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A L F O N S G. B U E K E N S A N D G I L B E R T F. F R O M E N T
Rijksuniuersiteit Gent, J. Plateaustraat 22, Gent, Belgium
The thermal cracking of propane was studied in a flow apparatus between 625' and 850' C. and a t
atmospheric pressure. Fairly complete product distributions, including those for C4, C5, and Ca hydro-
carbons, were established and a reaction scheme was deduced. The order of the propane decomposition
was determiined by comparing experiments with different degrees of feed dilution and found to vary with
conversion and temperature. When the rate was fitted by means of a first-order kinetic expression, the
rate coefficient decreased with increasing conversion. This so-called "inhibition" was expressed mathe-
matically by considering the rate coefficient to b e a hyperbolic function of conversion. The activation energy
of the first-order rate coefficient increases with conversion. Finally, rate equations based on the radical
nature of the process are discussed.
A
a
DE BOODT
PAUL
STEACIE
LAIDLER
9 KERSCHENBAUM
BUEKENS
x = 30%
x x = 60%
a x = 90%
log Ti [E :(set)-']
BUEKENS
8 KO
1:x. 30%
~ 60%
2 : :
3:x 8 90%
"C
99
1
Figure 2. Arrhenius diagram
Point values of rate coefficient, k
Analysis Propane flow range, 0.4 to 10 moles per hour, and thus a
residence time of 0.04 to 1 second and a Reynolds number of
T h e reactor effluent stream was analyzed on a Wilkens
8 to 200.
Moduline 202 gas chromatograph with hot wire detector. Dilution factor, 6 (molar ratio of nitrogen to propane),
T h e columns used are described in Table 11. 0 to 10.
The carrier gas was hydrogen, unless otherwise mentioned. The analysis of the propane was as follows: propane 98.9
The peak surfaces were measured by means of a mechanical mole %, ethane 0.3 mole %, propylene 0.2 mole %,2-methyl-
integrator. Calibration factors determined for nitrogen, propane 0.6 mole %, sulfur 10 p.p.m. Before a series of experi-
methane, ethane, ethylene, acetylene, propane, propylene, ments the reactor surface was deactivated with CS2 at tem-
and benzene were in excellent agreement with those published peratures between 450' and 550' C.
by Rosie and Grob (1957).
The material balance of the experiments checked within 1%.
Experimental Results The results are presented in two ways: in conversion us.
The experiments covered the following range of variables : V/F, diagrams and in product distribution or selectivity dia-
Temperature, 625' to 850' C. grams. The diagrams of the first type are more directed
Pressure, atmospheric; maximum pressure, 1.3 atm. toward a kinetic analysis, those of the second type toward a
absolute. study of the reaction mechanism.
438 I&EC P R O C E S S D E S I G N A N D D E V E L O P M E N T
' 0 ° 1 800°C
s-
x
50,
25
Figure 5. Total conversion of propane and conversion to primary products as a function of V / F , at 800" C.
IO
Figure 6. Selectivity diagram for temperature range 725" to 750" C.
The ethyl radicals may then form ethane. methylacetylene, and propadiene (or allene) are dehydrogena-
One possible termination reaction is the recombination of tion products of ethylene and propylene. The single curve
two methyl radicals drawn for these products is to be regarded as a mean curve,
since the dehydrogenations are temperature-dependent. T h e
2CHsO + C2He rate of these reactions is lowered when the reactor wall is pre-
treated with CS2. At a conversion of 95% the selectivity for
which also produces ethane. acetylene amounts to 1.8%-the equilibrium value-without,
Figures 6 and 7 show how the selectivity for ethylene and but only to 0.6% with pretreatment. The activation energies
methane increases with increasing conversion, while that for are estimated to be 90,000, 80,000, and 70,000 cal. per mole
propylene and hydrogen decreases. T h e ethylene-propylene for acetylene, allene, and methylacetylene formation. T h e
molar ratio rises from 1.0 a t zero conversion to 3.7 a t 85% and temperature effect on the 1-butene formation is undeniable.
6 a t 95% conversion. The selectivities go through a maximum for a propane con-
I n the technical literature the product distribution is often version of 40 to 50%; below that conversion 1-butene is the
referred to the amount of ethylene produced. When propane most important secondary product. The decrease in selectivity
is cracked to 90% conversion under industrial conditions, 33 kg. beyond the conversion is probably due to isomerization into
of propylene are produced per 100 kg. of ethylene (Burke and 2-butene and 2-methylpropene and also to dehydrogenation
Miller, 1965). The figure obtained in this study is 36.6. into 1,3-butadiene.
For methane the figures are 61 and 62; for the secondary There are several possibilities for the formation of 1-butene.
products, 7 and 7 (1.3-butadiene) and 4 and 3 (butenes). One possibility is:
Secondary Products, T h e selectivities of the principal
secondary products are shown in Figure 8. Acetylene, 2C2H4 S CH&H2CH=CHz (1)
40
30 -
20 -
IO .
.
I
T . '.. T _c -- T T.
' T
.
T T
TT 'ZH6,
10 20 30 40 x59. 60 70 80 90 1 0
Several objections may be formulated against this reaction traced back to the temperature dependence of the radical
as the principal source of 1-butene. Indeed, the conversion to concentrations. When compared at the same inhibition level,
1-butene is higher than the equilibrium conversion of Reaction these concentrations vary with temperature according to an
1. Furthermore, the selectivity for 1-butene increases with Arrhenius-type relation, so that an activation energy may be
temperature, whereas the equilibrium conversion decreases used to characterize their temperature dependence. From
with temperature. Finally, Reaction 1 was found by Krauze the simulation of the cracking of propane on a digital computer
et al. (1935) to have an activation energy of 37,700 cal. per a value of about 48,000 cal. per mole may be derived for the
mole, considerably less than that for total propane decom- "activation energy" of the methyl radical, while that for the
position. A comparison of selectivities at equal conversion for allyl radical must be between 20,000 and 30,000 cal. per mole
different temperatures indicates that the activation energy of (Buekens, 1967). I t follows that the apparent activation
1-butene formation is approximately 15,000 cal. per mole energy for 1-butene formation according to Reaction 2 must lie
higher than that of propane decomposition, which varies between 70,000 and 80,000 cal. per mole, in agreement with
between 52,000 and 64,000 cal. per mole. the experimental results.
For all these reasons, a more plausible way for the pro- As mentioned above, 1-butene isomerizes partially into
duction of 1-butene is the recombination between methyl and 2-methylpropene and 2-butene. The selectivity for 2-butene
allyl radicals: does not exceed 0.3%. 2-Methylpropene could not be
ki2
separated completely from I-butene by gas chromatography.
CH3" C3Hb0 --t C4H3 (2) For propane conversions of 90 to 95% the amount of 2-methyl-
propene was estimated to represent some 40% of the sum of
where the allyl radicals are formed according to: 1-butene and 2-methylpropene.
C3Hrj + R" -+ C3Hb" + RH (3)
The 1,3-butadiene selectivity, also represented in Figure 8,
was found to be practically independent of temperature. If
Reaction 2 requires no activation energy. Therefore, the 1,3-butadiene were formed by dehydrogenation of 1-butene,
temperature dependence of the 1-butene formation has to be the selectivity would decrease at high propane conversions,
2.4 .
s
2.0 -
*
t
2
t-
1.6 -
u
W
-I
W
* 1.2 -
0.8.
~ H c / / CH
2C2H4 + CHFCH-CH=CHZ + Hz
CzHs'
CH3'
++ RC3H5'
H
- 7
I-butene
J.
-
+ 2-butene +
1
1,3-butadiene +
Hz
2-methylpropene
a conclusion set forward by Schneider and Frolich (1931). C2&' + C3H5' I-pentene
-{
-+
The Csand Cg hydrocarbons are mainly dienes and aromatics
and are probably formed by condensation reactions of ethylene C3H70+ C3H50 4-methyl-1-pentene
l-hexene
and propylene. The following products were identified :
pentadiene, isoprene, methylpentadienes, cyclic dienes such as
cyclopentadiene and probably cyclohexadiene; olefins such as Kinetic Study
I-pentene, 1-hexene, and 4-methyl-I-pentene; cyclic olefins Equivalent Reactor Volume. One of the main problems
such as cyclopentene and cyclohexene; and aromatics such as encountered in the derivation of rate equations for homogene-
benzene and toluene. ous gas-phase reactions from experiments in tubular flow
The formation of aromatics increases rapidly a t high con- reactors is the longitudinal temperature profile. Indeed, it
versions. I t is strongly dependent on wall effects. is not possible to distinguish sharply between preheat and
Reaction Scheme. To conclude this discussion of the reaction sections as can be done in fixed-bed catalytic reactors.
product distribution, the following reaction scheme may be If the rate is to be determined a t a reference temperature,
set u p : say TR, and if the reaction volume is counted from the point
Hz + CzHz where TR is reached, an error is introduced by neglecting the
CHI
7
+ CzH4
\
-
7
'/z(Hz -t G H s ) +
conversion accomplished in the section below TR. A similar
situation occurs at the outlet, where the conversion continues
to some extent at a temperature lower than TR. To
C3HS 4 H z + CsHs 3 correct for this and to compare experimental data at the same
reference temperature TR,use can be made of the equivalent
L /
Hz + C3Hs * '/2(Hz + Ce"o) reactor volume concept introduced by Hougen and Watson
(1947). The equivalent reactor volume, V, is defined as that
volume which, at reference temperature TR, would give the
same conversion as the actual reactor, with its temperature
profile. I t follows that
T h e reactions of this scheme probably proceed over radicals
almost entirely. An additional set of reactions is required to TT
dV = - dV' (4)
explain the formation of ethane and olefins: ~ T R
exp( -")
RT R
Conversion
Order
0.022
1.36
0.058
1.21
0.067
1.14
. . . 0.238 0.412
1 0.99 0.96
inhibition, which is mainly determined by the relative rates of This shift in activation energy may explain the spread of the
reaction of the chain-carrying radicals with propane and values reported in the literature, probably obtained a t different
propylene. For this reason k/k,, the ratio of the point value levels of inhibition.
of the rate coefficient a t conversion x to the point value at zero I t is of importance to present point values of the rate co-
conversion, may be written: efficient, too. Indeed, most of the k values reported in the
k k(R") (C3Hd literature are point values. Furthermore, if a relation is to be
- k(Ro)(C3Hd + k"(Ro)(C3Hd
- E
established between the over-all rate coefficient and the inti-
k,
mate nature of the reaction, point values are of more direct
Since the selectivity for propylene is almost independent of interest than integral values. Equation 6 suggests a hyper-
the pressure, the extent of inhibition is in first approximation bolic law for the variation of point values k, with conversion:
determined by the conversion, so that Equation 6 is obtained:
k0
k=-
1 + ax (7)
+I
-1
-2
i ORDER
1/2 1 I20 3/2
Figure 9. Determination of reaction order
tR = 675OC. V / F , = 7.86 x = 0.0253, dilution factor 6 = 0
V / F o = 13.50 x = 0.0259, dilution factor 6 = 6.43
sider the drop in k as zero conversion is approached, of course. 625 0.0548 7.345
650 0.1819 11.720
T h e “initial value,’’ k,, and the inhibition coefficient, a, the 675 0,3298 3.696
constants of the empirical hyperbolic law describing the in- 700 0.9452 6.505
hibition, were determined in the following way. 725 1 ,7800 5.896
750 2.2140 2.371
When the expansion factor equaIs 2, the combination of 775 4,0760 1.128
Equation 7 with the continuity and rate equations leads to: 800 9.3580 1.799
825 13.9500 1.375
-dx- - kOCt(1 - x )
d-
v (1 + ax)(l + x)
(8)
FO
With an equation of this form k, and a may be calculated
Upon integration and rearrangement, Equation 8 gives: from a set of experimental x us. C,V/Fo values by linear re-
gression. T h e results are shown in Table v.
V
C,k, -= -a 2 In (1 - x) + 2x + - - 2 In (1 - + x
X2
2) Figure 10 shows a k us. V/Fo or x curve and compares experi-
FO 2 mental and calculated E values at 775’ C. The calculated E
(9) values were obtained from:
a = 3.01 X lO5exp
(2:3
___
30y0 conversion:
6OYc conversion :
90% conversion:
I.'
T h e point values are lower than the integral values, of where 0 = C1 -
course, while the activation energies are higher, as may be FO
foreseen from the trend observed in Figure 1 .
The inaccessible radical concentrations may be eliminated
The activation energies given here are lower than those
from this expression with the help of the so-called steady-state
usually reported. No effect of heat transfer limitations may be
approximation. According to this concept, introduced by
involved: T h e thermocouples are inserted in the gas stream
Bodenstein, the radical concentration does not vary rapidly
itself, not on the wall. However, De Boodt (1962) obtained a
beyond the initial startup period. A balance on the pro-
value of 53,300 cal. per mole in a flow apparatus of different
duction and consumption of CH3' and H' then leads to ex-
construction than the one used in this study, while Kershen-
pressions for the concentrations of these radicals as a function of
baum and Martin (1967) came to an expression for the first-
the propane concentration. After substitution of these ex-
order rate coefficient in the temperature range 800' to 1000' C.
pressions into Equation 10 the following rate law, which is of
(Table I) which is in remarkable agreement with the equation
first-order with respect to propane, is obtained, provided no
given here for k,.
distinction is made between n- and isopropyl radicals and
Radical Mechanisms. T h e over-all order of propane de-
composition depends upon the conversion and temperature.
ki << k3.
2+6
The rate of reaction of titanium-metal sponge with nitrogen in argon-nitrogen gas mixtures was studied
a t 900" C. The reaction rate is dependent on the partial pressure of nitrogen in the gas phase. At least
three titanium-nitrogen solid phases are formed as the reaction proceeds, and the rate-controlling mech-
anism is believed to b e the diffusion rate of atomic nitrogen through the TiN,(G) phase. A single relation
has been developed which describes the titanium-nitrogen reaction kinetics of argon-nitrogen mixtures.
Additional mathematical relationships were developed to permit estimation of the required size and useful
lifetimes of titanium-sponge gettering beds designed to remove a nitrogen impurity from otherwise pure
argon.
increasing utilization of large inert-gas enclosures has made of the kinetics of the titanium sponge-nitrogen reaction
Tied to interest in purification systems capable of removing
HE
with nitrogen present in otherwise pure argon. A reaction
oxygen, nitrogen, and water vapor contaminants from large temperature of 900" C . was chosen for this study asacompromise
volumes of inert gas, particularly helium and argon. Chemical between good reaction kinetics and ease of containment of the
gettering methods are often employed to maintain a pure titanium sponge. Previous work (Wasilewski and Kehl,
atmosphere. I n a system of this type, a n activated sorbent 1954) showed that the titanium-nitrogen reaction rate increases
such as molecular sieves (product of the Linde Division, Union with temperature from 750" to 1400' C. Holvever. the exist-
Carbide Corp.) can be used to remove water vapor, and a rela- ence of a titanium-nickel liquid phase (Hansen and Anderko,
tively low-temperature gettering material (such as manganous 1958) above about 955°C. prevents containment of titanium
oxide a t 150" C.) can be used to remove oxygen. T h e removal sponge in stainless steels or other nickel alloys a t the higher
of nitrogen presents a greater problem because of its lower temperatures
chemical reactivity.
Interest in the use of titanium as a nitrogen-gettering material Equipment
has stemmed from several advantages that titanium possesses A diagram of the experimental system is shown in Figure 1.
over gettering materials now commonly used. Titanium-metal An argon-nitrogen mixture of carefully controlled composition
sponge, a high-surface-area form suitable for gettering opera- was continuously circulated through a small bed of titanium
sponge. This bed was composed of eight removable sections
tions, is available a t a relatively low cost and requires no pre- hereafter called sample beds. Each sample bed consisted of
treatment before use. Neither the oxide nor nitride reaction 1 to 10 grams of -8 +IO-mesh titanium sponge (see Table I )
products of titanium are pyrophoric, and they can be handled contained in a 2-inch 0.d. by 0.5-inch high circular tray, the
in air. Both titanium and its reaction products have low bottom of which was constructed of two layers of 70-mesh
stainless steel (Type 310) screen. Figure 2 shows the titanium
toxicity. sponge in a sample bed. Lava (aluminum silicate) spacers
T o investigate the possible utilization of titanium as a get- were used between the individual sample beds to facilitate their
tering material for nitrogen impurities in argon, a study was removal.