Article pubs.acs.

org/IECR

Catalytic Wet Oxidation in Three-Phase Moving-Bed Reactors: Modeling Framework and Simulations for On-Stream Replacement of a Deactivating Catalyst
Ion Iliuta and Faca l Larachi*
Department of Chemical Engineering, Laval University, Queb ec, G1 V 0A6, Canada
S Supporting Information *

ABSTRACT: Phenol wet oxidation over deactivating catalysts in three-phase moving-bed reactors was simulated by formulating and solving a two-scale, nonisothermal, non-steady-state model to highlight the strength of on-stream catalyst replacement, in comparison to catalyst-batch xed-bed reactors. Simulation results indicate that three-phase moving-bed reactors oer a promising alternative to xed-bed reactors. The autonomy of xed-bed reactors is limited due to severe reduction of catalyst activity, while in moving-bed reactor congurations, the decline of pollutant conversion is reduced with increased solid velocity, to compensate for the decrease in catalyst activity loss. The xed-bed reactor operates in non-steady-state mode, because of the continuous decline of catalyst activity while moving-bed reactors evolve to steady-state operation after a transient period. Decreasing the reactor feed phenol concentration and increasing liquid residence time in the reactor and feed temperature are the best ways to oppose rapid deactivation of catalyst in moving-bed reactors.

INTRODUCTION Water is becoming an increasingly coveted commodity, so regional and planetary policies are being implemented for the safeguarding and economical exploitation of water resources and for the ecient treatment of contaminated industrial and domestic water euents. Wastewater management is a perennial problem facing in the rst place the industries. Because of the reinforcement of regulations for the quality control of euents, the manufacturing industries must minimize their emissions of organic and inorganic wastes using ecient routes via the socalled atom economy concept, which consists of maximizing atom utilization from the raw materials to the nal products.1,2 In addition, it is vital to develop highly ecient processes with the ability to destroy the hazardous xenobiotic pollutants that are contained in the residual waste euents. Wastewater produced in many industrial processes contains organic compounds in the range of few hundred ppm to a few thousand ppm, which cannot be addressed economically via incineration or biological processes. Within this niche of concentrations and toxicity, catalytic wet oxidation (CWO) is vouched as the most suitable disposal routes. CWO is a pollutantdestructive wastewater technology based on catalytic oxidative breakdown of water-soluble organics. Recourse to solid catalysts oers a practical technological alternative to noncatalytic or homogeneously catalyzed routes,3,4 because treatments can be carried out under relatively mild temperature and pressure, at notably shorter residence times within compact installations; besides, catalysts, in principle, can be easily recovered, regenerated, and reused. Laboratory tests reveal that CWO is so versatile that wastewaters containing a broad spectrum of organic and/or inorganic pollutants including carbon, oxygen, nitrogen, halogen, sulfur and phosphorus-bearing molecules are tackled eciently. However, despite its success in laboratory testing, industrial-scale application of the CWO process is limited,5,6 mainly because of a lack of stable catalytic performances over
2012 American Chemical Society

suciently long periods of time. It has been demonstrated that catalyst deactivation can take place because of active-phase leacho, the formation of carbonaceous deposits, catalyst sintering, metal oxidation, inactive metal, or metal oxide deposition.7,8 Given the potential of CWO, over the last three decades, a great deal of research has been conducted on various aspects of process including catalyst development and deactivation, CWO reaction pathways and kinetics, and eects on total organic carbon (TOC) removal of temperature, pressure, and pH. In contrast, the literature still remains short about remediation steps for catalyst deactivation and operation windows in which deactivation of the catalyst is minimized and high selectivity is maintained. For example, there is a lack of information about the types of three-phase reactors most suitable for implementing catalytic wet oxidation in the presence of deactivating catalysts.9 Therefore, it is vital to explore novel reactor congurations for handling CWO while accounting for the complex chemical kinetics, interphase and intraparticle heat and mass transport phenomena, thermodynamics, ow patterns and hydrodynamics. This contribution is oered in this direction and continues our endeavor10,11 to develop conceptual models for the prediction and simulation of catalytic wet air oxidation multiphase reactors. In this work, we investigate the applicability and eectiveness of three-phase moving-bed reactors for CWO under catalyst deactivation conditions. The study attempts to set the CWO reactor modeling by integrating the complex physical and chemical processes at the catalyst and reactor levels. Therefore, a two-scale, nonisothermal, non-steady-state model was developed to account for a relatively detailed gasliquid dynamics
Received: Revised: Accepted: Published:
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October 2, 2012 December 9, 2012 December 10, 2012 December 10, 2012
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Figure 1. Deactivationreaction network for phenol CWO with the formation of carbonaceous foulant.8

that was associated with the deactivation-reaction network kinetics, the descriptions of thermodynamics and thermal eects, and the impact of on-stream catalyst replacement on the moving-bed-reactor performances. We will analyze, through

THREE-PHASE MOVING BED REACTOR MODEL Reaction Network. Catalytic oxidation of aqueous phenol over a deactivating MnO2/CeO2 oxide catalyst8,12 (deactivation induced by formation of carbonaceous deposits on active sites) shows that, apart from the main reaction, where phenol is converted to total inorganic carbon, other lump reactions are also possible. Figure 1 shows a multiple deactivationreaction network describing phenol CWO reaction.8 The network, in which all the intervening species are grouped into four carbon lumps, is represented by a sequence of elementary steps according to the LangmuirHinshelwoodHougenWatson

simulations, the behavior of a three-phase moving-bed reactor for CWO, which we will compare to a standard xed-bed reactor.

Figure 2. Time-dependent phenol conversion for dierent values of interstitial solid velocity: (a) H = 1 m, vs S = 0.0015 m/s, vsg = 0.0283 m/s; (b) H = 2 m, vs S = 0.003 m/s, vsg = 0.04 m/s.
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Industrial & Engineering Chemistry Research approach. Chemisorbed phenol (lump A) is converted to chemisorbed oxidation intermediate lump B, which, in turn, breaks down into oxidation end-product lump C (total inorganic carbon). Lumped species A, B, and C can instantaneously adsorb or desorb. Concomitant with these steps, a foulant (lump W) is formed by a series of complex polymerization reactions between lumps A and B and is adsorbed irreversibly on the catalyst surface progressively blocking access to the active sites. The LangmuirHinshelwoodHougenWatson kinetic model developed by Hamoudi et al.,8 based on this deactivation reaction network, was used to describe the evolution of the various carbon lumps, as well as the catalyst activity decline during phenol wet oxidation:8
rA = k 2K1CA CC 1 + K1CA + K3C B + K3
(1)

Article

rB =

(k 2K1CA k2 K3C B) 1 + K1CA + K3C B + K 3 CC

(2)

(k4K1CA + k4 K3C B) d = dt 1 + K1CA + K3C B + K 3 CC

(3)

Reactor Scale Model. A co-current unidirectional downward gasliquid viscous Newtonian ow through a porous moving/xed bed with constant bed void fraction and singlesized catalyst particles is considered. The catalyst bulk ow is downward and driven by gravity with catalyst grains partially wetted by the liquid lm. The solid pellets within the reactor were assumed to move steadily in a close-packing fashion. The gas is ideal and the liquid is incompressible. Moreover, the following general assumptions are made in developing the modeling framework: (i) the organic pollutants are nonvolatile, keeping the oxidation reaction solely in the liquid phase; (ii) the catalyst particles are internally completely wet; (iii) whereas diusion of reactants inside the catalyst particle occurs in the liquid; (iv) no correction of eective diusivity is made to account for catalyst progressive deactivation due to carbonaceous deposits; (v) water evaporation is described using mass and energy conservations with interfacial water vapor pressure equated to saturated vapor pressure. The catalyst migration time being relatively large, compared to liquid mean residence time in the reactor, the three-phase moving-bed reactor can be viewed as a pseudo-two-phase (gas liquid) ow xed-bed system. The ratio between interstitial liquid and solid velocities is at least of the order of 600. Consequently, the non-steady-state ow model is based on the macroscopic volume-average forms of the transport equations for multiphase systems developed for xed-bed reactors.13 The general model equations consist of volume conservation, continuity and momentum balance equations for both gas and liquid, species conservation equations in the liquid and gas, and the overall gas + liquid + solid energy (heat) balance: Conservation of volume: S + g = Gas and liquid continuity equations:
(g g ) + (g g ug ) = 0 t z (SS ) + (SS uS) = 0 t z
(5) (4)

Figure 3. Time-dependent axial distribution of catalyst deactivation function for dierent values of interstitial solid velocity (H = 2 m, vs S = 0.003 m/s, vsg = 0.04 m/s, r/rp = 0.934): (a) us = 0 m/s; (b) us = 2 105 m/s; (c) us = 104 m/s.

Gas and liquid momentum balance equations:

(g g ug ) + ug (g g ug ) z t 2 u P g = g ge 2 g + g g g Fg S Fgs z z
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(6)

(7)

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Figure 4. (a) Phenol conversion vs time at dierent values of catalyst particle diameter. (b) Eectiveness factor vs catalyst particle diameter at dierent reaction times (H = 1 m, vs S = 0.0015 m/s, vsg = 0.0283 m/s, us = 2 105 m/s).

( SuS) + uS (S SuS) t S z S 2u P = SSe 2S S + SS g + e [Fg S + Fgs] FSs z g z

(8)

(SC B, S) t

z C B, p 2(SC B, S) eff = DS DB, p 2 r z

(SuSC B, S)

as(1 )e
r = rp

(10)

Species balance in liquid phase with axial dispersion:

(SCA, S) t + (SuSCA, S)

(SC H2O, S) t

(SuSC H2O, S) z
2 eff DH 2O, p

z CA, p 2(SCA, S) eff = DS DA, p 2 r z

= DS
as(1 )e
r = rp

2(SC H2O, S) z

C H2O, p r 1 RT
r = rp

as(1 )e

(9)
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sat (kga)H2O (PH PH2O, g ) 2O

(11)

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(SCO2, S) t = DS + (SuSCO2, S) z
2 eff DO 2, p

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2(SCO2, S) z

CO2, p r
r = rp

as(1 )e

PO , g 2 + (kSa)O2 C O2 , S He RT O2

(12)

Species balance in (plug-ow) gas phase:

PO2, g PO2, g g + ug g RT t RT z PO , g CO2, p 2 eff C = (kSa)O2 O2 , S DO2 , p He RT r O2 as(1 )(1 e)

r = rp

(13)

sat (g PH2O, g ) + (ug g PH2O, g ) = (kga)H2O (PH PH2O, g ) 2O t z

(14)

Overall heat balance equation with plug-ow solids:

(SS cpS + g g cpg + (1 )p cps) T t T z

+ (SS uScpS + g g ug cpg + (1 )p uscps) = SSeff ,z Tp 2T eff p 2 r z

as(1 ) (kga)H2O
r = rp

sat (PH PH2O, g ) 2O

1 Hev ,H2O RT

(15)

Gas and liquid velocities at the inlet are specied in Dirichlettype boundary conditions. At the outlet, an open boundary condition was used,14 which implies, except for pressure, zero gradients for all ow variables normal to the outow boundary. The liquid holdup at the reactor inlet was calculated assuming ug/z = uS /z = 0 and combining eqs 7 and 8:
Fg S Fgs S S F 1 + e + 1 + e Ss + (S g )g = 0 g S g S S

(16)

The initial and boundary conditions for eqs 915 are as follows:
t = 0, z > 0 Pj , g = P jin ,g , Cj , S = Cjin ,S T = T in
(17)

t > 0, z = 0

Pj , g |z = 0 = P jin ,g , Cj , S z
z = 0+

uSSCjin , S = uSSCj , S|z = 0+ DS S

t > 0, z = 0

(18)

Figure 5. Catalyst deactivation function as function of time and space for dierent values of wetting eciency (H = 1 m, vs S = 0.0015 m/s, vsg = 0.0283 m/s, us = 2 105 m/s, r/rp = 0.934): (a) e = 0.65, (b) e = 0.85, and (c) e = 1.0.

(uSSS cpS + ug g g cpg + us(1 )p cps)T in= (uSSS cpS + ug g g cpg + us(1 )p cps)T |z = 0+ T SSeff ,z z z = 0+

t > 0, z = H

Cj , S z
z=H

= 0,

T z

=0
z=H

(20)

(19)
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Pellet-Scale Model. Description of the simultaneous transport across, and consumption within, each catalyst particle
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Figure 6. Phenol conversion versus time for dierent values of wetting eciency (H = 1 m, vs S = 0.0015 m/s, vsg = 0.0283 m/s, us = 2 105 m/s).

requires simulation of time and space mapping of species concentrations and temperature, as well as catalyst activity loss rate /t. To accomplish this task, and assuming spherical grain symmetry, the catalyst particle-scale mass and heat balance equations to be solved are
p Cj , p t Cj , p 1 = 2 r 2Djeff + usp + jrjp ,p z r r r Cj , p
(21)

eff p

Tp r
r = rp

s s = gs(T p T )(1 e) + Ss(T p T )e

(26)

t > 0, z > 0, r = 0

Cj , p r

=0

Tp r

=0

(27)

j = A, B, H 2O, O2

t > 0, z = 0, r > 0 Tp = T |z = 0+

Cj , p = Cj , S |z = 0+

=1
(28)

(1 p) =

(Ct) (Ct) + us(1 p) t z K3C B, p)Ct (k4K1CA, p + k4

(22)

t = 0, z > 0, r > 0

Cj , p = Cin j,S

=1

Tp = T in
(29)

CC , p 1 + K1CA, p + K3C B, p + K3

(pS cpS + p cps)

+ us(pS cpS + p cps) z t Tp eff 1 = p r 2 + ( Hr ,A )rAp 2 r r r

Tp

Tp

(23)

The corresponding boundary and initial conditions are given as

t > 0, z > 0, r = rp j = A, B, H 2O
eff DO 2, p

Djeff ,p

Cj , p r
r = rp

= kSs , j(Cj , S Cj , s)e

(24)

Reactor-Scale Closure Laws. In the momentum balance described by eqs 7 and 8, a set of constitutive equations is required for the interfacial drag forces. The assumption of bed partial wetting entrains that the gas-phase drag has contributions due to eects located at the gasliquid (Fg S ) and gas solid (Fgs) interfaces. Similarly, the resultant of the forces exerted on the liquid phase involves two components: (i) the drag force (FSs ) experienced by the liquid due to shear stress nearby the liquidsolid boundary, and (ii) the gasliquid interfacial drag due to slip between uids (Fg S ). Assuming a trickle ow regime, the double slit analogy provides satisfactory approximations for the liquidsolid, gassolid, and gasliquid drag forces:15
a 2(1 )2 E S e 2 s 1 FSs = e Cw 3 S 36 + a (1 ) E2 S |vs S|vs SS (1 + g S)Cwi s 3 6 S

CO2, p r
r = rp

= kSs ,O2(CO2, S CO2, s)e PO , g + kgs ,O2 2 HeO2CO2, s(1 e) RT

(25)
375

(30)

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Figure 7. (a) Phenol conversion vs time at dierent values of supercial liquid velocity. (b) Eectiveness factor versus supercial liquid velocity at dierent reaction times. (c) Reactor temperature versus dimensionless axial distance for dierent values of supercial liquid velocity after 25 h (H = 1 m, vsg = 0.0283 m/s, us = 2 105 m/s).
2 2 E as (1 ) g Fgs = (1 e) 1 Cw 2 3 36

E2 as(1 ) C | | v g sg vsg wi 3 6

To represent the gasliquid relative motion intervening in Fg S , the eect of slip between gas and liquid is taken into account by means of a velocity ug,i at the gasliquid interface derived in the work of Iliuta et al.15 and estimated from the double slit model as
(31)

72 1 P S + S g S ug , i = 2 2 2 E1 (1 ) as e S 2 H P + + g g (e S) H
(33)

as2(1 )2 g E E 2 1 + 2 Cwi(1 + g S) Fg S = e Cw 2 36 6 [ (S /e)] g S v ug , i sg e [ (S /e)]2 g as(1 )g

S vsg ug , i g e

(32)
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In eqs 15 and 19, the condition us = 0 designates the solids stationary (or xed bed) interstitial velocity and us 0 is the average solid interstitial velocity in the case of three-phase moving-bed reactor. Model Parameters. The correlations for mass- and heattransfer coecients developed for two-phase downow xedbed reactors (listed in Table S1 in the Supporting Information) were considered appropriate in moving-bed reactors, considering
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Figure 8. Steady-state catalyst deactivation function versus dimensionless axial distance for dierent values of supercial liquid velocity (H = 1 m, vsg = 0.0283 m/s, us = 2 105 m/s, r/rp = 0.934).

the very low ratio between interstitial solid and liquid velocities, where the moving-bed reactor can be viewed as a pseudo-twophase ow xed-bed system. The Ergun single-phase ow parameters can be set either by measurements of single-phase pressure drops16 or estimated from literature correlations.17 Regarding the interaction parameter (g S ), which accounts for the interaction between the gas and liquid, it is bounded within the range 110 in two-phase downow xed-bed reactor: under no interactions (trickle ow regime), the value is close to unity, whereas, at high gas-to-liquid ratios and high-pressure conditions, it can be as high as 10. This interaction function can be estimated using a correlation that was proposed by Iliuta et al.15 The diusivity of each component in the liquid phase was calculated using the Wilke4Chang method.18 The eective diusion coecients were evaluated assuming a tortuosity factor of 3. The correlations for the viscosity of the gas mixture, the thermal conductivity of the gas and liquid mixture, the eective thermal conductivity of the catalyst particles, and the -phase eective thermal conductivity in the axial direction are presented in Appendix 1, which is given in the Supporting Information.8,18,2228 The extent of backmixing in the liquid phase was quantied in terms of axial dispersion coecient, evaluated using a comprehensive Bodenstein number correlation.19 The wetting eciency was evaluated using the neural network correlation developed by Larachi et al.20 The kinetic parameters of the catalytic wet oxidation of phenol were taken from Hamoudi et al.8 and are summarized in Table S2 in the Supporting Information. Operating Conditions. The characteristics of the porous MnO2/CeO2 catalyst particles, the design and geometric parameters and the operating conditions are listed in Table S3 in the Supporting Information. With water being the overwhelming compound and the phenol concentration being relatively small, the physical properties specic to water are used for the liquid phase. Moreover, because of the moderate severity of the simulated oxidation (0.5 MPa and 80 C) and dilute water conditions, it is not necessary to use detailed equations of state (EOSs) for the uid phases. Fugacity and activity coecients, as well as the compressibility factor for oxygen and water, are all assigned
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values of unity. Raoults and Henrys laws are assumed to be valid for water and oxygen, respectively. Method of Solution. To solve the system of partial dierential equations (PDEs) given above, we discretized in space and solved the resulting set of ordinary dierential equations (ODEs). The spatial discretization is performed using the standard cell-centered nite dierence scheme, at the reactor level (60 grid points), and the method of orthogonal collocation, at the catalyst particles level. The number of collocation points specied for the catalyst particles was restricted to 8. The GEAR integration method for sti dierential equations was employed to integrate the time derivatives. The relative error tolerance for time integration in the present simulations is set at 107 for each time step. Fortran 77 software on an Intel Core 2 Duo Processor E7500 was used to generate the numerical platform.

RESULTS AND DISCUSSION A series of simulations was rst carried out to investigate the performance of the phenol CWO process for dierent solid velocity values. The potential and limits of the moving-bed reactor under dierent operating conditions then were investigated. For the base case, the characteristics of the porous MnO2/CeO2 catalyst particles and the operating conditions are listed in Table S3 in the Supporting Information. Because the outer shell of the catalyst surface (r/rp > 0.8) is most sensitive to deactivation (large catalyst particle diameter), our analysis is restricted to this thin peripheral shell. For the operating conditions simulated in this study, phenol CWO is likely to be a liquid-reactant-limited process,21 taking into account that the ratio between liquid reactant ux (phenol) and gas reactant ux (oxygen) to catalyst particles is small ( < 1). Figure 2 shows the time-dependent phenol conversion at different values of solid interstitial velocity in two reactor congurations operated under high-concentration phenol-containing wastewater conditions (phenolic carbon concentration = 0.06 mol carbon/L). The wetting eciency is ca. 65% (reactor 1, see Figure 2a) and 80% (reactor 2, see Figure 2b), so that the bed does operate with partially wetted catalyst particles. Under xed-bed
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Figure 9. (a) Phenol conversion versus time for dierent values of supercial gas velocity. (b) Eectiveness factor versus dimensionless axial distance for dierent values of supercial gas velocity after 25 h. (c) Reactor temperature versus dimensionless axial distance for dierent values of supercial gas velocity after 25 h (H = 1 m, vs S = 0.0015 m/s, us = 2 105 m/s).

conditions (us = 0), phenol conversion rapidly declines, because of a severe reduction of catalyst activity, especially in the entrance region of the bed, as exemplied in the catalyst activity proles shown in Figure 3a. The autonomy of the xed-bed reactor congurations would be ca. 1 day before the catalyst gets severely coked, after which point spent catalyst burno and regenerability become important issues for long-term exploitation of the catalyst. On the other side, under movingbed conditions (us > 0), the time decay of phenol conversion is reduced by increased solid velocity substantially compensating for the decrease of catalyst activity loss, as exemplied in Figures 3b and 3c. The decline in phenol conversion becomes virtually marginal at us 2 105 m/s in both moving-bed congurations, under high-concentration phenol-containing wastewater conditions. Figure 3 shows that after a transition period, which shrinks as solid velocity increases, the activity function of the MnO2/CeO2 catalyst will remain constant and, consequently, the moving-bed reactor attains a steady state (Figure 2). Therefore, if xed-bed reactors operate in
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nonsteady state due to a continuous decline of catalyst activity, moving-bed reactors, in contrast, have a tendency to attain steady state after a transition period. The model predicts a higher conversion of phenol for movingbed reactors when the catalyst particle diameter is reduced (see Figure 4a). The reduction of catalyst particle diameter improves the wetting eciency, thus ameliorating the transport of liquid reactant to the catalyst. In addition, a decrease in catalyst particle diameter promotes larger values of the eectiveness factor (Figure 4b), which reect into larger values of phenol CWO reaction rate and phenol conversion, alike. The increase of the eectiveness factor and the decrease of catalyst activity with time are counterbalanced, and, as a result, the performance of the moving-bed reactors is not signicantly aected as time progresses. Because phenol catalytic wet oxidation is liquid-reactantlimited, an increase in wetting eciency provides faster transport of the liquid reactant to the catalyst. In addition, as catalyst wetting improves, the decline in time of activity of the MnO2/CeO2 catalyst is attenuated (Figure 5). As a result, the model predicts
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Figure 10. Steady-state catalyst deactivation function versus dimensionless axial distance for dierent values of supercial gas velocity (H = 1 m, vs S = 0.0015 m/s, us = 2 105 m/s, r/rp = 0.934).

Figure 11. Steady-state catalyst deactivation function versus dimensionless axial distance for dierent values of the feed temperature (H = 1 m, vs S = 0.0015 m/s, vsg = 0.0283 m/s, us = 2 105 m/s, r/rp = 0.934).

better performance of moving-bed reactors as wetting eciency improves (Figure 6). Increasing the supercial liquid velocity reduces phenol conversion (Figure 7a), despite an increase of catalyst wetting eciency and eectiveness factor (Figure 7b), and temperature in the reactor (Figure 7c). The moving-bed reactor performance decreases as the supercial liquid velocity increases, because of the lower liquid phase residence time and lower catalyst activity (Figure 8). Catalyst deactivation at higher supercial liquid velocity due to extension of carbonaceous deposits results into a lower reaction rate and, consequently, a lower phenol conversion. Increasing supercial gas velocity similarly reduces phenol conversion (Figure 9a), even if the e ectiveness factor is
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higher (Figure 9b). The moving-bed reactor performance decreases as the supercial gas velocity increases, because of the lower gas phase residence time, lower temperature (Figure 9c), and lower catalyst activity (Figure 10). Lower temperature in the catalyst bed at high gas velocities is the result of amplication of heat removal due to water evaporation. An option to compensate catalyst deactivation in the movingbed reactor is to increase the reactor feed temperature (see Figure 11). For the reactor operation conditions of Figure 11, the increase of catalyst activity at the reactor exit with 60% requires an increase in feed temperature from 80 C C to 110 C. The moving-bed reactor performance increases as the
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Figure 12. (a) Phenol conversion versus time for dierent values of feed temperature. (b) Eectiveness factor versus dimensionless axial distance for dierent values of feed temperature after 25 h. (c) Reactor temperature versus dimensionless axial distance for dierent values of feed temperature after 25 h (H = 1 m, vs S = 0.0015 m/s, vsg = 0.0283 m/s, us = 2 105 m/s).

feed reactor temperature increases (Figure 12a), because of the higher reaction rate and higher catalyst activity. However, the increase in phenol conversion is limited by the decrease of the eectiveness factor (Figure 12b) and the increase of reactor temperature dierence (Figure 12c). The temperature gradient (Tin Te) in the catalyst bed increases as the feed temperature increases, because of additional water evaporation, but certainly the water evaporation process does not signicantly inuence the performance of the moving-bed reactor. An additional alternative to diminish catalyst activity loss is through decreasing the phenol concentration in the reactor feed. For wastewaters with small phenolic carbon concentration, the decline in catalyst activity along the moving-bed reactor is virtually marginal (Figure 13). As in the case of xed-bed reactors (Figure 14), to treat highconcentration phenol-containing wastewaters a priori, dilution before the inlet into the CWO moving-bed reactor is suggested.
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CONCLUSION Phenol catalytic wet oxidation (CWO) over deactivating catalysts in moving-bed/xed-bed three-phase reactors was simulated using a two-scale, nonisothermal, non-steady-state model to account for gasliquid hydrodynamics coupled with a deactivationreaction network kinetics and descriptions of thermodynamics and thermal eects. This study is the rst of its type to address phenomenological modeling of phenol CWO in three-phase moving-bed reactors as a promising alternative to xed-bed reactors with deactivating catalysts. Other issues about catalyst handling outside the reactor when using the moving-bed option were not considered. Continuous catalyst regeneration strategies, such as bypassing catalyst particles moving downward, because of gravity, in a moving bed can be found elsewhere.29 The simulation results indicate that liquid-reactant limited reactions such as phenol CWO are better performed in movingbed reactors rather than xed-bed reactors. The autonomy of xed-bed reactors is limited because of the inevitable reduction of catalyst activity, whereas in moving-bed reactors, the time
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Figure 13. Steady-state catalyst deactivation function versus dimensionless axial distance for dierent values of phenolic carbon concentration (H = 1 m, vs S = 0.0015 m/s, vsg = 0.0283 m/s, us = 2 105 m/s, r/rp = 0.934).

Figure 14. Catalyst deactivation function versus dimensionless axial distance for dierent values of phenolic carbon concentration xed-bed conguration (H = 1 m, vs S = 0.0015 m/s, vsg = 0.0283 m/s, r/rp = 0.934, t = 25 h).

decay of phenol conversion is reduced by the increase in the solid velocity (us), to compensate for the decrease in catalyst activity loss. The decline in phenol conversion in moving-bed reactors operated under high-concentration phenol-containing wastewater conditions is virtually marginal for us 2 105 m/s. The xed-bed reactor operates in non-steady-state mode due to a continuous decline of catalyst activity, whereas moving-bed reactors have a tendency to operate in steady-state mode after a period of transition. Decreasing the phenol concentrationin the reactor feed and increasing liquid residence time and feed temperature are found to be the best ways to diminish catalyst deactivation in moving-bed reactors.
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The moving-bed conguration, such as that observed in the on-stream catalyst replacement (OCR) technology that has been proven and operated by ChevronTexaco in hydrodemetallization of heavy petroleum residua or the Institut Franca is du Pet role three-phase moving beds could be a viable option for CWO to counterbalance the compulsory shutdowns of packed beds due to deactivation.30,31 Obviously, moving-bed technology is more prohibitive than xed-bed technology and can be justied only if important capital savings can be accomplished through reactor size reduction and savings on catalyst amounts, because CWO does not yield marketable products but treated waters. We hope the present eort will shed some light to devise experimental
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Industrial & Engineering Chemistry Research studies to test the value of this new type of reactor in the realm of CWO.
Greek Letters

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ASSOCIATED CONTENT

S Supporting Information *

Appendix 1. This material is available free of charge via the Internet at http://pubs.acs.org.

AUTHOR INFORMATION

Corresponding Author

*Tel.: (418) 656-2131, Ext. 3566. Fax: (418) 656-5993. E-mails: ion.iliuta@gch.ulaval.ca (I.I.), faical.larachi@gch.ulaval.ca (F.L.).
Notes

The authors declare no competing nancial interest.

ACKNOWLEDGMENTS Support from the Natural Sciences and Engineering Research Council of Canada, the Canada Research Chair Green Processes for Cleaner and Sustainable Energy and the FQRNT-funded Center in Green Chemistry & Catalysis (CVCC) is gratefully acknowledged. NOTATION as = bed specic surface area, m2/m3solid cp = specic heat capacity of -phase, J/(kg K) Cj = concentration of lump j, kmol/m3 3 Cjin S = j-component concentration in feed stream, kmol/m Cp,j = heat capacity of species j, J/(mol K) Ct = mole total sites concentration, kmol/ms3 Ct = mole total active sites concentration, kmol/ms3 dp = particle diameter, mm, m 2 Deff j,p = eective diusivity of species j inside the particle, m /s DS = liquid axial dispersion coecient, m2/s E1, E2 = Ergun constants Fg S = gasliquid drag force, N/m3 Fgs = gassolid drag force, N/m3 FSs = liquidsolid drag force, N/m3 H = bed height, m Hej = Henry constant, mS 3/mg 3 k, k = lumped rate constants, mol/(kg min) kga = gas side volumetric gasliquid mass transfer, 1/s kgs = gassolid mass transfer coecient, m/s kSa = liquid side volumetric gasliquid mass transfer, 1/s kSs = liquidsolid mass transfer coecient, m/s K, K = adsorption equilibrium constants, m3/kmol Mj = molecular mass of species j, kg/kmol P = reactor pressure, Pa Pj = partial pressure of species j, Pa rj = reaction rate, kmol/(kgcatalyst s) r = radial position within catalyst particle, m rp = radius of catalyst particle, m t = time, s T = temperature, K Tc = critical temperature, K u = average interstitial velocity of -phase, m/s vs = supercial velocity of -phase, m/s X = phenol conversion yj = mole fraction of species j in gas phase z = longitudinal coordinate, m
382

= deactivation function gs = gas-particle heat transfer coecient, J/(m2 s K) Ss = gas-particle heat-transfer coecient, J/(m2 s K) Hev = enthalpy of evaporation, J/mol Hr = reaction enthalpy, J/mol g = gas holdup S = liquid holdup p = particle internal porosity = ratio between the liquid reactant ux and gas reactant ux to the catalyst particle = eectiveness factor e = external wetting eciency = thermal conductivity of -phase, J/(m s K) ,j = thermal conductivity of species j in -phase, J/(m s K) eff ,z = axial eective thermal conductivity of -phase, J/(m s K) eff p = eective thermal conductivity of catalyst particles, J/(m s K) = dynamic viscosity of -phase, kg/(m s) = density of -phase, kg/m3 p = particle density, kg/mp3 sc = catalyst bed density, kg/m3 g S = gasliquid interaction factor A = phenolic carbon, A lump B = carbon of oxidation intermediates, B lump C = carbon of fully mineralized products, C lump e = reactor exit g = gas phase in = reactor inlet S = liquid phase p = catalyst particle s = solid phase, surface of the catalyst particle

Subscripts/Superscripts

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