510 zyxwvutsrqponmlkjihgfedcbaZYXWVUTSRQPONMLKJIHGFEDCBA zyxwvutsrq

zyxwvuts
Ind. Eng. Chem. Fundam. 1984, 23, 510-512

(150) Prydz. R.; Straty, G. C. Natl. Bw. Stand. Tech. Note 1970, No. 392.
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(London) 1908%205, 99. Accepted April 3, 1984

COMMUNICATIONS

Gas-Liquid Mass Transfer Data in a Stlrred Autoclave Reactor

A novel experimental technique for measuring volumetric mass transfer coefficients in a stirred autoclave reactor
is proposed. The method is based on pursuing the instationary pressure drop due to mass transfer under isochoric
conditions. The usefulness of the technlque Is demonstrated for the Fischer-Tropsch slurry system.

In a recent communication to this journal, Huff and and interpretation. However, when determining the ki-
Satterfield (1982) gave a detailed description of a me- netics of gas-liquid-solid catalyst systems, rate data may
chanically stirred autoclave which was used to study the be falsified by mass transfer limitations. In the case of
Fischer-Tropsch synthesis in a slurry phase. As pointed Fischer-Tropsch synthesis it is particularly the mass
out by these authors, in such an experimental unit all transfer a t the gas-liquid interface which may be impor-
phases are completely mixed under appropriate operating tant. In a study of this synthesis on a reduced fused
conditions, which facilitates and simplifies data evaluation magnetite catalyst, Satterfield and Huff (1982) showed
0196-431318411023-051l$Ol.50/0 0 1984 American Chemical Society
 zyxw
zyx
zyxw
Ind. Eng. Chem. Fundam., Vol. 23, No. 4, 1984

and a t a low gas flow rate (all valves VI to V4 open) the

liquid was saturated with gas a t atmospheric pressure.
511 zyxwvutsrqpo

zy
After about 30 min valves V3 and V4 were closed. Then
the pressure in the vessel was increased to the desired
value. After stopping the stirrer and closing valve VI, valve
V3 was opened. If temperature equilibrium was rees-
tablished (after 20-50 s) the stirring was started and the
pressure was recorded. The desired stirrer speed was
reached in less than 0.5 s (90% was reached in about 0.2
8 ) . Without stirring, the pressure drop was around 0.1
kPa/s, while during the mass transfer measurements with
the stirrer in action the pressure drop varied from 4 kPa/s
at 300 rpm to 400 W a / s at 1300 rpm. Therefore, the mass
transfer rate before starting the stirrer is negligible.
The Henry constant defined by zyxwvutsrqponmlkjihgfedcbaZYXW
H e = p/cL* (1) zyxwvutsr
can be calculated from the pressure pf measured a t steady
state by
Pf - Pa VL
Figure 1. Experimental setup for isochoric measurements. He = --RT
PO - Pf vG
that in their autoclave unit mass transfer resistances were
significant below stirrer speeds of about 400 rpm. where pa is atmospheric pressure and pois the pressure
It is important to notice that the occurrence of mass a t t = 0 before starting the stirrer. VG and VL are the gas
transfer limitations influences product selectivity, i.e., the and liquid volumes, respectively. VG was determined
paraffii-to-olefi ratio. From the temperature dependency separately and included the pressure vessel, the connecting
of the observed rate data, Satterfield and Huff (1982) line, and the gas volume in the autoclave.
computed hydrogen mass transfer coefficients (kLa/(1- The mass transfer coefficient kLa is determined from
tc)). The purpose of this brief communication is to show the p vs. t curve. The governing mass balance of the liquid
that little modification is needed to determine mass phase is given by

zyxwvutsrqpo
trabfer coefficienb directly in autoclaves as described by
Huff and Satterfield (1982)and in less detail by Bauer and (3)
Dyer (1982)as well. In addition, solubility data of the gas
in the liquid phase can be obtained. The liquid phase concentration cL is coupled with the gas
The apparatus used in this study was a commercial 1-L phase pressure by
stainless st el autoclave of 80-mm diameter (Type 1220
t!
E. Haage ompany, Muhlheim/Ruhr). Stirring of the
(4)
liquid (slurry) phase was done by a magnetically driven
turbine agitator 48 mm in diameter. Thermowells were
installed to measure the temperature in the gas and liquid which upon integration leads to
phases. The autoclave was equipped with a number of
ports and valved for the gas inlet and outlet, liquid charging
gas, and liquid sampling etc. The autoclave was connected
with a highly resolving pressure sensor (Setra System Inc., Using the initial condition p = poat t = 0, it follows from
type 205/2)and a pressure vessel of 1 dm3 volume. The eq 1, 3, 4,and 5
experimental setup used for kLa and solubility measure-
CYPO - kLART
ments is given schematically in Figure 1.
The measurements are based on an isochoric method, ln-=a- t (6)

zyx
CUP-P VG
i.e., the pressure drop is monitored under constant-volume
conditions. The method requires exact temperature con- where
trol, i.e., the pressure vessel, the connecting line, and the 1
a=--+- vG

zyxw
autoclave must be kept a t the same temperature. The (7)
liquid in the autoclave was heated and the temperature He VLRT
was controlled by the electric furnace and temperature
controller supplied by the autoclave manufacturer. Using p = - +P-a - PI VGPO
this heating equipment, the temperature of the gas phase He VLRT
in the autoclave differed from that of liquid phase by 20 Hence, when plotting In I(apo- P)/(ap - @)Ivs. t the mass
to 30 K depending on the set temperature. Therefore, a transfer coefficient kLa = kLA/ VL can be obtained from
special device was constructed for heating the upper part the slope
of the autoclave and its cover. Thus it was possible that
gas and liquid in the autoclave could have the same tem- "G
perature. Also, the pressure vessel and the connecting line kLa = slope X -
aVLRT
were temperature regulated by separate controllers.
Measurements were done under conditions where the The method was employed to determine volumetric mass
various temperatures measured and controlled did not transfer Coefficients for the Fischer-Tropsch slurry system,
differ by more than 2 K. which was studied in the autoclave shown in Figure 1. As
The measuring procedure was as follows. The autoclave liquid, a molten wax (Vestowax SH 105, melting point
was charged with liquid (500 to 700 cm3). Under stirring about 105 "C)was used. The kLa values of various gases
512 zyxwvutsrqpo
zyxwvutsrq
Ind. Eng. Chem. Fundarn,, Vol. 23,No. 4, 1984

zyx
1/He

is small, Le., about 0.05 for the experimental setup used

and the systems studied.
a for Hz, Nz,
Figure 3 shows k ~ data CO, and COz as a
function of the stirrer speed. kLa increases strongly if n,
> 700 rpm. From a log-log plot of kLa vs. n, it is found
that

zyxwvuts
kLa a nS3.9*0,3 (11)
which is in agreement with Satterfield and Huff (1982).
However, the kLa values of the present study are smaller
! izyxwvutsrqponmlkjihgfedcbaZYXWVUTSRQPONMLKJIHGFEDCBA
than those reported by Satterfield and Huff. Obviously,
Figure 2. Experiinental data plotted according t o eq 6. Hydrogen a less effective impeller was employed by us. The dif-
mass transfer at various impeller speeds. ferences of kLa observed for the gases used are due to
differences in diffusivities. The Wilke-Chang correlation
(Wilke and Chang, 1955) and the empirical equation given
by Sovova (1976) were used to estimate the diffusivities.
These correlations give quite differing results. However,
log-log plots of kLa vs. D indicate penetration theory be-
havior for both sets of diffusivity estimations.
Acknowledgment
S.L. thanks the Alexander von Humboldt-Foundation.
Support from Deutsche Forschungsgemeinschaft is
gratefully acknowledged.
Nomenclature
A = interfacial area, cm2
a = specific interfacial area (referred to liquid volume), cm-'
c L = concentration of gas in liquid phase, mol/cm3
cL* = equilibrium concentration of gas in liquid phase,
mol/cm3
kL = liquid side mass transfer coefficient, cm/s
n, = stirrer speed, rpm
pa = atmospheric pressure, Pa
p f = steady-state pressure (at t
pi = liquid phase partial pressure, Pa
- m), Pa

p o = initial pressure (at t = O), Pa

R = gas constant, cm3 Pa/mol K

on stirrer speed.

zyxwv
Figure 3. Dependency of volumetric mass transfer coefficients (kLa)

zyxwv
T = temperature, K
t = time, s
V , = gas volume, cm3
VL = liquid volume, cm3

zyxwvutsrqp
were measured up to 6 MPa and temperatures ranging Registry No. HP, 1333-74-0; N P ,7727-37-9; CO, 630-08-0; COz,
from 180 to 280 O C . 124-38-9.

zyxwvu
In the following figures some typical result,s are given.
In Figure 2 experimental data for the H2-Vestowax system Literature Cited
(no catalyst present) are plotted according to eq 6 for three Bauer, J. V.; Dyer, P. M. Chem. f n g . Prog. Sepl 1982, 51.
Huff, G. A.; Satterfield. C. N. Ind. Eng. Chem. Fundem. 1982, 2 1 , 479.

zyxwvuts
impeller speeds at 220 "C. The partial pressure of the Peter, S.; Weinert, M. 2. Phys. Chem. (Frankfurt am Main) 1955, 5 , 114.
liquid wax phase ( p J was estimated from the Antoine Satterfield, C. N.; Huff, G. A. ACS Symp. Ser. 1982, No. 196, 225.
Sovova, H. Collect. Czech. Chem. Commun. 1978, 4 7 , 37 15.
equation using the constants reported by Sudheimer Sudheimer, G. Thesis, Technlsche Hochschuie Darmstadt, Darmstadt, FR
(1982). The Henry cofistants needed to calculate CY and Germany, 1982.
p from eq 7 and 8 are obtained from the final pressure Wilke, C. R.; Chang. P. AIChEJ. 1955, 1 , 264.
value by eq 2. They are in agreement with the data re- Fachbereich Chemie- Technische Stanislaw Ledakowicz'
ported by Peter and Weinert (1955). For instance, He =: Chernie Hubert Nettelhoff
1.80 X lo7 kPa cm3/mol was found for the CO-wax system llniversitat Oldenburg Wolf-Dieter Deckwer*
at 200 "C and 1.22 MPa while from Peter and Weinert's D-2900 Oldenburg, FRD
data a value of 1.84 X lo7 is calculated for 203 "C and the
pressure range 0.2 to 1 MPa. In addition, it should be Received for review August 29, 1983
mentioned that the kLa determination by the applied Accepted April 10, 1984
isochoric method was only slightly influenced by the exact
value of the Henry constant as the ratio
'Wi Technical University, Chemical Engineering Department, PL-90924
Wz, Poland