STATIONARY CATALYTIC KINETICS VIA SURFACE

CONCENTRATIONS FROM TRANSIENT DATA

METHANOL DEHYDRATION

K. KLUSkEK* and P. SCHNEIDER

In&Me of Chemical Process Fundamentals, Czcchoslovak Academy of Sciences, 16502 Prague CSuchdol,
c7&choslovakia
(Aecrgted 20 March 1!82)

Ahdrsc-A novel approachto the analysis of the transient data from CSTRis ilhwtratcdon the catalyticdehydration
of methanol. The method allows to determine adsorbed amounts of reaction eomDooeotsunder reaction cooditioos
and it is appliilc in eases where at least one reaction compcoaot is not (or slighly) adsorbed. Beenuse new types
of data can bc obtained in this way a deeper discrhinatioo between rival kioetic models is possible. The method
oeroh also determination of total cooceotratioo of active sites on the catalyst surface. Comparison of transient
bata analysis with the steady-state results is presented.

INTRODUCTION utilized up to now, namely, the determination of ad-

In applied catalysis, the kinetic studies arc usually pcr-
formed in order to obtain rate expressions enabling
simulation of catalytic reactor behaviour. It is obvious
that those rate cxprcssions are the more valuable the
bcttcr they express the true reaction mechanism. Usu-
ally, stcady+tatc data from isothermal laboratory reac-
tors arc compared with sets of rate expressions
gcncratcd for dilfcrcnt assumed reaction mechanisms. In
this way, a small group of statistically indistinguishable
rate equations is usually obtained among which no fur-
ther discrimination is possible due to the inherent
experimental uncertainty of the data. At this point,
measuring at dif[erent temperature levels or increasing
the number of experimental data in the most sensitive
regions and/or increasing the experimental accuracy can
be of help. Another possibility is to use experimental
information of other kind. Such information can be
obtained, e.g. from kinetic measurements performed
under transient (unsteady-state) conditions. Most
frequently, the response of a laboratory catalytic reactor
is evaluated, following a perturbation of the reactor
steady-state. Different types of perturbations have been
used in this respect, viz. change of reactor feed-com-
position, change of feed-rate. temperature change etc.
(for review see Rcfs. [1,2]), For evaluation of the tran-
sient response data two basic approaches are used: (a)
extraction of qualitative information on reaction
mechanism from the shape of the response curves; (b)
quantitative comparison of experimental responses with
responses generated for different kinetic models. In the
latter case it is essential that the reactor flow pattern is
simple enough, so that unsteady-state material balances
for all reaction components can bc formulated.
There appears another way of analysing the transient
response data, the potential of which has not been fully
*Author to whom corrcspondeoeeshould be addressed.
1523
sorbed amounts of reaction components under reaction
conditions. The prerequisite of this approach is simple
stoichiomctry of the catalytic reaction in which at least
one of the reaction components is not adsorbed. In spite
of this constraint, great many reactions can bc analyscd
in this way. The method will, however, fail if reaction
components will adsorb not only on catalytic active sites;
in these eases there exist no simple relation between
reaction rate and (total) surface coverage.
We shall illustrate this approach on gas phase dchy-
d&ion of methanol (140T, atmospheric pressure)
catalyscd by a macmreticular sulphonated styrenc-
divinylbcnzcne copolymer (I)
2 C!HaOH+(CH,kO + H,O.
(4 (E) (w) (0
(In this reaction dimcthyl ether (E) is the unadsorbcd
component-see further). Methanol dehydration was
studied in a continuous stirred tank flow reactor (CSTR)
with vibrating piston. In the reactor used, the ratio of
catalyst particles to gas phase volumes was about 0.11.
i.e. high enough to permit obtaining meaningful transient
kinetic curves,
Three kinds of experimental data were obtained: (a)
start-up transient response curves following the in-
stantaneous replacement of inert feed-gas (nitrogen) by
nitrogen-mcthanol4methyl ether-water mixture with
varying concentrations of components; (b) steady-state
data for different feed-compositions and rates; (c) shut-
off transient curves following the instantaneous cut-off
of reaction components in tbe reactor feed and flushing
of the reactor with nitrogen.
Cntdyst. Macroreticular sulpbonated styrenedivinyl-
benzene copolymer (25% divinylbenzene; VI?SPL, Pardu-
1524 K. Kr.usiiCa~and P. Scu~sr~ss
=.
. ing the step-change reactor response with the theoretical
Fig. 1. Reactor scheme.
hick) with particle size 0.32-0.63 mm was used. Sur-
face area (BET) 61 m*/g; pore volume 0.584cm3/g.
The absence of intraparticle diffusion e&& was verified
experlmcntally by changing the particle size.
Reactor. The CSTEt reactor with vibrating piston (see
Sunderland[3]) is schematically shown in Fig. 1. The
total reactor volume was about 15 cm3, the volume of
catalyst charge approx. 1.5 cm3. The piston 1 was driven
through a piston rod 2 by means of a commercial loud-
speaker @Ohm, 1OW) fed by amplified signal with
frequency 20 Hz from a tone generator. The amplitude of
piston reciprocation was 4 mm. The catalyst (about 1.1 g)
was placed in eight cylindrical holes 3 communicating
with the piston cylinder 4 via channels 5. The main feed
inlet 6 was below the piston; outlet of the reaction
mixture 7 was at the top of the reactor. Part of the inert
gas feed 8 entered the reactor through the piston rod
sheath 9, thus preventing backtlow and possible conden-
sation on the cool part of the piston rod. The reactor was
placed in an electrical resistance oven with temperature
control +O.lC (thermocouple 10). The low volume feed-
and outlet-lines made from stainless steel capillaries (i.d.
1.6 mm) were kept at 120-140C by electrical heating
tapes. Ideality of reactor mixing was verihed by compar-
one. The absence of external mass transfer limitation
was checked by changing the piston frequency iu steady-
state runs.
Trunsienf run. Before the start of the run the reactor
conditions were stabilized under nitrogen Bow (inlets 6,
8). At the beginning of the start-up period part of the
entering nitrogen 6 was replaced by a stream of gaseous
methanol (or a mixture of methanol with reaction
products) in such a way that the total volumetric (molar)
feed-rate was unchanged. Total feed rate varied between
0.08-1.1 cmls; i.e. the mean residence time was l&150 s.
(The amount of nitrogen entering through port 8
represented always 20% of the total feed-rate). The
reaction mixture from the outlet 7 was periodically
analysed by gas chromatography. After the reactor
steady-state was attained (about 1-3hr) the shut-off
transient was initiated by replacing the feed of the reac-
tant 6 by the same feed-rate of nitrogen. The gas mixture
leaving the reactor 7 was again analysed periodically.
The course of inlet and outlet reactor concentrations is
illustrated in Fig. 2.
Chronatographic analysis. The reaction mixture was
separated at 180C in a 50 cm column (i.d. 2 mm) packed
with equal amounts of Spherocarb (80/120mesh) and
Porapak P (SO/l20 mesh). Hydrogen (20 cm3/min) was
used as carrier-gas; detection was by thermal conduc-
tivity. Sample composition was determined from peak
areas using calibration factors. The duration of the
analysis was about 2 min. Through the use of a special
sampling-storing valve[4] (0.2cm3 samples) it was pos-
sible to analyse the reaction mixture in very short time

Cl
0 m32030405060708090
t.min

Pi. 2. Time profiles of reactor-feed (a) and autlet (b) com-

position (0. CD.@, l denotes methanol. dimethyl ether, water
and nitrogen, respectively).
 balance (1)

RA = d( W/FY). (1)

Because in reaction (I) the total number of moles is not

:
x
Fig. 3. Steady-state methanol consumption rates. Feed com-
position (mol percent) methanolMiiethy1 ether/water/nitrogen:
1, 8010/0/20;2, W201012Wk~~wo/20; 4 W0/20/20; 5,
intervals, independent on the length of chromatographic
analysis.
From the data obtained during the steady-state periods
of the runs, methanol consumption-rates, R,+, were cal-
culated using the steady-state form of the reactor mass
changed, x can be expressed as x = (PA- pA)/pAo, me
obtained results are shown in Fii. 3 for feeds with
ditTerent composition. The equilibrium conversion of
methanol dehydration, cakulated[5] for the most un-
favourable cases (i.e. runs with highest concentration of
products in the feed) is still about 90%; therefore, the
reverse reaction is neglected in the following analysis.
Using @ experimental points (RA, pA. pE, pw), the
adequacy of 6 rate equations was verified by nonlinear
regression with sum of squared deviations between
experimental and calculated RAs as the objective func-
tion (s). In developing these equations it was assumed
that under steady state conditions the ad-
sorption/desorption steps are very rapid (equilibrium
steps) and the rate determining step is the surface reac-
tion. In view of the previous results [6] we postulated the
existence of only one kind of active centers on which
methanol is adsorbed with dissociation. Concentrations
of adsorbed species, ql (i = A, E, W), and of vacant
sites, SZ,,can be expressed, then, as
uKAFA~p
qA = 1+ 2(KApA)* + &pB + Kwpw (2)

Table 1. Rate equations

Model Surface reaction rate Rate eauation

1 r=kq2 (6) (kL2) KApA / [l + 2(K$Qos5 + KKPK + %%I2 (12)
A

2 r = k $ qf pA (7) (kL3) K,P; / [l + ~(K,P,)"' (13)

+ KEPE + %%J3
22 (ki4, K,p; / [l + 2<KApA)o's + KKpE +
3 r = k qA qf i+, (8) (14)
'tupw14
2
4 r = k s, qf (9) (kL3) KApA / [l + ~(K,P,)"~ + %PE + K"+13 (15)

5 r = k qA qf (10) (kL2) (K,P,)-~ , [l + 2(KAPA)o'5 + spE + *I2 (16)

6 r=kqA (11) (kL)tKApA) o-5 / [l + 2(KA+,)o-s + ~PK + K+$l (17)

Table 2. Optimum oarameters sets

l.loael Rate KA Kw s
KE min
+
cons t&t (l/kPa) (umol/g El)2

1 403.0 1.46 x 1O-3 1.68 x LO-' 3.14 x 10'2 2.00

2 12.7 5.61 x 10-l 1.68 x LO-' 1.13 x 10-l 1.23

3 20.5 2.54 Y 10-2 6.23 x 10 -6 2.41 x 10-2 1.32

4 592.0 1.40 x 10-3 2.14 x lo-' 1.67 x 10-2 4.17

5 275.0 2.58 x 10-l 1.67 x 10-l 4.28 x 10-l 4.64

6 99.6 1.05 x 10-l 3.25 x 10-l 1.50 x 101 5.22

+First te,.-X in paranthesis in the rat0 eqUatiOn naEratOr (Table 1). DiEbMlSiOn
follows from surface reaction rate equation (Table 1); r, q, pA expressed in

wuol/g.s, pmol/g, kPa, resp.

1526 K. KWSMBKand P. !Scmmme~

LKap, 8 = Wqdt). (24)

= = 1+ ~(X~A) + Kgp~ + &pw (3)
Then, the component mass balance have the form
L&p
qw = I+ 2(K_~_4)~+ K&z + Kw,,, (4)

(i=A,E, w). (25)

e=L-a-qa-qw (5)
The considered alternatives of rates of surface reac-
tions, r, are summarised in Table 1 together with the.
resulting rate equations. Tabk 2 presents the optimum
sets of rate constants, adsorption coefficients, K,, and
minimum S (&&.
Through application of the Beale statistical dis-
crimination test171 it can be concluded that the first 3
mechanisms are statistically indistinguishable wbereas
representation of experimental data by the remaining
rate equations is significantly worse. In all of the ac-
ceptable mechanisms, rtdswption of dimethyl ether is
negligible (KS + 0).
(ii) Transient data
If the reactor operating in the steady-state (either with
zero or linite conversion) is perturbed, at time f = 0, by a
step-change in the composition of feed, such that after
the perturbation the molar feed-rates of components
equal R and the feed-composition is characterised by p?
(i = A, E W), a new &ad&state IS achieved only at
infinitely long time. From the practical point of view,
however, the transient levels off at some finite time t*.
During the transient period O-t*, the mass balances of all
components can be formulated using the following terms
for molar amounts of components i = A, E, W: reactor
inUow (A) and outflow (SB,):
& = HP 1.pi(t) dt (19)
reaction source
%* = w Rrdt (20)
amount present in the reactor gas-phase at t = 0 (S,) and
t = P( 8,)
91 = PJ(O)VI&T (21)
% = p,(P) VI&T (22)
amount adsorbed on the catalyst surface at t = 0 (99 and
t = t*(Y)
4 = Wq,@) (23)
iEquations (6)_(V) appear ia Table 1.
Because Fps are known and the time profiles pi(t) can
be measured, it is possible to evaluate terms .& Q, gJ
and & Terms 9, and %+equal zero in the start-up and
shut-off transient runs, respectively. Further sim-
pliication results from the stoichiometry of reaction (I)
which couples the rates of formation RI appearing in
terms %,: %._,= - 2%= = - 2Zw. From the an$ysis of
steady-state data (&do, see Table 2) as well as from
the vefy ra$id dimetbyl ether transient (Fig. 2) it is
obvious that its adsorption is negligible in comparison
with methanol and water, i.e. 9~ = 9~ = 0. Thus, the
mass balances form a system of three equation; with
three unknowns (for the start-up run: WAgA, %iA,%; for
the shut-off run: Cg,, QtA,SW) from which the a&orbed
amounts of methanol and water (for the start-up run
q,,(t*), qw(t*); for the shut-off run qn(0). qw(0)-see
eqns (23) and (24)) can be evaluated for the composition
of the gaseous reaction mixture in the corresponding
steady-state. If the start-up and shut-off runs follow
immediately one after the other (as shown io Pig. 2), and
no irreversible adsorption takes place, then
qAt) starCup= - qr(0).hut-oS7
(i=A, IV). (26)
Using the procedure described above the adsorbed
amounts qr and qw were evaluated for the start-up and
shutoff tiansients corresponding to steady-state rates RA
shown in Fig. 3. In some cases, eqn (26) was not satisfied
within f 15 per cent due to experimental errors; such
data points were rejected.
In all the three favorite mechanisms resulting from the
analysis of steady-state reactor data (eqns 12-14) the
same multicomponent adsorption isotherm applies, viz.
eqns (2) and (4). To verify its validity, the adsorbed
amounts of methanol and water under reaction con-
ditions (qA, qw), obtained in the above described way
from the analysis of start-up and shut-off transients,
were fitted simultaneously by eqns (2) and (4). The
obtained adsorption equilibrium constants of water and
methanol (K..+= 8.83 X lo-kPa_, K,,/ =3.08x
lo- kPa-) agree reasonably well with the values given
in Table 2 (model 1). Even the total concentration of
active sites L = 0.52 mmol/g) corresponds well with sur-
face exchange capacity (0.32 mmol/g) obtained by rate
determination of the condensation of phenole and
acetone[8]. Figure 4 compares the experimental ad-
sorbed amounts qA, qw with the calculated adsorption
isotherms (eqns 2 and 4). Due to the weak dependence of
qw on pa, the calculated water adsorption isotherms for
the highest and lowest values of pa achieved in experi:
mental runs (57.9 kPa and 8.8 kPa.resp.) do not differ

.~
0
Pi. 4. AdEiolptionisothemls
20 40
o.kPo
of methanol (qAvs p,j Ad water (qw
vs pw). Water i~~~tb~nnsI,2 cabinted from eqn (4) for pA =
8.8 kPa (1) and p,, = 57.9 kPa (2). Methanol isotherms 3. 4 Cal-
culated from eqo (2) for pw = 10.2kPa (3) and for pw = 45.3kPa
(4). Points: experimental values (0, water; 0, methanol).
widely. ft can be seen that the experimental qw points
fall around the two limiting calculated curves 1 (for
pA = 8.8 kPa) and 2 (for PA = 57.9 kPa). The methanol
adsorption is much lower than that of water: therefore,
also in this case, the calculated methanol isotherms qA vs
Fig. 5. Surface teaclioa rates: a, r = kqAz;b,
pA is not strongly affected by the gas-phase concen-
tration of water (see lines 3, 4 in Fig. 4 for limiting
experimental water partial pressures 10.2kPa and
45.3 kPa: resp.).
1527
Thus, the evaluation of adsorbed amounts of reaction
components frdm the reactor transients supports the
description of adsorption equilibrium used in the three
favorite reaction mechanisms (12)-(14).
It is obvious from Table 1 that these mechanisms diier
only in the description of the rate determining surface
reaction (eqns 68). Having available the methanol reac-
tion rates, R,, and the amounts of adsorbed reactant (qA)
as well as of vacant active sites (4, = L - qA - qw) it is
possible to verify the form of the expression for the rate
of surface reaction in much the same way as in homo-
geneous reactions, e.g. graphically. From the depcn-
dences for the three favorite mechanisms: R.. vs qA2
(Fig. 54, RA vs pAqA2qt (Fig. 5b) and RA vs pAq,+*e*
(Fig. 5c), only the first one fulfills the expected linear
relationship, thus demonstrating that the rate eqn (6) is
the most plausible one.
The rate constant of the surface reaction determined
from the slope of the linear R, vs qr2 plot, k=
1.83 g/mmol.s, is not too diflerent from the value k=
1.49g/mmol.s which follows from the analysis of the
steady state rate data (ML*= 0.403 mmo1lg.s; see Table 2)
and L = 0.52 mmol/g determined from adsorbed amounts
of methanol and water (qA, qw) under reaction con-
ditions.
r = kpAqAzq,;c, r = kpAqAzq,+=.
rmlMloN
A,& W methanol, diiethyl ether, water
F molar flow-rate
k rate constant of surface reaction
1528 K. KLUSAEEK and P. SCHNEIDER

K* adsorption equilibrium constant REFERENCE9

L total concentration of active sites [I] Kobayasbi M. and Kobayasbi H., CutuL Rev. Sci Engng
partial pressure 197410 139.
PI
(21 Bennet C. O., CahL Reu. Sci Engng 1976 13 121.
P pressure [3] Sunderland P. and El Kanzi E. M. A., Aduan. Chem. Ser.,
4194s concentration of adsorbed species and of free Chem. React, Engng-ZI 19743 133.
active sites, resp. [4I KlusUek K.,and Schneider P., J. Chmtnatogr. in press.
rate of surface reaction 151KlusB&k K. and Schneider P., Chem. P&m. 198030 81.
[6J Thsnh L. N., Setinek K. and Befinek L., COILCzech Ckem.
R,' rate of methanol consumption Commun. 197237 3878.
f time [7] Hanfil V.. Mitscbka P. and BerAnek L., 1. Caraf. 1%9 13
W catalyst weight 435.
X methanol conversion [SI Jeidbek K., CON.Czech. Chem. Commurr 197944 2612.

superscript
0 reactor feed