Chemical Engineering Science 65 (2010) 47924802

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Chemical Engineering Science

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Passivity based control of reaction diffusion systems: Application to the vapor recovery reactor in carbothermic aluminum production$
S. Balaji, Vianey Garcia-Osorio, B. Erik Ydstie
Department of Chemical Engineering, Carnegie Mellon University, 5000 Forbes Ave, Pittsburgh, PA 15213, USA

a r t i c l e in f o
Article history: Received 20 January 2010 Received in revised form 18 May 2010 Accepted 20 May 2010 Available online 1 June 2010 Keywords: Aluminum Shrinking core model Gassolid non-catalytic reaction Moving bed Inventory control Passivity

a b s t r a c t
We develop a passivity based controller for a reaction diffusion system. The model used in the simulation study describes the vapor recovery reactor used in carbothermic aluminum reduction. It takes into account, non-catalytic gassolid reactions, the moving bed of solid particles and the shrinkage of the unreacted particle core. The reaction diffusion system is solved using the nite element method. We use passivity based control to adjust the carbon feed and the heat input to achieve the required conversion and maintain the temperature along the reactor. The efciency of the reactor is determined by calculating the extent of vapor recovery and the conversion of carbon particles. The sensitivity of different parameters such as solid ow rate and column height based on the reactor performance is also determined. We show that the control scheme based on the inventory balances performs well under various operating conditions. & 2010 Elsevier Ltd. All rights reserved.

1. Introduction The conventional approach for the control of distributed parameter systems discretizes the partial differential equation into a large system of ordinary differential equations through nite difference or nite element method (Ray, 1978; Christodes, 2001a). Although controllers now can be designed based on the classical theories like pole placement, linear quadratic or predictive control, erroneous conclusions may result concerning the stability, controllability and observability of the system (Aling et al., 1997; Balas, 1986; Christodes, 2001b). This is due to the fact that a highly reduced model cannot represent a DPS accurately. On the other hand, a high order model is computationally expensive making it unsuitable for real time controller implementation. High dimensionality can be avoided using the concepts of singular perturbation and inertial manifolds. These methods rely on time-scale separation and temporal averaging. They can be applied to systems where the fast dynamics dissipate (Christodes, 2001b; Brown et al., 1990; Smoller, 1996). Classical control methods like the Lyapunov method can now be applied (Christodes and Daoutidis, 1998; Christodes, 1998; El-Farra et al., 2003). An extension of this method to predictive control can

Corresponding author. Tel.: + 1 412 268 2235; fax: + 1 412 268 7139.

This work was supported by ALCOA Inc.

E-mail address: ydstie@andrew.cmu.edu (B. Erik Ydstie). 0009-2509/$ - see front matter & 2010 Elsevier Ltd. All rights reserved. doi:10.1016/j.ces.2010.05.037

be seen in Kazantzis and Kravaris (1999). Sliding mode control has also been proposed to control the DPS systems (Hanczyc and Palazoglu, 1995; Sira-Ramirez, 1989). Other approaches of controlling nonlinear PDE systems include control using symmetry group representation (Godasi et al., 2002), generalized invariants (Palazoglu and Karakas, 2000). In this study, we focus on the control of distributed parameter systems using passivity based control based on feedback from spatial rather than temporal averages. In particular, we use feedback from inventories. The passivity theory can be used as a guideline to design a control system for large scale, distributed parameter systems (Desoer and Vidyasagar, 1975). Willems (1972a, b) developed a systems perspective for passivity and dissipativity and linked the concept to state space representations. Byrnes et al. (1991) showed that passivity and Lyapunov stability is equivalent for a class of feedback systems using geometric methods. Van der Schaft (1996) developed control methods linking passivity and L2 stability, while Krstic et al. (1995) linked passivity and nonlinear adaptive control. Ydstie and Alonso (1997) and Alonso and Ydstie (2001) advanced the idea of combining thermodynamics and passivity and showed that passivity could be motivated using a storage function related to the available work and Gibbs tangent plane criteria for phase stability. The inventory control concept was rst formulated and tested by Farschman et al. (1998). According to this strategy, any process system can be represented based on inventories. Based on the balance equation of the inventories, simple control schemes can be implemented for stable operation of the system. An inventory

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is an extensive measure of the thermodynamic state of the system. Some examples of system inventories are total internal energy (U), total volume (V), total mass (Mi) of species i present in the system. A system is said to be passive, if the inventories converge to their setpoints and the state variables of the system converge to their stationary passive state. Inventory based calculations ignore or overlook the detailed structure of the dynamics. However, ultimately we obtain a reduced order model by averaging over space rather than time, resulting in a coarse grained view of the system dynamics. Thus, the resulting set of equations to be solved will be the model equations in addition with the macroscopic or integrated conservation equations. The control design is achieved using either Lyapunov or passivity design techniques. A description of this approach and its application to nite dimensional systems with and without input constraints is given by Farschman et al. (1998). Ydstie and Jiao (2004) applied inventory and ow control to a oat glass production system and Ruszkowski et al. (2005) tested this control for a 1D transport reaction process system. Control of particulate processes described by population balance equations with the concept of system inventories (Duenas Diez et al., 2008) is a good example of the inventory based control applied for an integro-partial differential equation system.

Entropy S (Z)

A1

Z1

Z2
Fig. 1. Entropy function.

equations @rx, t zx, t @f x, t sx, t @t @x 4

2. Passivity of transport reaction systems

+2 called the statespace. Let Z Let S be a convex subset of Rn + denote an arbitrary point. For example, we can have Z U , V , M1 , . . . , Mnc , X T , where U is the internal energy, V is the volume, Mi is mass or moles of chemical component i and X can correspond to the charge, degree of magnetization, area, momentum, etc. In this case, Z is called the Gibbs ensemble. We assume that there exists a C1 function, S : S/R , called the entropy such that:

where x is the position and t is the time. f(x,t) represents the ux density and sx, t represents the density of production. rx, t and z(x,t) are the molar density and local state of the system, respectively. These variables are connected to the macroscopic balances @Zi pi t fi t @t yi hZi via the relationships 5

 For any positive constant l, SlZ lSZ (S is positively  

homogeneous of degree one). For all points Z1 , Z2 A S and any positive constant l, SlZ1 1lZ2 Z lSZ1 1lSZ2 (S is concave). T @U =@S 4 0 (the temperature is positive).

fi t f Li 1 , t f Li , t
pt Z
Li Li 1

6 Z
Li Li 1

sx, t dx, Z

rx, tzx, t dx

Fig. 1 shows the entropy function S(Z). Using the C1 property we dene the intensive variables, so that wT @S @Z 1

We see from gure that the intensive variables are dened as the tangent hyperplane to the entropy function. The slope of the tangent line, w1 denes the intensive variables at the particular point Z1. A non-negative function, called a storage function can be dened now so that for any pair of points Z1, Z2 in S we have A1 Z2 SZ1 wT 1 Z2 Z1 SZ2 Z 0 2

where i 1,2,y,N with N denoting the number of spatial subdivisions of the system. This is useful in exploiting the distributed nature of the system with more accuracy. Here, we have included one dimension only. In the above equations, the sign is chosen such that it is positive for ow into the system and negative for ow out of the system. We normally divide the ux density into orthogonal components (in the sense of GibbsDuhem) so that f x, t fconv x, t fdiff x, t where fconv x, t rx, t zx, t u 9 8

It is easy to verify geometrically that A1(Z2) is non-negative as shown in Fig. 1. Inequality (2) also follows from Youngs inequality applied to the concave function S. From Eq. (2) and the Euler identity for homogeneous function S(Z) wTZ, we have A1 Z2 wT 1 Z2 SZ2 3

From the Gibbs tangent plane condition, the two points Z1 and Z2 are in equilibrium if and only if A1(Z2) 0. It is easy to see that this condition is equivalent to w1 w2. The function A, therefore, measures the distance from an arbitrary, xed reference point S . A coarse grained transport reaction system is dened locally by the set of conservation laws for z written as partial differential

with u as the center of mass velocity. The division into diffusive and convective terms can be motivated on physical grounds and corresponds to a separation into Eulerian and Lagrangian components. We now dene an augmented storage function W so that Z Li 1 1 T W t Ax, t dx yi y 10 i yi yi Z 0 2 Li Therefore, the dissipation equality for process systems is given by (Ruszkowski et al., 2005) Li 1 Z L i1  dW dyi ~T X ~ lw ~ w ~ ~ Ts ~ dx yi y 11 f f i  dt dt Li Li

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From the above equation, we can see that the storage function W ~ lw ~ jLi 1 is decreases if the right hand side is negative. The term f
Li

~T X ~ represents deviadue to deviations in boundary conditions, f ~ Ts ~ tions due to convection, diffusion and heat conduction, w represents deviations due to chemical reaction and power of compression and yi y i dyi =dt is the product of the system input and system output (inventory control). In the current study, the focus is on the passivity based control of a vapor recovery reactor (VRR) used in carbothermic aluminum production for enhanced performance. A shrinking core model has been used along with a one-dimensional heterogeneous model to represent the reactor behavior appropriately. This choice was motivated by the modeling and experimental studies (Garcia-Osorio et al., 2001; Fruehan et al., 2004) carried out in the past. In the next section we show how this process ts into the control theory developed above.

A counter-current vapor recovery reactor (VRR) with carbon feed has been proposed to solve these problems. In the VRR, the carbon reacts with the aluminum compounds in a series of heterogeneous noncatalytic reactions, forming solid and gas products (refer Fig. 3). The important solid product is aluminum carbide which is indeed required in the smelting stage of the aluminum process. The gaseous product is hot carbon monoxide gas, which can be used for other purposes like generating electricity or for syn-gas production. The ow sheet for the aluminum production is based on the Reynolds process (Fig. 2, Kibby and Saavedra, 1987). The feed (Al2O3 +C) is heated to around 2000 3 C in the smelting stage where carbide containing slag and gases are produced based on the reaction: Al2 O3 C-Al4 C3 Al2 O3 slag COAl2 OAlg
3

12

The slag is then heated to above 2100 C, producing a carbon containing aluminum alloy which oats on the slag and gas as shown below: Al4 C3 Al2 O3 slag -AlCl COAl2 OAlg 13

3. Carbothermic aluminum process: control challenges The HallHeroult electrolytic process is the only technically and economically feasible process to produce aluminum today. However, it carries the demerits of high capital cost and high energy requirements. Thus, with a view of devising a more energy efcient process, the carbothermic reduction process has gained a signicant interest in the aluminum industries (Motzfeldt et al., 1989; Bruno, 2003; Choate and Green, 2006; Garcia-Osorio, 2003). The main advantages of the carbothermic process are that it promises to reduce capital and operating costs by 25% or more. One disadvantage with the carbothermic reduction process is that it is carried out at very high temperatures 4 2200 3 C (Johansen et al., 2000). The operational challenges are signicant due to the high temperature and signicant amounts of aluminum leave the main reactor in the form of aluminum and aluminum oxide vapors since the operating conditions are close to the boiling point of Aluminum 2520 3 C. The aluminum containing vapors cannot be recovered through simple cooling since a backward reaction produces a signicant amount of aluminum oxide in the form of molten slag and ne particles which reduce the process efciency and its operability.

The aluminum alloy is sent to the purication stage where the carbon is separated. The amount of aluminum and aluminum sub-oxide escaping from the smelting stage is quite high and therefore must be recovered for improved efciency. As simple cooling is infeasible for such systems, a vapor recovery reactor is used instead. The VRR is charged with carbonaceous material to produce aluminum carbide, which is recycled back to the smelting stage (Fig. 2). The reaction between aluminum vapor and carbon to form aluminum carbide production is slightly exothermic which leads to further heating of the charge in the column. However, a slight increase in temperature is advantageous since it accelerates the reaction thereby improving production efciency and operability. The main control challenges for the process are:

 A highly nonlinear systemthermodynamics plays a major

role in the extent of conversion and the system is a multiphase reactor system which can be represented appropriately only with a nonlinear model. Distributed parametric systemthere is a signicant difference in temperature along the system along with the shrinkage of the carbon particles and hence the conversion and slag formation vary spatially.

Vapor Recovery Reactor

Smelting Process

Gas Fluxing - Purification

Fig. 2. Simplied diagram of Reynolds process for carbothermic aluminum production.

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 Highly integrated with recyclesfrom Fig. 2, it can be inferred

that there are many recycle streams integrated with the smelting process (product Al4C3 is recycled from both the VRR and the purication stage). A multi-phase reaction system which demands complex models for accurate prediction of the process.

reactions shown in (14) and (15). The modeling approach is based on the idea that the reactions occur in spherical carbon particles whose dimensions are negligible when compared with the overall size of the column. With this assumption, the mass balance equation for the reactants (in vapor form) is written as

eB
The available control variables are:

@ci @c @2 c vg i Deb, i 2i si , @t @z @z

i Al2 O, Al

16

 Heat input to the smelting process and the VRR.  Carbon feed to the smelting process and the VRR.  Alumina feed to the smelting process and the VRR.
In the present work, we concentrate on modeling and control of VRR only. The proposed control strategy will be extended to the entire process in a future paper.

Similarly, the mass balance of the solid reactant (carbon) is written as 1eB @cs @cs @cs vs DeC 2 sC @t @z @z 17

The solid concentration cs is related to the extent of conversion by cs cs0 1X Substituting (18) in (17), @cs0 X @cs0 X @2 cs0 X sC vs DeC @t @z @z2 The mass balance for the gas product is The vapor recovery unit recovers the aluminum gases escaping from the smelting stage. Carbon particles are fed from the top and the aluminum vapors enter from the bottom of the reactor (counter-current operation). Almost instantaneous chemical reaction takes place due to the high temperature. A mass transfer limited reaction mechanism therefore describes the reaction rate accurately. It is also assumed that the diffusion of gases into the solid product layer is the controlling mechanism. This assumption is based on both experiments carried out at ALCOA and lab scale experiments in the Department of Materials Science and Engineering at Carnegie Mellon University (Bruno, 2004; Fruehan et al., 2004). The mechanism is captured well by postulating the shrinking core model. Fig. 3 shows a schematic representation of the vapor recovery reactor. The main chemical reactions that take place in VRR are given by 2Al2 Og 5Cs 2Al4 C3s 2COg 4Alg 3Cs 2Al4 C3s 14 15 1eB Cps rs @cCO @CO @2 cCO vg Deb, CO sAl2 O @t @z @z2 19 18

4. The vapor recovery reactor

eB

20

where eB is the bed void fraction, si is the rate of reaction of species i and X is the solid conversion. si is negative for reactants and positive for products. The mixing in axial direction (which is due to turbulence and presence of packing) is considered in the model by superposing a dispersion transport mechanism. The ux associated with this mechanism is described by an expression analogous to Ficks law for mass transfer. The proportionality constant is the dispersion coefcient Deb. Froment and Bischoff (1990) summarized the experimental results concerning the dispersion coefcient in the axial direction. In these correlations, the dispersion coefcient is a function of the Peclet number (based on the particle diameter) and Reynolds number. The dispersion coefcient in the axial direction is obtained from Garcia-Osorio and Ydstie (2004). The energy balance for the solid reactant is given by
n X @ Ts @ Ts @2 Ts vs Cps rs kfs 2 haTs Tg DHi si Q @t @z @z i

21 5. Model description In this section, we elucidate the model used to describe the mass and heat transfer in a non-porous moving bed for chemical where Q is the energy from an external heat source to maintain the temperature along the reactor. The energy balance for the vapor is given by eB Cf rf @Tg @Tg @2 Tg vg Cf rf kf haTg Ts 0 @t @z @z2 22

C Solid Feed

CO Gas Out

Q Heat Input

Moving Bed System

where a is the specic surface area per unit volume, h is the gas solid heat transfer coefcient obtained using the RanzMarshall correlation (Themelis, 1995), DHi is the enthalpy of reaction for species i and vg is the velocity of the gas stream. In this simulation, the momentum balance is not solved explicitly. To compensate for this, the change in velocity is computed with a corresponding change in the temperature of the gas stream. The relation is written as   Tg 23 vg vg0 Tg0 5.1. Reaction modelproduct layer diffusion controlled

Al2O, Al, CO Vapors

C, Al4C3 Product Stream

Fig. 3. Vapor recovery reactor.

The model takes into account the external transfer of the gas species onto the surface of the solid particle, the diffusion through the pores of the solid product layer and the heterogeneous chemical reaction at the surface of the solid reactant. When the

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chemical reaction at the interface is almost instantaneous, the resistance offered by the reaction is negligible when compared with that of the diffusion through the product layer. Thus, the overall rate is controlled by the diffusion of the reactants through the product layer. The rate of diffusion is obtained by making pseudo-steadystate approximation (Bischoff, 1963; Luss, 1968). That is, the rate of accumulation of the gas species in the product layer is negligible when compared with the diffusive uxes (Szekely et al., 1976). Further modeling assumptions are:

cAl 0, t cAl0 ,

 dcAl   0 dz z L  dcAl2 O   0 dz z L

cAl2 O 0, t cAl2 O0 ,

cCO 0, t cCO0 ,

 dcCO   0 dz z L  dT g   0 dz z L

Tg 0, t Tbottom ,

 The size of the particle is considered constant during the

course of the reaction.

 Sintering is neglected.  The reactions are bi-directional i.e. reversible.

Ts L, t Ttop ,

 dT s   0 dz z 0 32

X L, t 0, The reaction rate per particle for Eqs. (14) and (15) is given by the shrinking core model as reported by Garcia-Osorio et al. (2001) for the aluminum, carbon system.
4pr 2 De, Al2 O    2 dcAl2 O 4pDe, Al2 O KE, Al2 O c 4prc rC drc  cAl2 O CO  1 dr KE, Al2 O 1 KE, Al2 O bAl2 O dt 1
rc r0

 dX   0 dt z 0

24 4pr 2 De, Al   2 4pDe, Al dcAl 1 4prc rC drc  cAl  1 1 dr bAl dt KE, Al r c r0 25

The initial conditions are established such that only pure carbon particles are present inside the column at time t 0. The boundary conditions at the column end (z L) assume that the gas product stream is removed immediately from the unit (Amundson, 1956). The equilibrium constants were calculated using the database FACT (Pelton and Degterov, 1999; Pelton and Bale, 1999) developed by Pelton and Degterov for the Al2O3 Al4C3 system. Eqs. (16)(22) with reaction rates corresponding to Eqs. (26)(28) now correspond to the course grained system (4).

where De,Al and De, Al2 O are the effective diffusivities of aluminum and aluminum sub-oxide vapors, respectively, in the product layer. KE, Al2 O and KE,Al are the equilibrium reaction constants for reactions (14) and (15), respectively, rc is the radius of the unreacted carbon particle and r0 is the total radius of the particle. Therefore, the reaction rate of each chemical species derived for Eqs. (24) and (25) is (Smith, 1981):    31eB Deb, Al2 O cCO 1 1 1 KE, Al2 O sAl2 O c 26 Al2 O 3 KE, Al2 O 1 KE, Al2 O rc r0 r0

6. Method of solution The model consists of six PDEs with the physical parameters like density, viscosity as a function of the state variables. The reaction rate is non-linear resulting in a set of partial differential equations with a high degree of non-linearity. The proposed equations are solved by nite elements method using the Multiphysics modeling software COMSOL (2005). In this work, the equations are implemented and solved on a one-dimensional domain. Mesh renement is carried out until the solution reached convergence. Four hundred and eighty mesh points were used with 5766 degrees of freedom to solve the equations with required accuracy. A transient analysis with direct linear system solver (UMFPACK) is used to solve the PDEs simultaneously.

sAl

   31eB Deb, Al 1 1 1 1 cAl 3 KE, Al rc r0 r0

27 28

sCO sAl2 O

The effective diffusivity for the product layer was calculated by Fruehan et al. (2004) through experiments. The reaction rate for the solid particle is determined by RC dnC d 4 3 2 dr c rC prc 4prC rc dt dt dt 3 29

7. Results (open loopbase case) Table 1 shows a list of parameters used for the base case simulation. The simulation results showing the conversion of Al, Al2O vapors and carbon particles until the system reaches steadystate are shown in this section. The various lines in Figs. 47 represent the proles at different time instances. Fig. 4 shows the
Table 1 Model parameters (base case). Parameter D De,i vg vs Z r0 Tbottom B s Parameter name Diameter of the column Effective diffusivity of species i in the solid product layer Gas velocity Solid velocity Height of the column Radius of the pellet Temperature at the bottom of the vapor recovery unit Bed porosity Solid density Nominal value 0.15 m 0.8 10 4 m2/s 1.28 m/s 7 10 4 m/s 0.30 m 0.0125 m 2230 K 0.25 2267 kg/m3

Therefore, the reaction rate of an unreacted carbon particle is obtained by combining Eqs. (24) and (25) with Eq. (29) (Missen et al., 1999):    1 1 1 1 Deb, Al bAl cAl KE, Al rc r0    cCO 1 1 1 KE, Al2 O Deb, Al2 O bAl2 O cAl2 O 30 KE, Al2 O 1 KE, Al2 O rc r0 The relation between the radius of the unreacted carbon particle (rc) and the initial particle radius (r0) is rc r0 1X cAl z, 0 0, Tg z, 0 Tg0 ,
1=3

31

The initial and boundary conditions are as follows: cAl2 O z, 0 0, Ts z, 0 Ts0 , cCO z, 0 cCO0 X0

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Fig. 4. Normalized Al vapor concentration vs normalized column height.

normalized concentration of Al vapors with respect to the normalized column height at various time instances. The steady-state prole is clearly seen in the gure for the operating conditions specied in Table 1. Fig. 5 represents the concentration prole of the aluminum sub-oxide (Al2O) along the reactor. Comparing the concentrations of aluminum and aluminum suboxide at steady-state we observe that the conversion of aluminum sub-oxide is less when compared with that of aluminum. Therefore, the percentage recovery of aluminum vapors is higher than that of the aluminum sub-oxide vapors. Figs. 6 and 7 show the gas temperature and the solid particles temperature along the reactor, respectively. In the energy balance three heating mechanisms are considered: (a) heat exchange between the gas and the solid, (b) heat generation due to the exothermic reaction and (c) heat from an external source. For the base case simulations, the energy from the external heat source is not considered and equated to zero. However, it is one of the manipulated variables for the proposed control strategy which will be discussed later (Section 10). The proles show that the heat transfer coefcient is high enough to heat the solid particles to a required high temperature. Also, due to the exothermic

Fig. 5. Normalized Al2O vapor concentration vs normalized column height.

Fig. 7. Normalized carbon temperature vs normalized column height.

0.9 0.8 Carbon Conversion (X%)

0.6

0.4

0.2

0 1
Nor

0.8 0.6 mali zed Colu 0.4 0.2 mn Heig ht ( * z)

1600 1200 1400 800 1000 600 200 400 Time (s)

Fig. 6. Normalized gas temperature vs normalized column height.

Fig. 8. Plot of carbon conversion with respect to normalized column height and time.

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nature of the reaction, there is a slight increase in both the gas and the solid temperature when the system progresses towards the steady-state behavior. Fig. 8 shows the solid conversion against both time and axial distance. It is seen that almost 65% carbon conversion is obtained. A signicant conversion is seen as the solid is fed at a very low ow rate. The conversion proles shown above are highly dependent on many operating parameters like vapor ow velocity, solid ow velocity and length of the reactor. If there is any impurity in the solid feed or the solid feed is a mixture of alumina (Al2O3) and carbon (C), then the percentage ratio of alumina to carbon in the feed will also be an important deciding factor for the enhanced performance of the VRR. However, in the present study, a pure carbon feed is assumed and issues of impurities are not addressed.

8. Sensitivity analysis As already pointed out, the efciency of the vapor recovery reactor is highly dependent on the operating conditions. Having modeled the moving bed characteristics of the VRR, the effect of solid ow rate, vapor ow rate and reactor dimensions (reactor length) can be determined. In this section, the sensitivity of the above-mentioned parameters are analyzed by varying the particular variable with all other variables constant. The solid (carbon) ow rate and the vapor ow rate are interdependent as the performance of the reactor is based on the extent of conversion. The extent of conversion in turn is dependent on the contact time between the carbon particles and the vapors. That is, the contact time is a function of both solid and vapor ow rate. Thus, a single variable (Vratio) which is the ratio of the vapor ow rate to the solid ow rate can be considered to determine the effect of ow rates. Table 2 gives the values assumed for the analysis. For every column height, the ow ratio (Vratio) is varied. The values in the table are normalized using the respective parametric values from Table 1. The performance of the reactor is calculated in terms of the aluminum recovery from both Al and Al2O vapors. The aluminum recovery is estimated by using the following expressions: Al2 ORecovery 1 CAl2 O jz 1 CAl2 O jz o 33

Fig. 9. Normalized steady-state carbon temperature for varying carbon ow rate.

Table 3 Recovery and solid conversion for Z 0:5. Vratio 0.5 0.75 1 Al2O (%) 43.31 41.36 39.23 Al (%) 66.51 64.12 61.43 XT (%) 23.72 33.73 41.67

Table 4 Recovery and solid conversion for Z 1. Vratio 0.5 0.75 1 Al2O (%) 58.20 57.12 53.27 Al (%) 82.61 81.57 77.70 XT (%) 32.38 49.17 64.02

Table 5 Recovery and solid conversion for Z 2. Vratio Al2O (%) 75.36 76.61 68.83 Al (%) 95.69 96.36 91.54 XT (%) 42.48 70.31 93.22

AlRecovery 1

CAl jz 1 CAl jz o

34

The conversion of carbon particles (X) for both the reactions is also tabulated. The conclusions of this sensitivity analysis are the following. (a) Al2O and Al gas conversions increase with increasing solid ow rate, while solid conversions decrease. This is due to the fact that by increasing the solid ow rate, the amount of solid that the gases contact increases. Increasing the solid ow rate decreases the solid residence time inside the column; therefore the extent of reaction decreases leading to less solid conversion. (b) For the same ratio of gas and solid ow rate, longer columns lead to higher solid conversions due to high residence time. The carbon temperature prole along the reactor for varying carbon ow rate is shown in Fig. 9. It is seen that, as the ow rate
Table 2 Sensitivity analysis variables.
n Vratio (vn g /vs ) Zn

0.5 0.75 1

0.5 0.5

0.75 1

1 2

is increased, the outlet temperature decreases. Although, as per Tables 35, the conversion of aluminum vapors increases with increasing carbon ow rate, the exit temperature of the solids is reduced. As described already in Fig. 2, the product (Al4C3) and the unreacted carbon must be fed back to the smelting process. Therefore, before feeding into the smelting process, the solids must be heated to the required temperature for the reactor sustainability. Thus, in nding an optimum value for the solid ow rate, attention must be given to the exit temperature in addition to the extent of vapor conversion. Similarly, in Fig. 10, the effect of longer beds on the carbon temperature is shown. As the reactor height is increased, the time for heat transfer also increases. Thus, the solid particles are heated signicantly and hence the exothermic nature of the reaction is clearly seen.

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The control system converges to zero error if the uncertainty can be modeled as a constant offset. Let us consider a dynamic system represented as dx f x g x, u, d, dt y hx x0 x0 39

The model equations (16)(31) used in this study can be easily represented as the above dynamic system. If the inventories of the system are denoted by Z, then the inventory balance for the proposed dynamic system is (Ruszkowski et al., 2005): dZ x fy, u, d px dt 40

Fig. 10. Normalized steady-state carbon temperature for varying column height.

9. Inventory control Farschman et al. (1998) used the macroscopic balance @v fm, z, d pm, z, d @t 35

where, px @Z =@xf p ; and fy, u, d @Z =@xg p p is the production rate, pn is the production rate at steadystate and f is the supply rate. Based on this, many control schemes like onoff control, PID control, gain scheduling, nonlinear control can be implemented based on the objective function, constraints and performance criteria. For example, if a proportional-integral control is formulated, the control law would be   Z t K fy, u, d pp Kc Z Z c Z Z dt 41

tI

where Kc is the controller gain, tI is the integral time constant and Z is the inventory.

to derive control structures for chemical processes. We have indicated that the ux and production variables depend on vectors of manipulated variables m, state variables z and disturbances d. We furthermore note that Eq. (35) is a positive system since the state consists of elements that are non-negative. All states of the system are stabilized (in the sense of Lyapunov) if the total energy and the total mass are bounded. We now have the following result. Let vn denote a time-varying reference. Then, the synthetic input and output pair as given below is passive: u fp e vv dv dt

10. VRR control study The objective is to control the total carbon holdup (Mc, carbon inventory) and the total internal energy (Uc) of the system. The manipulated variables are carbon feed and the amount of heat energy supplied from an external heat source (Q). Writing a simple balance equation for carbon in the reactor and implementing the inventory control gives Z Kc , 1 t c c Jout Kc, 1 Mc Mc Mc Mc dt 42 Jin

tI, 1

36

T Let V 1 2vv vv . The vectors u and e are related in a passive manner which can be easily veried. By differentiating V we get

_ eT e _ v _ eT u _ eT v V

37

The inputoutput pair is called synthetic since it does not necessarily correspond to what is directly measured and manipulated in the real process. A control strategy which ensures that an inventory asymptotically tracks a desired set point is called inventory control. It follows from the stability of feedback systems and Eq. (36), that inventory control is input/output stable when we use feedbackfeedforward control in the form dv ^ m, z, d p ^ m, z, d uf C e 38 dt ^ denotes the estimate of the net ow and p ^ In this expression f denotes the estimate of the net production. Furthermore, let ~ ff ^ and p ~ pp ^ . The operator C(e), which maps errors into f synthetic controls, should be strictly input passive (see Appendix). We can then use the stability of the feedback systems to show ~ p ~ to set point errors is given that the gain from the error d f by inverse of the L2 gain of the operator C. The stability result developed (Ruszkowski et al., 2005) requires that the mapping ^ m, z, d is invertible with respect to the manipulated variable m. f

c where Jc in is the total ux of carbon entering the system and Jout is the total ux of carbon leaving the system. As per the simulations, the effect of integral action to control the carbon inventory is almost negligible. However, for completeness, the integral term is included in the equation. Similarly, inventory balance equation for the total internal energy is given by Z t ^ Q mout h ^ K Uc U Kc, 2 Uc Uc dt 43 min h c, 2 out c in

tI , 2

From simulation results, the second controller to maintain the energy inventories by changing the amount of heat Q supplied to the system results in offsets with a simple proportional control. Thus, integral action becomes inevitable for the second controller. Both the controllers are implemented simultaneously as a given disturbance will affect both the inventories. The resulting equation for the manipulated variablescarbon feed and the external heat source is directly implemented into the boundary condition and the model equations, respectively. The corrective action governed by the control strategy is a simple expression (Eqs. (42) and (43)) with integral terms built in it. By incorporating such expressions in the model equations (which is a system of PDEs) results in an integro-partial differential equation system. The control action is calculated and implemented under the common platform of solving PDEs in COMSOL Multiphysics. The control action is initially tested with changes in set points for both the carbon hold up and the internal energy of the system.

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In Fig. 11, the step changes made in the carbon hold up reference prole and the corresponding change in the carbon inventory is shown in the rst subplot. A closer view of the change at a particular step change is shown in the second subplot. The corresponding change in manipulated variable is shown in Fig. 12. Similarly, the change in reference value for the energy inventory and the equivalent changes made to the system by the controller are given in Fig. 13. The heat supplied by the external source is modied to match the energy inventory to the proposed set point (Fig. 14). Velocity of the vapor stream is believed to be a disturbance variable. Thus, the controller is tested for a change in the inlet velocity of the aluminum vapors. The set point for energy inventory (1.5e7 J) and the carbon holdup (0.33 mol) are now xed. The change in vapor velocity and the respective variations seen in the inventories and the manipulated variables are shown in Figs. 1517. From the results obtained, it can be inferred that the proposed control strategy performs satisfactorily in maintaining the inventories of the system at the specied level. Thus, based on the reactor conguration and the operating
Fig. 13. Set point changes in total internal energy of VRR and the corresponding inventory variations.
Carbon Holdup in VRR (mol)

0.5 0.45 0.4 0.35 Reference profile data2

0
Carbon Holdup in VRR (mol)

500

1000

1500 Time (s)

2000

2500

3000

0.39 0.38 0.37 0.36 0.35 0.34 1500 1550 1600 Time (s) 1650 1700 1750 Reference profile Actual profile

Fig. 11. Set point changes in total carbon holdup and the corresponding inventory variations. Fig. 14. Change in manipulated variableexternal heat source.

Fig. 12. Change in manipulated variablecarbon feed.

Fig. 15. Series of step changes in the vapor velocityas a disturbance to the system.

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4801

Total Internal Energy in VRR (J)

x 107 1.52 1.51 1.5 1.49 1.48 1.47 0 500 1000 1500 Time (s) 2000 2500 3000 Reference Profile Actual Profile

based on the passivity-based inventory control law. The total carbon hold up in the system and the total internal energy of the system are taken as controlled variables. The vapor velocity is considered as the disturbance variable with the carbon feed and the heat from an external heat source as the manipulated variables. From the results obtained, the proposed control performs well in controlling the inventories of the system through which other crucial parameters like the extent of conversion and the maximum temperature attained in the reactor can be controlled. Nomenclature b c Cpf Cps cS 0 Deb h KE kf kfs Nu Pr r0 rc Re t T0 vg vs X z DH stoichiometric coefcient concentration, mol/m3 heat capacity of uid, J/kg/K heat capacity of solid, J/kg/K initial concentration of solid (carbon), mol/m3 dispersion coefcient in axial direction, m2/s heat transfer coefcient, W/m2/K equilibrium constant thermal conductivity of uid, W/m/K thermal conductivity of solid, W/m/K Nusselt number Prandtl number radius of the pellet, m radius of the unreacted core pellet, m Reynolds number time, s initial temperature, K supercial gas velocity, m/s solid velocity, m/s extent of carbon conversion axial coordinate, m heat of reaction, J/mol void fraction uid density, kg/m3 solid density, kg/m3 reaction rate, mol/(m3 s) uid viscosity, kg/m s

x 106 Heat Supplied (Q, in J) 4.5 4 3.5 3 2.5 2 0 500 1000 1500 Time (s) 2000 2500 3000

Fig. 16. Closed loop simulation for the energy inventory.

Carbon Holdup in VRR (mol)

1.5 1 0.5 0 0.5 1 0 500 1000 1500 Time (s) 2000 2500 3000 Reference Profile Actual Profile

0.48 0.475 Carbon Feed 0.47 0.465 0.46 0.455 0.45 0 500 1000 1500 Time (s) 2000 2500 3000

eB rf rs s mf

Fig. 17. Closed loop simulation for the total carbon holdup.

Appendix A. Passivity theory Passivity theory integrates the effects of input and output variables in the analysis of stability and dynamic state evolution. Its applications extend to both linear and non-linear systems with intuitive and relatively simple results as passive systems are easy to control. Simple control strategies like PI or PID can be devised that stabilize the system at a specic operating point. Let us consider a system with input u and output y. Suppose that there exists a nonnegative storage (C1) function W(t), such that dW r f pvv bJxJ2 2 dt The system is 1. 2. 3. 4. Passive Strictly Strictly Strictly if b 0. input passive if x u and b 4 0. output passive if x y and b 4 0. state passive if x represents the state and b 0.

conditions, the inventory of the system can be changed such that the required conversion is attained. Also, the maximum temperature of the system can be controlled by controlling the energy inventory of the system.

11. Conclusions A distributed parametric model that describes the mass and heat transfer in a non-porous moving bed is developed in this work. The model can be employed to simulate the VRR operating in transient regime. The model takes into account the external transfer of the gaseous species onto the surface of the solid particle, the diffusion through the pores of the solid product layer and the heterogeneous chemical reaction at the surface of the solid reactant. The reactions are mass transfer limited and hence a shrinking core model is used to describe the reaction rate. A sensitivity study of the VRR has been performed using the model. The analysis reveals that the Al2O and Al gas conversions increase with increasing charcoal feed rate, while solid conversion decreases. For the same gas ow and solid feed rate, taller column leads to higher conversions. A control study has been carried out

The notation J J2 denotes the L2 norm for a function dened on a domain O such that for any square integrable vector x we have Z xT x dO o 1 JxJ2 2
O

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O is dened by the semiclosed set 0, 1 0, L and subsets thereof. Willems (1972b) proved that if W has a strong local minimum then there is an intimate connection between dissipativity and Lyapunov stability. In this case, W is convex and it is also a Lyapunov function. Byrnes et al. (1991) developed these ideas further and established conditions for stabilizability of nonlinear, nite dimensional systems using passivity. It was shown that a nite dimensional system is stabilizable if it is feedback equivalent to a passive system. These results suggest a close relation between passivity and the methods of irreversible thermodynamics.

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