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Review of Measuring Methods and Results in Nonviscous Gas-Liquid Mass Transfer in Stirred Vessels
Review of Measuring Methods and Results in Nonviscous Gas-Liquid Mass Transfer in Stirred Vessels
3, 1979 357
REVIEW
A search has been made for relations between published results about gas-liquid mass transfer in stirred vessels
filled with water. The dynamic gassing-out method, the sulfite method, the separate determinations of A and k,
as well as a number of other experimental methods were judged on their own merits. Most methods appear to
be of limited applicability, and the sulfite method is even more restricted in this respect. Correlation of the various
reports on mass transfer is possible with power per unit volume and gas superficial velocity. This requires a rigid
differentiation between water without and water with ions in solution. Among the equipment variables it is in particular
the position of the sparger which appears to be of influence.
complicated models for diffusion (Heineken, 1970, 1971; Corrieu et al. (1976) reported about it. This method
Linek, 1972, and Linek et al., 1973). particularly requires accurate modelling of gas phase
It is pertinent to ask whether one really has to perform mixing for correct interpretation of measured OTR and
all these extensive procedures. Van t Riet (1975) has CL values.
demonstrated that in Van de Sandes model the ultimate Separate Determination of A . The separate deter-
error in KLA < 6% for T~ I l,/kLA, while Lineks model mination of A is another measuring method, and may
(1972) implicates an error <3% for T~ 5 1/5kLA. By comprise light transmission techniques (Calderbank, 1958;
adhering to these limits, it is possible to measure accurately Lee and Meyrick, 1970). Lockett and Safekourdi (1977)
enough a usually acceptable maximum value by means of have inspected the reliability of the method more closely.
commercially available electrodes with r p = 2 or 3 s to kLA To obtain a representative average A value, determinations
= 0.1 sd. One need not employ models like those of Linek in various places in the vessel are necessary. The design
and Heineken until these limits are exceeded. of equipment with a view to determine only the kLA value
A response lag of the electrode also arises where the mass would be a rather complicated matter.
transfer boundary layer is of importance for the Clark cell. A can also be calculated by measuring holdup (t) and
In stirred vessels with the Clark cell in the impellar dis- bubble diameter (db).
charge flow the influence of this layer can nearly always
be neglected. For information on mass transfer boundary (5)
layers and probe response, see Robinson and Wilke (1973),
Dang et al. (1977), Linek and Benes (1977), and Linek and It is possible to determine db photographically by suction
Vacek (1976, 1977). and taking measurements (Kawecki et al., 1967). Direct
When the electrodes used respond very rapidly, mea- suction and measurements in a capillary have been per-
surements may give far too high values. Linek et al. (1973) formed by Reith and Beek (1970), Todtenhaupt (19711,
have attempted to explain this by pointing out that gas and Van de Sande (1974). The extent to which a given
bubbles are also recorded so that the electrodes have too sample is representative is a major, if not insurmountable
great a response. This claim has been worked out in more problem, particularly, because samples which vary in
detail by Votruba and Sobotka (1976) and Votruba et al. density are sucked up, resulting in a selection of bubbles
(1977). according to size by pressure distribution at the capillary
Quite a different problem is presented by the gas phase entrance. Besides, dissimilarity in velocity between
residence time. If this value is not much smaller than bubbles and liquid makes it impossible to suck up isoki-
l/kLA, measuring results can be affected a good deal. The netically. One can also determine d b in a direct manner
reason is that in such a case CGfrom eq 2 can no longer photographically, as done by Valentin and Preen (1962)
be regarded as constant. Dunn and Einsele (1975) have and Koetsier and Thoenes (1972).
reported an extensive analysis with correction graphs. Pros and cons are similar to the light transmission
A further elaborated model has been described by Dang technique. Moreover, this method is rather laborious
et al. (1977). It appears from these models that a t high (Landau et al., 1977).
kLA values corrections are often rather rigorously required Sulfite Method. This method is based on the reaction
and that, as a consequence, measurements will lose much of absorbed O2 with Na2S03. Copper and cobalt ions can
of their accuracy. Problems become more serious at larger be used as catalyst. Mostly, there is a concentration range
vessel diameter especially a t low superficial gas velocity in which the reaction proceeds so rapidly that the dissolved
values. T G is given by oxygen concentration in the liquid is nil. This implies that
the reaction largely takes place in the boundary layer and
tV - EHt that the driving force is larger than if there were only
TG=--- (3)
us.y4?rT2 us physically controlled absorption. The apparent kLA thus
determined should then be converted into the kLA for that
The / u s ratio is reasonably invariable at defined power absorption.
per unit volume and us values (Smith et al., 1977). For On application of the sulfite method this causes diffi-
this case, as eq 3 shows, T G becomes proportional to H , culties. The conversion makes it necessary to determine
which means that there is a maximum H, value up to which both the reaction rate constant kR and the order of the
kLA can be measured using this method. reaction, and, as appears from the literature, problems arise
Smith et al. (1977) have worked out an experimental here. As early as 1941 Fuller pointed out that kinetic
design in which after gassing out the oxygen all N2bubbles values respond quickly to any changes in the catalyst
are allowed to escape, and incorporated this in a model. concentrations. Also, Linek and Mayrhoferova (1970) and
However, the holdup has to be built up, which together Linek and Tvrdik (1971) point out that k R values cannot
with changes in concentration in the gas phase causes both be adopted from the literature because these are rather
A and C G to become functions of time. Therefore, this dependent on the purity of the product. This is related
method does not offer many advantages. to the fact that additions may well distort k R . Onken and
OTR and CL Measurements. Especially in fermen- Schalk (1977) have demonstrated that the addition of 5%
tation systems, OTR is determined by measuring the glycerin reduces hR by a factor of 25. (The great influence
oxygen concentration of the air inflow and air outflow. At which additions may have could account for the extremely
the same time, CL is measured with a Clark cell. It is then large role of viscosity as observed by Paca and Gregr
possible to establish kLA directly with eq 1. (1977).)
The order of the reaction in oxygen may vary from 1at
(4) a partial pressure of 1 atm to 2 at low partial pressures,
as demonstrated by Reith and Beek (1973). Articles by
Notably in systems where these variables are also mea- Reith (1970) and Reith and Beek (1973) show that due to
sured for other reasons, it is, therefore, easy to determine various problems results can be interpreted incorrectly.
kLA. Finns review (1967) mentions some advantages of I t is obvious that on application of the sulfite method,
this method, about which remarkably little has been reaction kinetics are difficult to determine and are much
published elsewhere. Recently, Mukhopadhyay (1976) and dependent on the concentrations and purity of sulfite and
Ind. Eng. Chem. Process Des. Dev., Vol. 18, No. 3, 1979 359
catalyst. They should, therefore, be established accurately As a model fluid it is only representative for strong ionic
for each single set of experiments. If in a publication such solutions.
data are lacking or other articles lay under contribution, Among the methods that involve separate determination
one has to interpret results very cautiously. To a somewhat of A and kL the light transmission technique is the most
lesser extent, this also holds for a mere comparison of, for reliable. The degree to which measurement is repre-
example, vessel parameters in one set of experiments where sentative and determination of kL are factors that influence
results need not be converted into physically controlled accuracy. Determination of A from bubble size, measured
kLA values. In the latter case, one should take extremely with suction into a capillary, can lead to difficulties due
good care that the liquids to be prepared are all of the same to unrepresentative samples. Direct determination using
composition. bubble size distribution measured photographically is
An additional problem is that for the sulfite technique tedious. Determination of kLA from OTR and CL is not
to be successful, high ionic concentrations (1 to 2 M) are well represented in the literature. It is a simple, reliable,
required. This implies that as compared to distilled water and straightforward method when the correct model for
A is much greater and that kL, too, can be affected. gas phase mixing is applied.
Therefore, the results are only applicable to one particular kLAResults
liquid, and cannot be simply extended to any other Power per unit volume and gas superficial velocity are
nonviscous liquid. On evaluation of the hL values re- major correlation coefficients for hLA. Therefore, equa-
ported, the influence of ions will be discussed in more tions of the following type are frequently found in the
detail. literature.
Finally, attention is called to an interesting observation
by Prasher (1975), who claims that while the specific
contact area exerts the same influence throughout the
vessel in case of an extremely rapid reaction, physically
controlled absorption varies according to the locally widely where P = gassed power input, V = liquid volume, U S =
differing degrees of turbulence and local bubble size. In gas superficial velocity, K = constant, and CY and /3 are
this connection, the two contact areas could not be exponents. When P is omitted, an equation like the one
compared readily. following can usually be adopted.
Other Measuring Methods. In addition to the sulfite kLA = KNalDaz(~S) (7)
technique, a number of other reactions have been applied
to assess mass transfer. The most commonly employed where N = stirrer diameter.
involves the measurement of C02,as performed by Mehta It is nearly always possible to convert eq 7 into eq 6. The
and Sharma (1971) for various liquid compositions. values found for CY and ,8 show a fairly great variation: 0.4
Robinson and Wilke (1974) combine C 0 2 absorption with < CY < 1 and 0 < p < 0.7. It is not unusual for the K value
dynamic gassing-out in order to permit a determination to remain unmentioned. For that matter, it correlates a
which they claim to be more accurate than the sulfite great deal with ct because P / V = lo3 - lo4. If a t a given
method (Prasher (1975) has criticized this approach). kLA and P/ V, a relatively small change is introduced into
CY,it causes great change in K.
In principle, as a reaction C 0 2 absorption is better Interpretation of the literature is, furthermore, ham-
controllable than the sulfite method. Yet some of the pered by two factors. (1) Where liquids of different ionic
objections inherent in the sulfite method (reaction kinetics strength, as in the case of sulfite subjected to the gass-
should be known beforehand and there remains an in- ing-out method, are used, any attempt to correlation af-
fluence of ions on A and hL) continue to exist. fords dissimilar results obtained under seemingly the same
In fact, a whole range of techniques can be employed. circumstances. (2) Relatively much store is set by the
Hydrogenation reactions, used by Van Dierendonck (1970), values of CY and 6. To what extent these can be varied
are found very suitable for the design of a hydrogenation without affecting the outcome significantly will be dis-
reaction. Several other reactions have been applied by cussed in more detail in the section on hLA. For that
Mehta and Sharma (1971) and Bossier et al. (1973). Miller reason, much consideration will be given here to the value
(1974) applies continuous C 0 2 absorption as a gassing-out of kLA itself, as it occurs in liquids of different ionic
method. strength.
This review of experimental methods to determine hLA Measurements in Ion-Free Water. First measure-
certainly does not pretend to be complete. Many methods ments in distilled water and tap water will be compared.
not mentioned here have been designed but usually these The salt concentration in tap water is approximately 0.02
are modifications of the techniques described, which means M, which causes no more than a minor increase in hLA (by
that they also have several of the reported advantages and 510%) over distilled water. In the following, these media
disadvantages in common. will be designated as pure water.
Conclusions Regarding Experimental Methods. The kLA in pure water has been determined in several
Dynamic gassing-out is a simple and reliable way of manners. Calderbank (1958,1959) makes use of the light
measuring mass transfer on the condition that probe transmission techniques to find A . Kawecki et al. (1967)
response time and gas phase residence time meet certain and Valentin and Preen (1962) have calculated A from the
requirements. Commercially available electrodes, with measured bubble size and holdup. In that case, kL remains
probe response time of 2-3 s, allow measurement up to kLA to be determined separately. Values reported in the lit-
= 0.1 s-l even without response models. Using these re- erature for hL in pure water vary from 1 to 6 X (see,
sponse models one can measure up to values several times for example, Calderbank and Moo-Young, 1961; Reith and
higher. The influence of gas phase residence time can be Beek, 1968; Linek et al., 1970; Valentin and Preen, 1962;
estimated simply from eq 3. Li et al., 1965; Robinson and Wilke, 1974). The k L value
Severe difficulties will be encountered using the sulfite used in the calculations in this review is 4 X which,
method. Even with the present knowledge reaction ki- judging by those mentioned in the literature, would appear
netics are still evasive and in any case the numerical values to be the best estimate. The most recent publications
would have to be established for each single experiment. reporting the determination of the kLA with the aid of the
360 Ind. Eng. Chem. Process Des. Dev., Vol. 18, No. 3, 1979
10-11
2.10
- 2 11
4.10' io3 + E (~rn-3)
Figure 1. Literature data and correlation equation at low superficial
gas velocities in pure water. Figure 3. Literature data and correlation equation at large superficial
gas velocities in pure water.
Van t Riet, K., Boom, J. M., Smith, J. M., Trans. Inst. Chem. Eng., 54, 124 Zlokarnik, M., Chem. Ing. Tech., 47, 281 (1975).
(1976). Zwietering, Th. N., Ingenieur, 75, 63 (1963).
Votruba, J., Sobotka, M., Eiotechnol. Bioeng., 18, 1815 (1976).
Votruba, J., Sobotka, M., Prokop, A,, Eiotechnol. Bioeng., 19, 435 (1977). Received for review J u n e 26, 1978
Westerterp. K. R., Van Dierendonck, L. L., De Kraa, J. A,, Chem. Eng. Sci., Accepted December 20, 1978
~.
18. 157 119631.
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ARTICLES
A workable method to calculate diffusion effects within pores of a catalyst pellet, for a complex reaction, has been
developed. Suitable rate equations have been selected to describe the rate of ammonia synthesis reaction over
catalysts of different make. This, in conjunction with the method developed to calculate the effectiveness factor,
has been used to obtain a mathematical model for ammonia synthesis reactors. Reactors having adiabatic catalyst
beds with interstage cooling as well as autothermal reactors have been considered. Plant data and simulation results
are, generally, in very good agreement.