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Paper 1 - Three-Phase Catalytic Reactors PDF
Paper 1 - Three-Phase Catalytic Reactors PDF
Abstract
This article aims at presenting both the general aspects and one working example of the so-called three-phase catalytic
reactors. Being a contribution at a Seminar on Catalytic Reactors the purpose is essentially didactic in showing the problems
met and how a few of them can be investigated and solved. Only trickle bed and slurry reactors are considered the most
important, probably, among the class of three-phase reactors. # 1999 Elsevier Science B.V. All rights reserved.
0920-5861/99/$ ± see front matter # 1999 Elsevier Science B.V. All rights reserved.
PII: S 0 9 2 0 - 5 8 6 1 ( 9 9 ) 0 0 0 7 7 - 2
224 G. Biardi, G. Baldi / Catalysis Today 52 (1999) 223±234
stirred reactors are also employed as multipurpose At low liquid and gas ¯ow rates, the two phases ¯ow
reactors in the ®ne chemical industry. Bubbling slurry with a low hydrodynamic interaction (low interaction
reactors are particularly employed in fermentation regime, trickling regime); the pressure drop has the
processes; here the solid phase is represented by the same order of magnitude as that arising from gas ¯ow
biomass, which acts as a biocatalyst in the production alone through a dry packing [5]. An increase of the
of enzymes or other products. liquid ¯ow rate, at a constant gas ¯ow rate, leads ®rst
The choice of a suitable reactor is strictly connected to the pulsing ¯ow, characterized by the formation of
with the requirements and characteristics of the pro- alternate slugs ± liquid-rich and gas-rich slugs ±
cess and the engineering aspects. Slurry reactors, travelling along the reactor (pulsing regime); the
either continuous or batch, require separation of the pressure drop increases remarkably, and shows a
catalyst that represents a cost and a further time of ¯uctuating behaviour. These ¯uctuations are due to
operation; moreover, abrasion of the catalyst with the formation of liquid bridges in the packing channels
generation of very ®ne particles may occur. Stirred caused by the thickness of the liquid ®lm and the
reactors have a high liquid holdup and a low (mass of waves on it generated by the gas ¯ow interaction.
catalyst/mass of liquid) ratio. As a consequence, they These bridges stop the gas in the channels, the pressure
are particularly interesting for highly exothermic reac- behind them increases and ®nally the liquid is blown
tions (temperature control of these reactors is not a up; then, the process is repeated.
dif®cult task); on the other side, a negative aspect is A further increase of the liquid ¯ow rate at rela-
represented by the occurrence of possible homoge- tively low gas ¯ow rates can give rise to a bubbling
neous side reactions. As batch reactors they must be ¯ow, where the liquid is the continuous phase and the
employed when particular policies of reactants feed gas is carried along the reactor as bubbles. On the
and temperature are adopted. other hand, at high gas ¯ow rates and low liquid ¯ow
Continuous ®xed bed reactors are generally rates, the spray regime exists, where the liquid is
employed for high throughputs and simple reactions. carried by the gas in the form of droplets.
A limitation, in certain cases, is represented by Fig. 1 represents a map of these regimes for liquids
temperature control, since they operate in an and gas similar to water and air, respectively; it is
adiabatic mode. Dif®culties may also arise from ¯uid certainly not exhaustive because the physical proper-
phases distribution, which may give rise to poor ties of the liquid (mainly the foaming characteristics)
performance or even hot spots and sintering of the have important effects not yet mapped.
catalyst. The data used for Fig. 1 were all taken at atmo-
spheric pressure. A recent paper by Wammes et al. [6]
shows a certain in¯uence of pressure (tests till 2 MPa
2. Fixed bed reactors were performed); these data were in qualitative agree-
ment with the trickle ¯ow-pulsing ¯ow transition
2.1. Hydrodynamic regimes diagram proposed by Talmor [7].
The regimes of interest in commercial units are
Fixed bed reactors are mostly employed with the trickling ¯ow and the pulsing ¯ow near the
cocurrent ¯ows of gas and liquid to avoid the transition between these two regimes. Pilot and
hydrodynamic limitation of ¯ooding. Downward bench-scale reactors are instead operated in the
¯ows (trickle-bed reactors) are much more widely trickling ¯ow at very low ¯ow rates per unit area.
used than upward ¯ows, because pressure drop is This causes problems in scale-up as will be shown
much less (in up¯ow, instead, hydrostatic head of later on.
the liquid must be overcome). In trickle-bed reactors, Also two phase up¯ow through a packed bed gives
the liquid trickles down over the packing in the form of rise to several regimes [8], but only the one where the
®lm or rivulets. The gas ¯ows cocurrently in the void gas is bubbling in the continuous liquid phase is of
space. practical interest. Up¯ow bubbling reactors may be
Depending on the relative ¯ow rate of the two employed for a highly exothermic reaction because of
phases, several regimes have been set up [4,5]. the relevant holdup of liquid.
G. Biardi, G. Baldi / Catalysis Today 52 (1999) 223±234 225
2.2. Micro- and macrokinetics where ks is the liquid±solid mass transfer coef®cient
and RA(cAs) is the kinetic rate inside the pellet at the
Microkinetics is generally described in terms of a interface liquid±solid concentration cAs.
series of elementary kinetic steps. The reaction is The gaseous reactant is transferred to the liquid
assumed to occur only in the porous solid catalyst phase by a two-step phenomenon: gas-to-liquid inter-
uniformly wetted by the liquid. The kinetics inside the face transport and liquid interface-to-bulk liquid trans-
pellet may be affected by diffusion phenomena in the port. Generally, the gas phase resistance is very weak
pores (assumed to be ®lled completely by the liquid) and ignored; the gas±liquid mass transport ¯ux (per
according to the Thiele modulus. These effects are unit reactor volume) is written as follows:
classically taken into account by the catalyst effec-
jA ÿ
kl a
cAl ÿ cA (2)
tiveness factor . Intrinsic kinetics and effectiveness
factor are determined in laboratory bench reactors where cA is the liquid concentration in equilibrium
(slurry or basket-type reactors), and great care must with the gas phase.
be devoted in order to de®ne them accurately. Macrokinetics refers to the distribution of reactants
The determination and the use of this kinetic infor- in the reactor, and concerns the reactor model.
mation is complicated by the fact that the reaction heat The complete, heterogeneous model assumes:
is released into the pellet and this may eventually lead
to temperature gradients inside the catalyst. However, the three phases are separated and continuous;
it was demonstrated [9] that when the pores of the the solid is in contact with the liquid only;
catalyst are full of liquid, the temperature gradients the particles are uniformly wetted;
can be ignored even in the presence of a highly the plug flow-axial dispersion model is adopted for
exothermic reaction. the fluid phases.
The reactants are supplied to the catalyst from the
liquid; at steady state, for each reactant, the following For a bimolecular reaction between a gaseous reac-
equation can be written: tant A and a liquid (nonvolatile) reactant B:
Vc A A B B ! P P
ÿks
cAs ÿ cAl RA
cAs (1)
Ac the model is written as follows:
226 G. Biardi, G. Baldi / Catalysis Today 52 (1999) 223±234
increase and the supply of the gaseous reactant will and liquid are assumed at thermodynamic equilibrium,
increase [27,28]. i.e. equal temperature, gas phase saturated by the
liquid. Assuming a piston ¯ow model, the distribution
of temperature is given by the following equation:
2.4. Heat transfer
d d
The effects of the heat generated by the reaction on
vl l cpl vg g
!I cpI !Cg cpl T
vg g !Cg C
dz dz
the reactor performance must be considered at three
ÿHr jRA
cAs ; cBs =A j: (13)
levels:
The gas phase has been considered as constituted
intraparticle temperature gradients;
partly by an uncondensable gas I, with a mass fraction
interphase heat transport;
!I, partly by vapour of a liquid component C (mass
temperature distribution in the reactor.
fraction in the gas: !Cg; vaporization heat: C). The
Intraparticle gradients of temperature depend on vapour partial pressure of C is calculated by vapour±
two parameters: liquid equilibrium relationship. Hence, two further
cAs
ÿHr Deff equations are needed: a mass balance of C and a
Prater number; (10) gas±liquid equilibrium equation:
eff Ts
E=RTs
Arrhenius number (11) vl;0 l;0 !C;0 vl l !Cl vg g !Cg (14)
!Cg f
!Cl ; . . . ; T: (15)
Solid±¯uid temperature differences are instead gov-
erned by the Biot number of the particle: The vaporization of part of the liquid caused by the
Bip hs dp =eff (12) reaction heat is a way to control the temperature rise
for highly exothermic reaction; to this aim, a volatile
It was demonstrated [9] that the gradients inside a solvent is added to the liquid reactants. Care must be
pellet with pores ®lled by the liquid are very weak due taken to avoid formation of dry zones due to evapora-
to the low value of Deff and the (relatively) high value tion because this will give rise to gas phase reactions
of eff. Moreover, if the particle is in contact with and enhance heat generation rate. In other words, the
¯owing liquid, (Bi)p is quite high because of the high mass ¯ow rate of the volatile solvent must be suitably
value of the heat transfer coef®cient. This means that higher than that evaporated by the reaction heat.
if the particle is evenly and effectively wetted, there Another temperature control policy is recycling of a
are no temperature gradients and the reaction at the cooled part of the outlet liquid ¯ow either at the inlet
particle level occurs isothermally. or along the reactor. In this way, however, the liquid
However, at low liquid velocities, thermal instabil- reactants are diluted and the reaction rate depressed.
ity can take place in trickle-bed reactors because of the For this reason, injection of cold gaseous reactants
uneven liquid distribution at the particle scale. Stag- along the reactor may be better; of course, the heat
nant liquid zones with very poor liquid renewal are capacity of the gas is low so that this method can be
very ineffective for heat transfer. The heat generated adopted only for middle conditions of reaction heat.
near these zones may give rise to a remarkable Less frequent, although ef®cient, is intercooling of
increase of temperature that may eventually lead to ¯uids between two sections of the reactor by heat
evaporation of the liquid. In the dry zone then, a much exchangers.
faster gas phase reaction can take place that enhances The model and the considerations are valid for
evaporation and increases the local temperature. A hot up¯ow and down¯ow reactors. Up¯ow reactors, how-
spot so generated can extend to all parts of the reactor ever, generally do not give rise to serious problems of
in particular operating conditions. This phenomenon temperature control, while care must be taken with
has been observed at the bench scale by Germain et al. trickle-bed reactors. Here, a high liquid super®cial
[29] and Hanika et al. [30,31]. velocity (>4 mm sÿ1) and good liquid distribution is
The distribution of the temperature in the reactor is required for good temperature control in commercial
essentially caused by a convective mechanism. Gas units. That notwithstanding, sometimes hot spots
G. Biardi, G. Baldi / Catalysis Today 52 (1999) 223±234 229
occur due to occlusion of some packing channel by Sometimes a better selectivity is also attained. This is
®ne particles. Downstream this occlusion, a dry cat- due to the particular hydrodynamics occurring during
alyst zone is formed, and gas phase reactions may take gas±liquid ¯ow in the small channels of the monolith.
place with an increase in the rate of generation of heat. First of all, the reactor operates with upward ¯ow;
This may eventually result in an enlargement of the secondly, the best regime is the one where alternate
dry zone, because of evaporation of liquid, an increase slugs of gas and liquid take place because there is an
of temperature and sintering of the catalyst. enhancement of mass transfer from gas to solid during
the period of thinning of the liquid ®lm (Fig. 3). The
2.5. Nontraditional fixed bed reactors disadvantages are cost of the monolith and uneven
distribution of gas and liquid. This is one of the most
To improve the performance of ®xed bed reactors, delicate problems and particular care must be dedi-
new reactors have been proposed; among them, cated in creating a suitable gas±liquid dispersion
trickle-bed reactors (periodically operated), monolith before entering the monolith [37].
two-phases reactors and structured catalyst reactors Structured packed beds have the advantage of a
can be cited. lower frictional pressure drop than the usual random
In a trickle-bed reactor (periodically operated) the one [38]. Application to gas±liquid reactions have
liquid feed is periodically changed between two been proposed recently by Mazzarino et al. [39,40]
extreme values (the minimum ¯ow rate is generally by using a Katapak±Sandwich catalyst, where the
null) with a square wave form. When the liquid ¯ow is catalyst beads are retained between two wire-mesh
cut off, the bed partially drains. This thins out the sheets, which can be shaped to obtain a macroscopic
liquid ®lm surrounding the particles with an increase open cross ¯ow structure. Upward ¯ow was adopted.
in the transport ¯ux for the gaseous reactant. When the The major advantage of this packing lies in the fact
liquid ¯ow rate is ®xed at the maximum value, there is that very small beads of catalyst can be used in order to
an ef®cient transport of the liquid reactants and pro- avoid reaction limitation due to internal diffusion.
ducts to and from the pellets. Interesting results were There is a good renewal of the liquid around the
obtained with this operating method in the case of particles, and suf®ciently high mass transfer coef®-
oxidation of SO2 to SO3 over carbon catalyst [32] and cients can be obtained. On the other hand, high values
for hydrogenation of a-methylstyrene [33]. No com- of liquid axial dispersion were measured, and only
mercial application of this operating way has been upward ¯ow can be adopted. Anyway, this or similar
performed until now. It may be observed, however, packings may be suitable in certain cases.
that unsteady reactors, when properly used, give sur-
prising results; hence, the periodic operations of ®xed
bed reactors must be considered a proposal worth to
consider.
Use of monolith reactors for two-phase reactors is
more mature from a technological point of view. The
hydrogenation of alkylanthraquinone in hydrogen per-
oxide production is a commercial example of the
application of monolith reactors for two-phase reac-
tion (Eka Nobel±Akzo Nobel). Several studies exist on
the topics starting from the pioneering work of Maz-
zarino and Baldi [34]; Irandust and Andersson [35]
and Cybulski and Moulijn [36] are the authors of wide
reviews on the application of monolith reactors for gas
and gas±liquid reactions. The essential behaviour of
this type of reactor is a lower pressure drop in com-
parison to trickle-bed and up¯ow reactors with com-
parable and even higher mass transfer coef®cients. Fig. 3. Slug gas±liquid in a channel of a monolith.
230 G. Biardi, G. Baldi / Catalysis Today 52 (1999) 223±234
3. A working example of slurry reactor the latter one seeming to be the most appropriate one
design and rating for industrial units.
In any case the gas phase reactant, H2, has to
As quoted before, slurry reactors constitute one type overcome a number of rate steps before reacting with
of three phase unit where one gas reactant and a solid the catalyst particle. They are:
catalyst are dispersed in a continuous liquid phase
1. Absorption into the liquid phase by mass transfer
where a second reactant showing a reduced, if any,
through the bubbles area.
volatility is present.
2. Diffusion from the gas±liquid interface into the
In order to get, a little bit, in depth into the problem,
bulk liquid phase.
putting into evidence its many facets and the involved
3. Diffusion from the bulk liquid phase to the catalyst
phenomena as well as the way to take them into
surface (external diffusion).
consideration aiming at a soundly based and reliable
4. Diffusion through the pore structure of the catalyst
model for rating and for designing purposes, we shall
while reacting with the liquid co-reactant on the
work out an illustrative example for an industrial
active sites.
hydrogenation reaction.
The chemical reaction can be put into the form: Hydrogen participates in all the four steps, the
liquid co-reactant and the product, taken as not vola-
A
l H2
g , HyA
l
tile, are involved in the last two steps, one in the
where the hydrogenated product is also a nonvolatile reverse order from the other.
species. Moreover, for process units where the liquid phase
For the purpose of clarity we shall consider the reactant constitutes essentially the liquid phase, its
problem in its simplest form; this means that the basic concentration does not vary in a signi®cant way so that
phenomena will be accounted directly, and modelled in looking for the rate determinating step as well as for
in the proper way whilst for secondary ones, assump- the importance of each individual resistance, only H2
tions will be made, whose validity has to be checked has to be accounted for or considered as the key
afterwards. reactant.
A number of industrial cases can be schematized as Modelling the steps just described enables one to
follows: establish the links relating the reaction microkinetics
to the global rate law (macrokinetics) as depending on
A pressurized stream of pure hydrogen is fed to the the parameters affecting each step.
reactor, sparged and broken up into bubbles under This can be done in terms of rates of disappearance
vigourous stirring so that a hydrodynamic bubble of hydrogen per unit volume of liquid phase for each
regime takes place and a rather complete mixed considered step, namely:
liquid phase exists. (1) Absorption rate. For almost pure hydrogen there
Absolute pressure range is 0.1±1 MPa. is no practical resistance, therefore the interface hy-
The volumetric power dissipation is lower than drogen concentration is in equilibrium with the gas
1 kW mÿ3. phase partial pressure according to the Henry's law.
A porous catalyst having size in the 101±102 mm
PH2 HE CHi 2 ;
range is used for a catalyst load amounting up to
5±6 kg mÿ3 of liquid phase. Generally speaking where PH2 is the partial pressure of H2 (Pa, atm), HE
both the stirrer speed and the specific power are the Henry constant (Pa m3 kmol mÿ1) and CHi 2 is the
high enough so as to completely suspend the solid liquid phase concentration of H2 at the gas±liquid
particles within the reactor. interface (kmolÿ3).
(2) Rate of diffusion from the gas/liquid interface.
These assumptions correspond to a scheme of per-
jRH2 j KL a
CHi 2 ÿ CHb 2
kmol mÿ3 sÿ1
fect mixing for the liquid±solid suspension; whilst, as
for the bubble phase, the extent of mixing can vary where KL is the mass transfer coef®cient in the liquid
from the plug ¯ow to the uniform gas phase behaviour, phase (m sÿ1), a the gas/liquid surface area (m2 mÿ3)
G. Biardi, G. Baldi / Catalysis Today 52 (1999) 223±234 231
and CHb 2 is the bulk liquid phase hydrogen concentra- Summing up and rearranging one gets
tion (kmol mÿ3).
CHi 2 1 1 1 1
(3) Rate of transport to the catalyst surface.
jRH2 j KL a mC KC aC K
jRH2 j KC aC mC
CHb 2 ÿ CHs 2
kmol mÿ3 sÿ1
which gives us the macrokinetic rate law as a function
where KC is the liquid phase transfer coef®cient for of each individual step and accounts for the relative
catalyst particles (m sÿ1), aC the speci®c surface area weight of the ``resistances'' taken into consideration.
of catalyst particles (m2 kgÿ1), mC the catalyst loading The role played by the catalyst charge is clearly
(kg mÿ3) and CHs 2 is the liquid phase hydrogen con- shown as well as the ways by which physical diffusion
centration at the catalyst surface (kmol mÿ3). phenomena and chemical reaction intervene in deter-
(4) Rate of diffusion and reaction within the catalyst mining the global rate.
particle. Of particular relevance appears to be the effect of
catalyst particle size DP included in the terms related
jRH2 j mc Rs
kmol mÿ3 sÿ1 to the transport to the catalyst surface
where is the effectiveness factor (dimensionless) and 1
Rs is the microkinetic reaction rate at the surface KC aC
conditions (kmol kgÿ1 sÿ1).
Due to the virtual constancy of the liquid coreactant, and to the reaction with possible internal diffusion
one can often assume that the microkinetic rate law is limitation
linear in H2 concentration; that means 1
Rs KCHs 2 K
6
where K is the ®rst order kinetic constant aC
(m3 kgÿ1 sÿ1). Dp p
According to the ®rst order kinetics, the dependence As a matter of fact the speci®c surface area of the
of the effectiveness factor on the Thiele modulus is catalyst particle is directly related to the size, while the
described by the classical expression mass transfer coef®cient is usually estimated accord-
3 ing to the law
Coth ÿ 1 KC Dp
2 Sh 2 0:6ReD SC
1=2 1=3
s DLH2
Dp Kp
whence one gets
2 DH2 ;eff
KC aC 1 Dÿ2 ÿ1:5
p 2 D p
Having as limit values
and in an asymptotic form
! 1; ! 0; 1
1 D3=2
p 2 Dp
2
3 K C aC
! ; !1
From the other side, as for the chemical kinetic
resistance corrected by the effectiveness factor, two
the above equations can be put into the form
asymptotic dependencies are to be considered:
jRH2 j 1
CHi 2 ÿ CHb 2 3 D0p 4 Dp
KL a K
jRH2 j As a whole the resistance terms associated with the
CHb 2 ÿ CHs 2
mC KC aC catalyst load
jRH2 j 1 1
CHs 2
mC K KC aC K
232 G. Biardi, G. Baldi / Catalysis Today 52 (1999) 223±234
may show, against particle diameter, three regimes one gets from runs 1 and 2 (Dp40 mm)
depending on the asymptotic slope; namely 1
r Dnp rb 5:0344
s
KL a
where by assuming that the mass transfer coef®cient per unit
n0: reaction within catalyst is the determinating volume is constant over the range of considered
step, catalyst loads.
n1: internal diffusion is the determinating step, Furthermore,
n1.52: external diffusion is the determinating 1 1
step.
rC rC 1;2 8:431
s kg mÿ3
KC aC K
The relevance of gas±liquid mass transfer limitation
From the last run (Dp80 mm) one can therefore
depends, moderately in the bubble regime, on the
estimate the term relevant to external/internal diffu-
power dissipated per unit volume, and mainly on
sion and kinetic resistance rcrr; one obtains
the amount of catalyst loaded into the reactor.
Such considerations must be taken in due account
rC rr 3 17:062
2:024 2
when investigating experimentally a stirred slurry
rC rr 1;2 8:431
reactor; the basic experimental factors, for a de®ned
geometrical con®guration, being ®xed as: One can fairly argue that the controlling step shows
a resistance increasing linearly with catalyst size at
H2 pressure, least over the size range investigated.
catalyst size, This corresponds, as previously said, to internal
catalyst load. diffusion strongly limiting the reaction rate. In other
words,
3.1. Working example 1
rC rr rr
A classical example taken by the literature [41,42] K
can illustrate very clearly the analysis to be performed and
in order to arrive at the determination of the rate law
and at its controlling phenomena. CHi 2 1 1 1
Isothermal runs were carried out on a pilot slurry jRH2 j KL a mC K
reactor to hydrogenate an unsaturated fatty ester to the gives the rate law of hydrogen disappearance as a
corresponding saturated one. Three of them can be function of H2 partial pressure, through the Henry law,
summarized in Table 1. of gas liquid volumetric mass transfer coef®cient and
By interpreting the last column of catalyst load.
CHi 2 =jRH2 j No information is available to separate the effect of
microkinetic reaction rate and of internal diffusion
in terms of the law
within the catalyst due to the apparent asymptotic
CHi 2 1 1 1 1 1 value of ef®ciency against Thiele modulus. To such a
rb
rC rr
RH2 KL a mC KC aC K mC goal runs with smaller particle size are required.
Table 1
Experimental runs for a hydrogenation reaction
Run PH2 CHi 2 Catalyst size Catalyst load RH2 CHi 2 =jRH2 j (s)
(atm) (kmol mÿ3) (mm) (kg mÿ3) (kmol mÿ3 sÿ1)
[32] P.M. Haure, R.R. Hudgins, P.L. Silveston, AIChE J. 35 (1989) [37] L.L. Crynes, R.L. Cerro, M.A. Abraham, AIChE J. 41 (1995)
1437. 337.
[33] A.T. Castellari, P.M. Haure, AIChE J. 41 (1995) 1593. [38] J.L. Bravo, J.A. Rocha, J.R. Fair, Hydrocarbon Processing 65
[34] I. Mazzarino, G. Baldi, in: B.D. Kulkarni, R.A. Mashelkar, (1986) 45.
M.M. Sharma (Eds.), Recent trends in Chemical Reaction [39] I. Mazzarino, A. Santos, AIChE Meeting, Atlanta, USA, 17±
Engineering, vol. 2, Wiley Eastern New Delhi, 1987, 21 April 1994.
p. 181. [40] I. Mazzarino, A. Santos, G. Baldi, International Conference
[35] S. Irandust, B. Andersson, Catal. Rev.-Sci. Eng. 30(3) (1988) ANIMP, Ancona, Ottobre, 1994, p. 373.
341. [41] W.A. Cordova, P. Harriot, Chem. Eng. Sci. 30 (1975) 1201.
[36] A. Cybulski, J.A. Moulijn, Catal. Rev.-Sci. Eng. 36(2) (1994) [42] H.S. Fogler, Elements of Chemical Reaction Engineering, Int.
179. ed., Prentice-Hall, Englewood Cliffs, NJ, 1992.