þ;
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