Diffusion–reaction–dissolution–precipitation model in a heterogeneous porous medium with nonidentical diffusion coefficients: Analysis and homogenization
Available accessResearch articleFirst published online November 9, 2022
Diffusion–reaction–dissolution–precipitation model in a heterogeneous porous medium with nonidentical diffusion coefficients: Analysis and homogenization
We study a pore-scale model where two mobile species with different diffusion coefficients react and precipitate in the form of immobile species (crystal) on the surface of the solid parts in a porous medium. The reverse may also happen, i.e. the crystals may dissolute to give mobile species. The mathematical modeling of these processes will give rise to a coupled system of ordinary and partial differential equations. We first prove the existence of a unique nonnegative global weak solution and then upscale the model from microscale to macroscale.
Several problems in the fields of chemical engineering, material sciences, soil mechanics, reservoir flow, groundwater flow, etc. can be studied in the context of porous media flow, cf. [5,28,29,38,47,48,56,57]. Crystal dissolution and precipitation is one such flow phenomena other than diffusion, advection, and reaction that plays an important role when the minerals are present in the given porous medium. Dissolution and precipitation of minerals have been widely studied in recent years by mathematicians, engineers, hydrologists, etc., cf. [24,25,37,43–45,47,49,51,53,55,57] and references therein. A porous medium is heterogeneous in nature with porosity and is composed of pore space and usually a connected solid matrix. It is important to model the transport processes in such a medium rigorously so that it depicts the real world situations as close as possible, therefore, in this context, the given porous medium may be treated as a multiscale domain, i.e. we describe the medium both at the micro scale and at the macro scale. The microscopic description of the medium models the transport processes rigorously, however, due to heterogeneity of the medium the micro scale models are not suited for conducting numerical simulations. We require the macroscopic description of the given porous medium where an averaged behavior of the domain and the transport processes are considered. This type of micro-macro scale modeling is widely considered in the literature, cf. [3,21,36,40,43] and references therein. The process to upscale from microscale to macroscale is called averaging/homogenization, cf. [1,14,21,41,42,44,56]. In our work, we shall use the periodic homogenization where we assume that the solid matrices are disconnected but distributed periodically in the given medium, see Section 2 for details. A natural porous medium has a complex geometry where the solid parts are connected and non-periodic but this periodicity assumption seems to be a good approximation to the actual domain.
The mobile species are usually present in the pore space whereas the crystals/minerals are present on the solid matrices/parts. The transportation of mobiles species is usually governed by diffusion, dispersion, or advection and is modeled by Fick’s law. The reaction amongst the mobile species is modeled by mass-action kinetics. The modeling of precipitation can be done with the help of mass action law and for the dissolution (adsorption) rate a multivalued function needs to be introduced. This idea has been explored in [25,53–55] and references therein. For equilibrium adsorption, a linear dissolution rate is proposed in [25]. The model proposed in [26,33] considered advection, diffusion, and reaction amongst mobile species where the authors have proved the existence of a global weak solution for a system of diffusion–reaction equations with identical diffusion coefficients. The existence theory in [26,33] resides on Schaefer’s fixed point Theorem and on the construction of a suitable Lyapunov functional which is used to obtain some a-priori estimates. The authors in [19] proved the global existence by considering a renormalized solution to circumvent the question of -boundness. The extension of these results from the case where all the species are mobile to a case where some of the species can be immobile can be found in [7,34,53,54]. The authors in [7] dealt with the adsorption reaction at the walls of the pore space and the existence of a global solution is proved. However, such a model with smooth rates is not suited for the case of precipitation-dissolution of minerals. To model the dissolution rate, we consider the multivalued discontinuous function as shown in [53,54]. For the case of one single kinetic reaction with one mobile and one immobile, the proof of the existence of a solution can be found in [24]. For a multispecies diffusion–reaction–dissolution system with identical diffusion coefficients, an existence theory is given in [31]. The homogenization of the model proposed in [31] is shown in [34].
In this paper, we consider a pore-scale model for a system of diffusion–reaction equations together with a dissolution and precipitation equation. The novelty of the current work is to consider the mobile species with nonidentical diffusion coefficients and Langmuir type reaction rate terms. In [46], the author has provided a survey on results related to the difficulties in the existence of a solution for a system of diffusion–reaction equations with different diffusion coefficients. Very recently, several results have been obtained on the existence of a global weak solution for a system of diffusion–reaction equations with certain restrictions on source terms, e.g., in [6,8,9,20]. However, for a system of diffusion–reaction–dissolution–precipitation model with nonidentical diffusion coefficients, the existence of solution still remains challenging. We will also obtain the macroscopic description of the pore scale model in this article.
We have organized the paper as follows: in Section 2, we introduce the periodic setting of the domain and the microscale model equations. Here we would like to mention that we have modeled the transport of mobile species in the pore space and dissolution and precipitation of minerals at the interfaces. In Section 3, we shall collect the mathematical tools required to analyze the model from Section 2. In Section 4, we shall prove one main Theorem of this paper, mainly about the existence and uniqueness of the solution. We employ Banach fixed point method to show the existence of a unique positive weak solution. Finally, in Section 5, we have obtained an anticipated upscaled model via asymptotic expansion and in Section 6, we derive the two-scale limit equations of the micromodel via two-scale convergence and periodic unfolding.
Mobile species in with crystal dissolution and precipitation on .
The model
To start with let us assume that be a (bounded domain) porous medium with a pore space and the union of solid parts such that , , union of boundaries of solid parts and outer boundary of Ω. Let be a unit representative cell which is composed of a solid part with boundary Γ and a pore part such that , and . For , we define the translated sets as and for and . Assume further that Ω is periodic (i.e. the solid parts in Ω are periodically distributed) and is covered by a finite union of the cells Y. To avoid technical difficulties, we postulate that the solid parts do not touch the boundary , solid parts do not touch each other and solid parts do not touch the boundary of Y. Let be the scale parameter and Ω be covered by a finite union of translated versions of cells such that for , i.e. , , and , see Fig. 1. We also define , , , . We set as the time interval for a , and as volume elements in Y and Ω, and and as surface elements on Γ and , respectively. The characteristic (indicator) function, , of in Ω is defined by
Now, let two mobile species and be present in whereas one immobile species (crystal) is present on . The species , and are connected via following reaction:
We make the assumptions that in the pore space no reactions amongst the mobile species are taking place and at the outer boundary no influx or outflux of and are present. However, as it can be seen in (2.1), we will impose a flux condition at the interface . The relation (2.1) signifies that one molecule of each and will give one molecule of via precipitation which will be modeled by the reaction rate term which comes from Langmuir isotherm. In case of dissolution on , one molecule of will dissolve to give one molecule of each and . The modeling of dissolution process is adopted from [25,53,54]. It is well-known that minerals have “constant activity”, i.e. the dissolution rate is constant if the mineral is present. If the mineral is absent, the dissolution rate can not be stronger than precipitation to maintain the non-negativity of the surface concentration, cf. [25,53,54]. This leads to a multi-valued dissolution term , where
Let the concentrations of , and be given by , and , respectively. Then, the above problem (model) can be expressed as a coupled system of ODE-PDEs as:
where is defined by
and . and are the Langmuir parameters for the mobile species and . The rate of dissolution is given by . Also, is the forward reaction rate constant for precipitation and denotes the dissolution rate constant. Let us denote the problem/model (2.3a)–(2.3k) by .
Mathematical preliminaries
Let and be such that . Assume that , then as usual , , , and are the Lebesgue, Sobolev, Hölder, real- and complex-interpolation spaces respectively endowed with their standard norms. We denote and . denotes the set of all Y-periodic γ-times continuously differentiable functions in y for . In particular, is the space of all the Y-periodic continuous function in y. For a Banach space X, denotes its dual and the duality pairing is denoted by . The symbols ↪, and denote the continuous, compact and dense embeddings, respectively. We define as
By Section 2, we note that . Since the surface area of increases proportionally to , i.e. as , we introduce the duality as
and the space is furnished with the norm
From here and on, we take . The Sobolev–Bochner spaces are given by: , , and , where is the distributional time derivative and their respective norms can be defined as and so on. The vector-valued function space is the solution space. A quadruple is said to be a weak solution of (2.3a)–(2.3k) if and
For a , let us define such that . We will make following assumptions for the sake of analysis:
.
for all , .
is Locally Lipschitz in , as
where is a constant. where . Here we use the Langmuir isotherm to model the forward reaction phenomenon.
and .
and , where , are positive constants.
We will now state the two main Theorems of this paper below: Theorem 3.1 for existence of solution of the micro problem and Theorem 3.2 for the homogenization of the micro problem .
Suppose the assumptions (A1)–(A5) hold true, then there exists a unique positive weak solutionofwhich satisfiesfor a.e., where C is a generic constant independent of ε.
Under the assumptions (A1)–(A5), there exist, as obtained in Lemma
6.2
, such thatis the unique solution of the problemsatisfying the a-priori boundwhereand the elliptic homogenized matrixandare defined byMoreover,are the solutions of the cell problemsforand for almost every.
This Section is devoted to establish the existence of a unique positive global in time weak solution of (). We will employ some regularization technique and Banach’s fixed point argument for the existence of solution. Finally, we will conclude this Section by showing that the solution is unique. First, we start with the non-negativity of the concentrations (weak solution of ()) which is obtained in the next Lemma.
The weak solution ofis nonnegative, i.e.a.e. inanda.e. on, respectively.
We choose test function negative part of . Then by (3.1a)
Since , and relying on (A2) we get the estimate
(4.1) in combination with (4.2) gives that
Therefore, for a.e. . Similarly, we can show for a.e. . Next, we put in (3.1c) which gives
Since , which implies . Hence, , i.e. for a.e. . □
The concentrationsandsatisfyanda.e. in, where the constantsandare independent of δ, ε.
We test (3.1a) with and get
Since and therefore
This gives
where γ is the Young’s inequality constant. Now to estimate the boundary term we use the trace inequality (A.3) and integrate both sides of (4.5) w.r.t. t to obtain
where and C are independent of ε and δ. As so (4.3) leads to
where . Now for we have
Then, Gronwall’s inequality yields
Similarly, for we obtain
□
The concentrationsandsatisfyanda.e. in, where the constantsandare independent of δ, ε.
Choosing in (4.6), we are led to
Similarly, for we get
□
The concentrationsatisfiesa.e. on, where the constantis independent of δ, ε.
We use in (3.1c) and integrate w.r.t. t to get
Thus, (4.7) leads to
Then, Gronwall’s inequality implies
□
The concentrationsatisfiesa.e. on, where the constantis independent of δ, ε.
By partial integration of (2.3i) and using (4.4) we obtain
□
Existence of solution
As we can see in the system of equations (2.3a)–(2.3k), the multivaluedness of the dissolution rate term in (2.3i) creates the main difficulty in analysis. We tackle the multivaluedness by introducing a regularization parameter and in order to prove the existence of a weak solution we replace by , where
For brevity of notation, we denote , and . First, we will establish the existence of solution of the regularized problem and then we perform to obtain the existence of solution of (2.3a)–(2.3k). The regularized problem is given by Find such that and
We consider the closed and convex sets
Now, we show the existence of solution by using a nested (Banach) fixed point Theorem, cf. Theorem 3.1 in [10] or, Lemma 3.80 in [23]. The argument goes like this: for arbitrary , we consider (4.9c) with , then by Picard–Lindelöf Theorem there exists a unique local solution since the r.h.s. of (4.9c) is Lipschitz. Again, for , (4.9b) with has a unique solution , where is a contraction map and has a fixed point in . This will imply further the existence of solution of (4.9b). Furthermore, for , the equation (4.9a) has a fixed point , where is a contraction map and has a fixed point in . In other words, the fixed points of and are the solutions of the problem (4.9a)–(4.9c).
There exists a constant, independent of δ and ε, such that
We fix an arbitrary and test (4.9b) with and the rest follows in the similar way as shown in [54], i.e.
where is the Young’s inequality constant. Again,
Now, applying trace inequality (A.3) and the inequality (4.10), the estimate for gives,
□
Givenfixed, letdenote the solution of (
4.9c
) then there exists a constant C, independent of δ and ε, such that
We know by Lemma 4.4
We put in (4.9c), then
The addition of the above two inequalities gives the desired result. □
Now, let with be the corresponding solution of (4.9c). In the next Lemma, we denote
and then by trace inequality (A.3),
where C is independent of ε.
Ifandare two solutions of (
4.9c
) andthen for a.e.we have,where,,andis the Lipschitz constant.
We use as test function in the variational formulation (4.9c) and simplify to get the inequality,
as is monotonically increasing and R is locally Lipschitz. Hence,
By Young’s inequality and trace inequality (4.11), we have
Therefore,
By Gronwall’s inequality,
Again, we test (4.9c) with and proceed in the similar way as above to obtain the estimate
□
For a.e.and awherewithfrom Lemma
4.8
and,are positive constants independent of δ and ε.
We take (4.9b) for and choose as the test function. The rest follows like the previous lemma. □
Now,
Inserting gives,
In the estimates, the constants , are independent of the initial data, as T is an upper bound of t, and can be bounded by a constant independent of t. In (4.12) does not depend on the initial data. So if, that is, then for μ small enough(but fixed) is a contraction on the closed set
and so by Banach’s fixed point Theorem it has a fixed point in this set. By Lemma 4.6, and satisfy a-priori estimate. Also with . So, can be used as initial condition for extending the time interval of existence from to , where . Since is independent of the initial data, we proceed in the similar fashion as above and by bootstrapping argument we can obtain the existence of solution for a.e. .
The fixed pointofbelongs toexists uniquely and satisfiesfor a.e., where the constantdoes not depend on δ and ε.
Let, arbitrary. A sequence is constructed by the iteration , . For we see that
So, is a Cauchy sequence in and is a closed subspace of a complete metric space and hence complete. So there exists such that as . Again,
This implies, . Therefore, is a fixed point of . If possible, let is another fixed point of . Now,
It’s a contradiction. So, has a unique fixed point . Again is uniformly bounded in . So it has a weakly convergent subsequence with as a weak limit. By construction all satisfy the initial and boundary data and
and satisfies
with as initial data. By Lemma 4.8 the sequence converges strongly to a limit in . We can pass to the limit in (4.13) and (4.14) since R and are continuous and obtain is a solution of the regularized problem.
Uniqueness: Let and be two solutions of the regularized problem related with the equations (4.9b) and (4.9c). Take and . Now by Lemma 4.8,
We apply Gronwall’s inequality and integrate w.r.t. t to get
Now, replacing θ by in (4.9b), we have
where
Now by the trace inequality (A.4)
Hence,
where . Setting implies , where . Therefore, Gronwall’s inequality gives,
By (4.15),
□
Now to show the existence of solution of (4.9a) and (4.9c), we define a fixed point operator and proceed in the similar way as before. This can be summarized in the following Lemma: Similarly, for we will get,
For each, the problem (
4.9a
)–(
4.9c
) has a unique solutionwhich satisfieswhere the constantis independent of δ and ε.
Now we have to send . For each , Lemma 4.11 provides the necessary estimates to pass the limit. Let, defined by, a.e. in . Now by compactness argument there exists a subsequence and such that for
weakly in ,
weakly in ,
weakly in ,
weakly in ,
weakly in ,
weakly in ,
weakly* in .
All bounds are inherited from Lemma 4.11 and by weak convergences (i)–(vi). , and satisfy equation (3.1a), (3.1b) and the ODE (3.1c). However, the second part of (3.1c) needs attention. We first consider the behavior of on . By the a-priori estimates of Lemma 4.11 and by Corollary 4 and Lemma 9 of [52] we get, for ,
Now by trace Theorem (cf. Satz 8.7 of [58]), we have
Since R is Lipschitz, strongly in and pointwise a.e. in . This and weak* convergence of implies , , satisfy (3.1c). Now we need to show that a.e. in . Let
Now, we decompose in almost everywhere sense, where and . We need to show that and in , while and in . Note that
Let such that for β sufficiently small. We write , where . Therefore, is an increasing sequence and since is bounded by Lemma 4.5, is also bounded and converges to its least upper bound, i.e. . So for any there exists such that . Hence for all δ small enough. So, . Also,
We choose and integrate w.r.t. t, then
Now, on taking we get
Hence, in . As therefore we have, a.e. in . Consequently, with . □
An anticipated homogenized model of the problem via asymptotic expansion
Homogenization is a mathematically rigorous approach for averaging differential equations. It gives the macroscopic description of a medium that is microscopically heterogeneous, i.e. it aims to replace a complex, rapidly varying heterogeneous medium with a simple, slowly changing homogeneous medium. In this Section, we will obtain the upscaled version (macroscopic description) of the problem by using asymptotic expansion (see Chapter 1.3.1 of [21]). Although asymptotic expansion is a formal method and does not address the convergence of the micro problem to the macro problem, it still helps us to obtain (or at least gives an idea of) the upscaled equations. Besides asymptotic analysis, we use two-scale convergence (see [1,2,30]) and periodic unfolding method (see [12,13,16,17]) in Section 6 to perform the homogenization of . Now, let
where , and are Y-periodic functions in . Moreover, . Now by (5.1) and (2.3a),
Now equating the coefficients of on both sides of (5.2) yields
We multiply (5.3) by and integrate w.r.t. y, then
Note that, since is periodic. From (2.3c) we see that,
We compare the coefficient of on both sides of (5.5), which gives
We put these in (5.4) to obtain,
Next, comparing the coefficients of on both sides of (5.2) leads to
From this it follows that is a linear combination of for all j, i.e. , where, for each , are the Y-periodic solution of the cell problems
Again, we compare the coefficients of on both sides of (5.2) to derive
Next, by integration by parts
since . Now comparing the coefficient of ε on both sides of (5.5), we have
Now (5.9) takes the form
From (5.8), we deduce that
where
For the boundary condition, we equate the coefficients of on both sides of (5.5) and obtain
For the initial condition, inserting (5.1) in (2.3d) yields
Equating the coefficient of we get
Similarly, the macromodel of the mobile species is given by
where
and is the solution of the cell-problem (5.7). We now find out the effective equation for the immobile species and for that we need to get rid of the multivaluedness in (2.3i). In order to do this, we replace by given by (4.8). Inserting (5.1) in (2.3i) and using series expansion we obtain
We will first simplify the r.h.s.
Therefore, we have
Upon comparing the coefficients of on both sides, we get
Now taking as shown in Section 4 (cf. [54,55]) we obtain
For the initial condition, comparing the coefficient of on both sides of
we can write . The required upscaled model can be summarized as For mobile species :
For mobile species :
For immobile species :
Proof of Theorem 3.2 (Homogenization of the problem via two-scale convergence)
Here we aim to transform the equations from the oscillating domain to a fixed domain by applying a rigorous approach of homogenization. As a first step toward achieving this aim, we need to extend the solutions from to . We also unfold the ODE to define the unfolded concentration on the fixed boundary Γ. We start with the following Lemma:
There exists a positive constant C independent of ε such that
The proof follows from the estimate (3.2c) and Lemma A.6. □
We can conclude the following convergence results upto a subsequence (still denoted by the same subscript) from the a-priori bounds (
3.2c
) and (
6.1
)
in,
in,
in,
in,
in,
in,
in,
in,
There existsandsuch thatand,
There existsandsuch thatand,
in,
in,
in,
in.
The results (i)–(vi) follows from the boundedness of , in and , in . We require some compact embedding results to establish (vii) and (viii). The sobolev space is compactly embedded in , that is for and . So for a fixed ε, the space by the Lions–Aubin compactness Lemma. Then by the trace inequality (A.5) we get
Let , then we proceed in the similar fashion to obtain for the second mobile species
The estimate (6.1) in combination with Lemma A.3 and Lemma A.5 gives (ix)–(xiii). The inequality
yields that is bounded in . So as an implication of Lemma A.5 we can conclude that in . □
The sequenceis strongly convergent toin. We can deduce therefore thatin.
The unfolded sequence of the immobile speciesis strongly convergent toin.
(i) Since R is Lipschitz, we can write
Now, we apply Minkowski’s inequality and Lemma 6.2 to obtain
Then we use Lemma A.10 together with Lemma A.8 to establish
(ii) We unfold the ODE (2.3i) by applying the boundary unfolding operator (A.7) and derive
For , we subtract (6.2) for from the choice of and get
We now multiply and integrate over to deduce
As a consequence of the monotonicity of with respect to we have
So we get the inequality
We then simplify each term of the r.h.s. We use Lemma A.9 to estimate the 1st term as
and the second term of the r.h.s. can be estimated as
We see that strongly in since is independent of y. It follows from Lemma A.9 and the first part of Lemma 6.3 that
Thus (6.5) takes the form
Putting together (6.4) and (6.6) we obtain
Gronwall’s inequality gives
By the completeness of the space , we can derive that in . That imply, in (cf. Lemma A.8) but we already prove that in . Hence . □
We make use of the two-scale convergence technique to obtain the macroscopic equations. We test the PDEs by where , in such a way that , , for . For the ODE we take as a test function such that . Now, multiplying the PDEs (2.3a) and (2.3e) by and and the ODE (2.3i) by ψ and adding up yields
Then integrate by parts in t to obtain
Now we pass in (6.7) and get
We now derive the two-scale limit equations by making special choices of the test functions. First we choose , , , all equal to zero and ψ as above with the property then we have the macroscopic equation for the ODE as
Next we choose as above such that and the remaining test functions all zero in (6.8) and that leads to
We then set all other test functions is equal to zero except to derive the cell problem:
For the choice of we have for , are the Y-periodic solution of the cell problems
Now for the choice of as above equation (6.10) can be rewritten as
which can be simplified as
where
After that we take as earlier and vanishing at and together with , , , ψ all zero and derive
We keep non-zero and all other test functions are equal to zero to compute the cell problem for :
So for the cell problems are given by (6.11a)–(6.11c). Recalling (6.13), we get the upscaled model for as
where
We now substitute (6.9)–(6.14) in (6.8) to identify the initial conditions. We define together with and and deduce
Similarly, setting all the other test functions as zero except and we have our initial conditions as and . We can calculate the final conditions as , and . We finally derive the strong form of the homogenized system as (3.3a)–(3.5c) by fixing .
Now we need to characterize the two-scale limit of the multivalued dissolution rate term. According to Lemma 6.3, in . Therefore by corollary on page 53 of [59], there exists a subsequence (still denoted by the same symbol) pointwise convergent to a.e. in . i.e.
While , so we have to consider two different cases.
Case 1: Let .
As is the pointwise limit of therefore for any there exists a such that . Let us choose such that . So by definition (6.3) we have as a consequence of weak convergence.
Case 2: Let .
Since thus for a test function we get
since ϕ is arbitrary, it follows that that means, in . Then
passing the limit leads to
i.e. and when on Γ. □
We can show the existence, positivity and uniqueness of a solution of the macromodel as below.
Positivity: We multiply (3.3a) by and integration over yields
The initial condition term in the r.h.s. vanishes due to (A1). Utilizing the ellipticity of the matrix A and the assumption (A2) we can write
Consequently, (6.15) takes the form
The same procedure leads to for a.e. . Next we use as a multiplier in (3.5a) and integrate over to get
Since for . Now as so and . Thus we have, for a.e. .
Existence: We can calculate the estimate (3.6) by proceeding as in Section 4. The proof of existence is based on Galerkin method since the source term .
Uniqueness: Suppose there are two weak solutions to the macroscopic equations (3.4a)–(3.5c). We denote , and . Now and satisfy the weak formulations
With the choice of and the monotonicity of , (6.17) takes the form
Gronwall’s Inequality implies
Take in (6.16) to obtain
Now using the ellipticity of B and the fact that is independent of y we get
So application of Gronwall’s Inequality gives
Consequently, We have from (6.18) that
Conclusion
We studied a system of diffusion–reaction equations coupled with a precipitation-dissolution model. We started with a micro model in a heterogeneous porous medium. We also assumed that the two mobile species have different diffusion coefficients. We first proved the existence of a unique global in time weak solution and further performed the homogenization of the micro model in this paper. The upscaled model has a similar form as the micro problem and it can be verified via numerical simulation that this method approximates the micro problem. The numerical validation for similar type of model can be found in [32,50]. This paper is the first part of the series of papers where we will explore the possibility of different diffusion coefficients of mobile species together with non-linear reaction rate terms. As mentioned earlier that having different diffusion coefficients raises serious questions on the existence of global in time solutions. To our knowledge for a general model, this question is still unknown and we will address this question elsewhere.
Footnotes
Acknowledgements
The authors are grateful to the anonymous referee(s) for his/her/their constructive inputs that helped us to considerably improve the initial manuscript. The authors are also thankful to the editor for a smooth and prompt communication regarding the manuscript.
Appendix
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