Kinetics of Hydroformylation of Ethylene in a Homogeneous

Medium: Comparison in Organic and Aqueous Systems

Raj Madhukar Deshpande, Bhalchandra Mahadeo Bhanage,
Sunil Sadashiv Divekar, Subbareddiar Kanagasabapathy, and
Raghunath Vitthal Chaudhari*
Chemical Engineering Division, National Chemical Laboratory, Pune411 008, I ndia
The ki neti cs of hydroformyl ati on of ethyl ene was studi ed usi ng HRh(CO)(PPh
3
)
3
and [Rh(COD)-
CI ]
2
/TPPTS catal yst i n tol uene and water medi a, respecti vel y. The rates were found to have a
fi rst-order dependence on the catal yst concentrati on. Si mi l ar trends were observed wi th respect
to parti al pressures of ethyl ene and carbon monoxi de, i n both sol vents. The di fference i n the
l ocati on of the maxi ma wi th respect to pressure i s due to the poor sol ubi l i ty of the reactants i n
water as compared to tol uene. The major di fference observed was a 1.5 order wi th hydrogen i n
tol uene compared wi th a fi rst order i n water. Rate model s were proposed to represent the data
observed.
Introduction
Hydroformyl ati on of ol efi ns i s an i mportant and
l argest scal e appl i cati on of homogeneous catal ysi s i n
i ndustry, used for the manufacture of C
3
-C
40
al dehydes
and al cohol s. Hydroformyl ati on of ethyl ene i s one such
exampl e l eadi ng to propi onal dehyde and n-propanol as
major products havi ng appl i cati ons such as sol vent,
i ntermedi ates i n the manufacture of pharmaceuti cal s,
pesti ci des, and perfumery products.
I t i s al so an i mportant step i n the new non-HCN route
for methyl methacryl ate manufacture (Schwaar, 1991).
Whi l e extensi ve work has been done on catal ysi s and
product di stri buti on/sel ecti vi ty i n hydroformyl ati on re-
acti ons, there i s l i mi ted publ i shed l i terature on the
ki neti c model i ng of hydroformyl ati on of ethyl ene. I n
thi s paper i nvesti gati ons on the ki neti c model i ng of
hydroformyl ati on of ethyl ene usi ng a HRh(CO)(PPh
3
)
3
catal yst i n an organi c medi um and a water-sol ubl e Rh/
TPPTS (TPPTS ) (tri phenyl phosphi ne)tri sul fonate so-
di um sal t) catal yst i n an aqueous medi um are reported.
The l atter case i s i mportant from the poi nt of vi ew of
separati on of products and catal yst, due to the l ower
sol ubi l i ty of propi onal dehyde i n aqueous medi um. The
reacti on i nvol ves si mul taneous absorpti on of three gases
wi th the catal yti c reacti on i n the l i qui d phase to produce
a si ngl e l i qui d product. A knowl edge of the i ntri nsi c
ki neti cs i s essenti al to attempt a systemati c anal ysi s of
the rol e of mass transfer i n such a system. Such a study
not onl y i s useful for the i mprovement of the catal yti c
system but al so provi des the basi c i nformati on for the
desi gn and scal e-up of sui tabl e reactors.
The ki neti cs of hydroformyl ati on of ol efi ns usi ng a
homogeneous HRh(CO)(PPh
3
)
3
compl ex catal yst has
been studi ed by many i nvesti gators (Deshpande et al .,
1988; Di vekar et al ., 1993). For hydroformyl ati on of
ethyl ene, however, the avai l abl e i nformati on i n the
l i terature i s scanty. A few reports descri be the ki neti cs
of thi s reacti on usi ng a supported Rh compl ex catal yst
(Arai et al ., 1975; Takahashi et al ., 1992). However,
on the i ndustri al scal e a homogeneous Rh compl ex i s
used, and hence i t i s more i mportant to i nvesti gate the
ki neti cs usi ng a sol ubl e Rh compl ex catal yst. Pol i evka
et al . (1980) have studi ed the ki neti cs of hydroformy-
l ati on of ethyl ene usi ng homogeneous Rh(CO)Cl (PPh
3
)
2
but i n a very narrow range of condi ti ons. They observed
that the rate versus ethyl ene pressure curve passes
through a maxi mum. The present work deal s wi th the
study of the ki neti cs of hydroformyl ati on of ethyl ene i n
an organi c medi um usi ng a HRh(CO)(PPh
3
)
3
catal yst
and i n aqueous medi um usi ng a [Rh(COD)Cl ]
2
/TPPTS
catal yst and devel opi ng rate equati ons.
I n thi s paper HRh(CO)(PPh
3
)
3
catal yzed hydroformy-
l ati on of ethyl ene has been i nvesti gated i n a tempera-
ture range of 333-373 K. The effects of catal yst
concentrati on, parti al pressure of CO, H
2
, and ethyl ene
on the rate of reacti on have been studi ed usi ng a sti rred
pressure reactor. The ki neti cs of ethyl ene hydroformy-
l ati on usi ng a water-sol ubl e [Rh(COD)Cl ]
2
/TPPTS cata-
l yst has al so been i nvesti gated at 313 K, wherei n the
effect of di fferent process parameters on the acti vi ty of
the catal yst has been observed. The ki neti cs i n these
systems have been compared.
Experimental Section
The reacti ons were carri ed out i n a sti rred batch
reactor manufactured by Parr I nstrument Co. (Mol i ne,
I L), havi ng a capaci ty of 300 mL. The reactor was
connected to a pressure transducer-recorder system for
moni tori ng of the pressure drop i n the reactor due to
the reacti on. The temperature of the reactor was
control l ed by means of a PI D control l er and automati c
cool i ng system. The catal yst/l i gand was charged al ong
wi th the sol vent i nto the reactor and heated to the
desi red temperature. Ethyl ene was charged i ndi vi du-
al l y i nto the reactor up to the desi red pressure unti l
saturati on. Thi s was fol l owed by CO and H
2
unti l the
requi red parti al pressure was attai ned. The whol e
operati on was done at very l ow agi tati on speed to ensure
that no reacti on took pl ace duri ng addi ti on of the
reactants. Fol l owi ng thi s, the agi tati on was i ncreased
* To whom correspondence shoul d be addressed. Fax: +91
212 333941. E-mai l : i hcu@ems.ncl .res.i n.
CH
2
dCH
2
+ CO + H
2
98
catal yst
CH
3
-CH
2
-CHO (1)
2391 I nd. Eng. Chem. Res. 1998, 37, 2391-2396
S0888-5885(97)00497-1 CCC: $15.00 1998 Ameri can Chemi cal Soci ety
Publ i shed on Web 05/09/1998
to 900 rpm and the recorder was swi tched on. The drop
i n the pressure of the reactor was measured for a fi xed
ti me. These data were used to cal cul ate the rates of
reacti on as fol l ows:
where V
L
) l i qui d vol ume i n the reactor (m
3
), V
G
) voi d
space i n the reactor (m
3
), Z ) compressi bi l i ty factor; R
) gas constant (MPa m
3
kmol
-1
K
-1
); T ) temperature
of the gas i n the reactor (K); P ) total pressure i n the
reactor at any ti me l ess vapor pressure (MPa), and P
0
) i ni ti al pressure i n the reactor l ess vapor pressure
(MPa). The rate of reacti on i s based on the 1:1:1
stoi chi ometry as shown i n eq 1. A typi cal pl ot of the
pressure drop wi th ti me i s shown i n Fi gure 1 for the
effect of P
CO
on the rate of reacti on at 373 K i n tol uene.
The anal ysi s of the product propi onal dehyde was done
on GLC usi ng a thermal conducti vi ty detector (TCD).
Onl y hydroformyl ati on products were observed i n the
reacti on crude. No hydrogenati on was observed. Hence,
the rates cal cul ated by eq 2 were the rates of hydro-
formyl ati on onl y.
Usi ng thi s method the effects of parti al pressures of
ethyl ene, CO, and H
2
and catal yst concentrati on on the
rates of reacti on i n tol uene and water were studi ed i n
the range of condi ti ons gi ven i n Tabl e 1.
Results and Discussion
(a) Studies in a Toluene MediumUsing a HRh-
(CO)(PPh
3
)
3
Catalyst. The effect of agi tati on speed
was fi rst i nvesti gated at the hi ghest temperature of
study (373 K) under standard condi ti ons, and i t was
observed that the rate was i ndependent of agi tati on
beyond 600 rpm. Al l reacti ons were hence conducted
at 900 rpm to ensure that the reacti on occurs i n the
ki neti c regi me. The effect of catal yst concentrati on on
the rate of hydroformyl ati on of ethyl ene was studi ed at
ethyl ene, CO, and H
2
parti al pressures of 0.689, 1.378,
and 1.378 MPa, respecti vel y, i n a temperature range of
333-373 K. The resul ts are shown i n Fi gure 2, whi ch
i ndi cate a fi rst-order dependence on catal yst concentra-
ti on. Thi s i s expected as enhancement i n the catal yst
concentrati on i ncreases the concentrati on of the acti ve
catal yti c speci es and hence the rate.
Effect of thePartial Pressureof Hydrogen. The
effect of the parti al pressure of hydrogen was studi ed
at ethyl ene and CO parti al pressures of 0.689 and 1.378
MPa, respecti vel y, i n a temperature range of 333-373
K and at catal yst concentrati on of 1.0 10
-3
kmol /m
3
.
The resul ts are shown i n Fi gure 3. I t i s observed that
the rate has a strong posi ti ve dependence on hydrogen
pressure of the order of 1.5. Si mi l ar trends were earl i er
reported by Deshpande et al . (1988) for hydroformyl a-
ti on of 1-hexene. At l ower P
H2
formati on of di meri c
speci es i s possi bl e as shown by (Evans et al ., 1968)
The formati on of such speci es wi l l l ead to a reducti on
i n the concentrati on of acti ve catal yti c speci es whi ch wi l l
be more pronounced at l ower hydrogen pressures.
Table 1. Range of Conditions Investigated for the Kinetic Study
descri pti on tol uene water
concentrati on of catal yst, kmol m
-3
(0.5-4.0) 10
-3
(0.2-1.0) 10
-3
parti al pressure of ethyl ene, MPa 0.414-2.756 0.414-2.067
parti al pressure of hydrogen, MPa 0.414-2.756 0.414-2.067
parti al pressure of CO, MPa 0.414-2.756 0.414-2.067
temperature, K 333-373 313
reacti on vol ume, m
3
10 4 2.5 10
-5
Figure 1. Typi cal absorpti on data for reacti on i n a tol uene
medi um. Reacti on condi ti ons: PH2
, 1.378, MPa; Pethyl ene, 0.689
MPa; concentrati on of catal yst, 1 10
-3
kmol m
-3
; temperature,
373 K.
Figure2. Effect of catal yst concentrati on on the rate of reacti on
i n a tol uene medi um. Reacti on condi ti ons: Pethyl ene, 0.689 MPa;
PCO, 1.378 MPa; PH2
, 1.378 MPa.
R )
[(1 - P/P
0
)P
0
]V
G
3ZRTV
L
(2)
2HRh(CO)(PPh
3
)
3
T [Rh(CO)(PPH
3
)
2
]
2
+ H
2
(3)
2392 I nd. Eng. Chem. Res., Vol . 37, No. 6, 1998
Besi des thi s, as shown i n Fi gure 4, the oxi dati ve
addi ti on of H
2
to acyl speci es i s the rate-determi ni ng
step i n thi s reacti on. A combi ned effect of these two
steps coul d gi ve an order of reacti on hi gher than uni ty.
Effect of the Partial Pressure of Ethylene. The
effect of the parti al pressure of ethyl ene was studi ed at
H
2
and CO parti al pressures of 1.378 MPa each, i n a
temperature range of 333-373 K and at a catal yst
concentrati on of 1.0 10
-3
kmol /m
3
. The resul ts are
shown i n Fi gure 5. I t i s observed that the rate i s
i nversel y proporti onal to the ethyl ene concentrati on and
shows a typi cal substrate i nhi bi ti on. The formati on of
al kyl ol efi ni c compl exes l i ke C
2
H
5
Rh(CO)
3
C
2
H
4
i n hy-
droformyl ati on of ethyl ene wi th a Rh
4
(CO)
12
catal yst has
been reported by Ki ng et al . (1980). I n the present
work, formati on of si mi l ar speci es i s possi bl e at hi gh
ethyl ene concentrati ons, resul ti ng i n a l owered concen-
trati on of acti ve catal yti c speci es and hence a reducti on
i n the rate of reacti on, as seen i n Fi gure 4.
Effect of the Partial Pressure of Carbon Mon-
oxide. The effect of the parti al pressure of carbon
monoxi de was studi ed at ethyl ene and H
2
parti al
pressures of 0.689 and 1.378 MPa, respecti vel y, i n a
temperature range of 333-373 K and at a catal yst
concentrati on of 1.0 10
-3
kmol /m
3
. The resul ts shown
i n Fi gure 6 i ndi cate a case of a typi cal substrate-
i nhi bi ted ki neti cs whi ch i s very wel l establ i shed i n
hydroformyl ati on reacti ons. Thi s trend i s observed
Figure 3. Effect of the parti al pressure of hydrogen on the rate
of reacti on i n a tol uene medi um. Reacti on condi ti ons: Pethyl ene,
0.689, MPa; PCO, 1.378,MPa; concentrati on of catal yst, 1 10
-3
,
kmol m
-3
.
Figure 4. Mechani sm of hydroformyl ati on usi ng a HRh(CO)-
(PPh3)3 catal yst.
Figure5. Effect of the parti al pressure of ethyl ene on the rate of
reacti on i n a tol uene medi um. Reacti on condi ti ons: PH2
, 1.378
MPa; PCO, 1.378 MPa; concentrati on of catal yst, 1 10
-3
kmol
m
-3
.
Figure 6. Effect of the parti al pressure of CO on the rate of
reacti on i n a tol uene medi um. Reacti on condi ti ons: Pethyl ene, 0.689
MPa; PH2
, 1.378 MPa; concentrati on of catal yst, 1 10
-3
kmol
m
-3
.
I nd. Eng. Chem. Res., Vol . 37, No. 6, 1998 2393
si nce, at hi gh P
CO
, i nacti ve di - and tri carbonyl acyl -
rhodi um speci es are formed, l eadi ng to a sharp drop i n
acti vi ty. At l ower P
CO
a posi ti ve dependence i s ob-
served, pertai ni ng to enhanced formati on of acti ve
catal yti c speci es HRh(CO)
2
(PPh
3
)
2
(Fi gure 4).
(b) Reactions in an Aqueous Medium Using a
[Rh(COD)Cl]
2
/TPPTSCatalyst System. The ki neti cs
of hydroformyl ati on of ethyl ene was al so studi ed usi ng
a [Rh(COD)Cl ]
2
/TPPTS catal yst system. The acti ve
catal yst here i s anal ogous to that i n a tol uene medi um.
The mai n objecti ve of thi s study was to i nvesti gate and
compare the hydroformyl ati on ki neti cs i n tol uene and
i n a reacti ve medi um l i ke water. Thi s i s i mportant si nce
water-sol ubl e catal yst i s bei ng commerci al l y appl i ed for
hydroformyl ati on of propyl ene to n-butyral dehyde by
Hoechst (Corni l s and Wi ebus, 1995, 1996). The effects
of catal yst concentrati on and parti al pressures of eth-
yl ene, CO, and H
2
on the rate of reacti on were studi ed
at a temperature of 313 K and 1000 rpm (to ensure a
ki neti c regi me).
I t may be noted that the catal yst concentrati on used
i n thi s case i s hal f that used i n the case of tol uene
mai nl y because the reacti on was found to be mass
transfer control l ed at a catal yst concentrati on of 1
10
-3
kmol /m
3
; al so, the pressures of CO, ethyl ene, and
hydrogen used for thi s study are 0.689 MPa each. The
catal yst was prepared i n si tu usi ng [RhCl (COD)]
2
and
TPPTS i n the rati o of 1:6.
The mai n objecti ve was al so to establ i sh the trends
i n an aqueous medi um and compare wi th those i n an
organi c medi um. Hence, the data were observed at a
si ngl e temperature of 313 K.
A fi rst-order dependence i s observed wi th respect to
the catal yst concentrati on as shown i n Fi gure 7. Thi s
trend i s si mi l ar to that observed i n the case of tol uene
as the reacti on medi um. The effect of the parti al
pressure of hydrogen al so shows a fi rst-order depen-
dence (see Fi gure 8). Thi s resul t i s markedl y di fferent
from the 1.5 order observed i n tol uene. Water bei ng a
pol ar sol vent, the formati on of di meri c speci es (eq 3) i s
not faci l i tated. Besi des, the formati on of such speci es
wi l l al so depend on the concentrati ons of other reactants
l i ke CO and ethyl ene. I t i s wel l -known that the
sol ubi l i ti es of al l three of these gases are much l ower
i n water as compared to tol uene (see Tabl e 2).
The rate versus CO parti al pressure passes through
a maxi mum as shown i n Fi gure 9. I n contrast, i n a
tol uene sol vent, onl y a negati ve order dependence i s
observed wi th P
CO
, i n the same pressure range (0.4-
2.76 MPa). Al though, the maxi ma wi th P
CO
have been
wel l documented i n hydroformyl ati on chemi stry, the
di fference i n the trends observed i n water versus those
i n tol uene i s due to the poor sol ubi l i ty of carbon
monoxi de i n water as compared to that i n tol uene. The
concentrati on of CO at l ow pressures i s too l ow to gi ve
the formati on of di - and tri carbonyl acyl rhodi um speci es
(see Fi gure 4), gi vi ng a posi ti ve order dependence wi th
respect to CO i n thi s range. The i nhi bi ti on observed at
Figure 7. Effect of the catal yst concentrati on on the rate of
reacti on i n an aqueous medi um. Reacti on condi ti ons: Pethyl ene,
0.689 MPa; PCO, 0.689 MPa; PH2
, 0.689 MPa; temperature, 313 K.
Figure 8. Effect of the parti al pressure of hydrogen on the rate
of reacti on i n an aqueous medi um. Reacti on condi ti ons: Pethyl ene,
0.689 MPa; PCO, 0.689 MPa; concentrati on of catal yst, 5 10
-4
kmol m
-3
; Rh/TPPTS, 1:6; temperature, 313 K.
Table 2. Solubility of Ethylene, CO, and H2 in Toluene
and Water
sol ubi l i ty, MPa m
3
kmol
-1
sol vent temperature, K ethyl ene hydrogen CO
water 313 40.33 191.06 211.04
tol uene 333 1.904 61.69 18.51
tol uene 353 2.791 90.69 23.02
tol uene 373 9.209 153.02 29.62
Figure 9. Effect of the parti al pressure of CO on the rate of
reacti on i n an aqueous medi um. Reacti on condi ti ons: Pethyl ene,
0.689 MPa; PH2
, 0.689 MPa; concentrati on of catal yst, 5 10
-4
kmol m
-3
; Rh/TPPTS, 1:6; temperature: 313 K.
2394 I nd. Eng. Chem. Res., Vol . 37, No. 6, 1998
hi gher pressures i s mai nl y due to the formati on of these
i nacti ve speci es.
Fi gure 10 shows the effect of the parti al pressure of
ethyl ene on the rate of reacti on. The trend i s si mi l ar
to that observed wi th carbon monoxi de. A fi rst-order
dependence i s observed up to an ethyl ene pressure of
al most 1 MPa, whereas i n the case of tol uene even at a
pressure of 0.4 MPa, a negati ve order i s observed. The
i nhi bi ti on wi th an i ncrease i n the ethyl ene parti al
pressure i s mai nl y due to the formati on of di ol efi ni c
speci es, as menti oned earl i er. At l ower ethyl ene parti al
pressure, i n an aqueous medi um, the concentrati on of
ethyl ene i s too l ow to generate i nhi bi tory speci es and,
hence, a fi rst-order dependence i s observed. Thi s can
be attri buted to the i ncreased formati on of acti ve al kyl
rhodi um speci es (Fi gure 4) and, hence, rate.
Kinetic Model. I n order to ensure that the data
observed are i n the ki neti c regi me, the rates were
compared wi th the maxi mum rates of mass transfer
possi bl e under reacti on condi ti ons (k
L
aA*). For thi s
purpose, the val ue of k
L
a was obtai ned as di scussed i n
the l i terature, for sti rred dead-end reactors of the same
type as used i n thi s work (Chaudhari et al ., 1987). The
k
L
a was found to be 0.1 s
-1
. The sol ubi l i ti es of ethyl ene,
CO, and H
2
i n tol uene and water were measured usi ng
a pressure absorpti on method, and the val ues are gi ven
i n Tabl e 2. The val ues of R
1
, R
2
, and R
3
as defi ned by
Chaudhari and Dorai swamy (1974) were cal cul ated.
These were found to be l ess than 0.12, even for the
hi ghest rates observed. Thi s confi rms the absence of
mass-transfer l i mi tati ons and, hence, the ki neti c regi me.
For the purpose of ki neti c model i ng the data at constant
catal yst concentrati on were used i n ei ther case.
A number of empi ri cal model s were exami ned to
represent the observed data. The best model was
sel ected on the basi s of the cri teri a of l east average error
between the predi cted and experi mental rates (
mi n
)
defi ned as
and the resul ts are presented i n Tabl e 3 for the studi es
i n tol uene medi um. The val ues of the constants were
eval uated usi ng an opti mi zati on routi ne (Marquardt
method). For thi s purpose i ni ti al guess val ues were
obtai ned by the graphi cal fi tti ng of the rate data to the
respecti ve model s. These val ues were used as the
starti ng val ues for the opti mi zati on program.
The model 5 coul d not be consi dered because i t gi ves
a negati ve val ue for parameter K
E
. Al so the trend wi th
k i s not accordi ng to that di ctated by thermodynami cs.
Si mi l arl y model s 3, 4, and 6 have i nconsi stent trends
i n the parameters K
B
and K
E
and hence were not
consi dered. Between the model s 1 and 2, the
mi n
val ues
were hi gher for model 2.
Table 3. Models Examined To Fit the Data on Ethylene Hydroformylation
model rate model T, K KB 10
-2
KE k mi n
a
1
k(A*)
1.5
B*E*
(1 + K
B
B*)
2
(1 + K
E
E*)
333 1.116 15.01 8.202 10
2
3.95 10
-11
353 1.268 23.97 8.873 10
3
2.12 10
-10
373 1.490 26.74 3.007 10
4
1.00 10
-9
2 k(A*)B*E*
(1 + K
B
B*)
2
(1 + K
E
E*)
2
333 1.000 26.47 2.920 10
2
2.350 10
-10
353 1.530 28.56 2.208 10
3
3.904 10
-9
373 1.820 58.84 1.520 10
4
7.140 10
-9
3
k(A*)
1.5
B*E*
(1 + K
B
B*)
2
(1 + K
E
E*)
333 0.944 27.69 1.490 10
2
3.830 10
-10
353 1.290 48.86 2.410 10
3
3.790 10
-9
373 1.780 43.45 1.704 10
4
2.350 10
-8
4
k(A*)
1.5
B*E*
(1 + K
B
B*)(1 + K
E
E*)
2
333 1.380 26.50 2.640 10
2
1.430 10
-9
353 1.010 47.71 2.830 10
3
3.180 10
-9
373 0.153 27.99 4.718 10
3
8.180 10
-6
5
k(A*)
1.5
B*E*
(1 + K
B
B*)
3
(1 + K
E
E*)
333 0.413 20.10 9.410 10
2
7.720 10
-11
353 0.375 -48.61 9.780 10
3
2.020 10
-9
373 0.009 42.20 2.880 10
3
2.210 10
-8
6
k(A*)
1.5
B*E*
(1 + K
B
B*)
3
(1 + K
E
E*)
333 0.924 16.98 5.630 10
2
1.260 10
-9
353 1.268 23.97 8.870 10
3
1.090 10
-8
373 0.023 645.79 2.190 10
4
2.020 10
-8
a
mi n i s mi ni mi zed sum of the squares of the di fference between observed and predi cted rates.
Figure10. Effect of the parti al pressure of ethyl ene on the rate
of reacti on i n an aqueous medi um. Reacti on condi ti ons: PH2
, 0.689
MPa; PCO, 0.689 MPa; concentrati on of catal yst, 5 10
-4
kmol
m
-3
; Rh/TPPTS, 1:6; temperature, 313 K.
R
1
)
R
k
1
aA*
(4)
R
2
)
R
k
L
aB*
(5)
R
3
)
R
k
L
aE*
(6)

mi n
)

i)1
n
(R
pred
- R
obs
)
2
(7)
I nd. Eng. Chem. Res., Vol . 37, No. 6, 1998 2395
The model chosen on the basi s of
mi n
was
Thi s model was found to predi ct the rate data wi thi n
an error of (8%, whi ch i s wi thi n the range of experi -
mental error. Thi s was found to be i n excel l ent agree-
ment wi th the predi cted rates, as i s cl ear from the l ow

mi n
val ue. The val ues of k, K
B
, and K
E
were eval uated
for al l three temperatures and are gi ven i n Tabl e 3. The
acti vati on energy was cal cul ated as 9.4 10
4
kJ/kmol .
A si mi l ar exerci se was undertaken for arri vi ng at a
rate model for reacti on i n an aqueous medi um. The rate
data obtai ned were found to be wel l represented by the
fol l owi ng form of rate equati on.
I n thi s case the model si mi l ar to model 2 (Tabl e 3)
was found to best fi t the observed rate data. A model
si mi l ar to model 1 (1.5 order wi th respect to A*) coul d
not predi ct the rate parti cul arl y for hydrogen depen-
dence.
Conclusions
The ki neti cs of hydroformyl ati on of ethyl ene was
studi ed i n tol uene and water medi a usi ng HRh(CO)-
(PPh
3
)
3
and [Rh(COD)Cl ]
2
/TPPTS catal yst, respecti vel y.
The rates were found to have a fi rst-order dependence
wi th respect to catal yst concentrati on. Si mi l ar trends
were observed wi th respect to the parti al pressure of
ethyl ene and carbon monoxi de, i n both sol vents. The
di fference i n the l ocati on of the maxi ma was attri buted
to the poor sol ubi l i ty of the reactants i n water as
compared to tol uene. The major di fference observed was
a 1.5 order wi th hydrogen i n tol uene versus a fi rst order
i n water.
The fol l owi ng rate model were found to represent the
data i n tol uene at 333-373 K:
The fol l owi ng rate model represented the data i n an
aqueous system at 313 K:
wi thi n 8% error.
Nomenclature
A* ) concentrati on of H
2
i n tol uene or water at a gas-
l i qui d i nterface, kmol /m
3
B* ) concentrati on of CO i n tol uene or water at a gas-
l i qui d i nterface, kmol /m
3
E* ) concentrati on of ethyl ene i n tol uene or water at a
gas-l i qui d i nterface, kmol /m
3
k ) reacti on rate constant i n eq 8, m
7.5
kmol
-2.5
s
-1
K
B
) constant i n eq 8, m
3
kmol
-1
K
E
) constant i n eq 8, m
3
kmol
-1
P ) total pressure i n the reactor at any ti me mi nus vapor
pressure, MPa
P
0
) i ni ti al pressure i n the reactor mi nus vapor pressure,
MPa
R ) gas constant, MPa m
3
kmol
-1
K
-1
T ) temperature of the gas i n the reactor, K
V
L
) l i qui d vol ume i n the reactor, m
3
V
G
) voi d space i n the reactor, m
3
Z ) compressi bi l i ty factor
Literature Cited
Arai , H.; Kaneko, T.; Kunugi , T. Catal yti c vapor phase hydro-
formyl ati on of ol efi ns over pol ymer i mmobi l i zed rhodi um com-
pl exes. Chem. Lett. 1975, 265-268.
Chaudhari , R. V.; Dorai swamy, L. K. Si mul taneous absorpti on and
reacti on of two gases i n a l i qui d/formati on of ethyl chl ori de from
ethyl ene and hydrogen chl ori de. Chem. Eng. Sci. 1974, 29, 349-
354.
Chaudhari , R. V.; Ghol ap, R. V.; Emi g, E.; Hoffmann, H. Gas-
l i qui d mass transfer i n Dead-End autocl ave reactors. Can. J .
Chem. Eng. 1987, 65, 744-751.
Corni l s, B.; Wi ebus, E. Aqueous catal yst for organi c reacti ons.
CHEMTECH 1995, 25, 33-38.
Corni l s, B.; Wi ebus E. Vi rtual l y no envi ronmental i mpact: the
bi phasi c oxo process. Recl. Trav. Chim. Pays-Bas 1996, 115,
211-215.
Deshpande, R. M.; Chaudhari , R. V. Ki neti cs of hydroformyl ati on
of l -hexene usi ng HRh(CO)(PPh
3)3 compl ex catal yst. I nd. Eng.
Chem. Res. 1988, 27, 1996-2002.
Di vekar, S. S.; Deshpande, R. M.; Chaudhari , R. V. Ki neti cs of
hydroformyl ati on of 1-decene usi ng homogeneous HRh(CO)-
(PPh
3)3 catal yst: A mol ecul ar l evel approach. Catal. Lett. 1993,
21, 191-200.
Evans, D.; Osborne, J.; Wi l ki nson, G. Hydroformyl ati on of al kenes
by use of rhodi um compl ex catal ysts. J . Chem. Soc. A 1968,
3133-3142.
Ki ng, R. B.; Ki ng, A. D.; Jr., I qbal , M. Z.; Tanaka, K. I ntermedi ates
i n the rhodi um catal ysed hydroformyl ati on of ol efi ns. Ann. N.Y.
Acad. Sci. 1980, 333, 74-79.
Pol i evka, M.; Uhl ar, L.; Macho, V. Hydroformyl ati on of ethyl ene
catal yzed by rhodi um compl exes. Petrochimia 1980, 20, 33-
41.
Schwaar, R. H. SRI -PEP Report 11DS, 1991.
Takahashi , N.; Takeyama, T.; Yanagi bashi , T.; Takada, Y. Com-
pari son of pentan-3-one formati on wi th propi onal dehyde forma-
ti on duri ng ethyl ene hydroformyl ati on over rhodi um/acti ve
carbon catal yst. J . Catal. 1992, 531, 1936-1938.
Received for review Jul y 11, 1997
Revised manuscript received February 12, 1998
Accepted February 12, 1998
I E970497U
R )
kA*
1.5
B*E*
(1 + K
B
B*)
2
(1 + K
E
E*)
2
(8)
R )
34550A*B*E*
(1 + 278B*)
2
(1 + 3829E*)
2
(9)
R )
kA*
1.5
B*E*
(1 + K
B
B*)
2
(1 + K
E
E*)
2
R )
34550A*B*E*
(1 + 278B*)
2
(1 + 3829E*)
2
2396 I nd. Eng. Chem. Res., Vol . 37, No. 6, 1998