Simulation of an Ethylene Oligomerization Reactor

System Using ASPEN

M . G . DOKURNO

Du Pont Canada Inc., Research Centre, P.O. Box 5000, Kingston, Ontario K7L 5A5

and

P . L. DOUGLAS

Department of Chemical Engineering, Queen’s University, Kingston, Ontario K7L 3N6

A reactor system for the production of alpha olefins (C4-C,&, by an ethylene polymerization reaction (oli-
gomerization) using an aluminum alkyl catalyst, has been simulated using ASPEN (Advanced System for Process
ENgineering) as the basis for the design of an alpha olefins production plant. An experimental plug flow reactor
622 cm long with an internal volume of 175 cm3 was built and operated at temperatures of 110°C to 130°C and a pressure
of 10 MPa. Measurements of the product composition were made and found to compare favourably with the simulation
results. The ASPEN plug flow reactor model used to predict output reactor composition is based on 64 possible
simultaneous chemical reactions involving 17 chemical species. Kinetic data required by ASPEN was obtained from the
literature and experimentation.
Experimental and simulation results are presented which show ASPEN to be an excellent process design tool.

On a simult un ensemble de rkacteurs pour la production d’olefines Alpha (C4-CI6)par polymkrisation de I’tthylhe
(oligomdrisation) catalysde par un alkyle d’aluminium. en utilisant ASPEN (Advanced System for Process ENgineering),
et dans le but de servir de base au calcul d’une wine de production d’olefines alpha.
On a construit un dacteur exp6rimental h tcoulement piston de 622 cm de longueur et de 172 cm’ de volume interieur
et on I’a fait fonctionner h des temperatures de 110 h 130°C et sous une pression de 10 MPa. On a fait des mesures de
la composition des produits que I’on a trouvees comparables avec les resultats de la simulation. Le modele ASPEN de
dacteur h tcoulement piston utilisC pour prkdire la composition ti la sortie du rtacteur comporte 64 reactions chimiques
simultantes possibles et I7 espkces chimiques difftrentes. Les donnees cinetiques ntcessaires pour ASPEN ont C t t
obtenues soit dans la littkrature soit par experimentation.
Les rksultats exp6rimentaux et ceux obtenus par simultion indiquent qu’ASPEN est un excellent outil de calcul de
procede.

Background

L inear alpha olefins, which have one double bond at the

terminal position of the paraffin chain, are important in
the manufacture of synthetic lubricating oils, special de-
tergents, plasticizer alcohols and ethylene co-polymers.
With the rising cost of feedstocks, it has been increasingly
important for the chemical industry to search for lower cost
starting materials. One relatively inexpensive feed which
can be oligomerized to produce higher alpha olefins is
ethylene.
The oligomerization of ethylene was first reported by
Ziegler (1952) and discussed in greater detail in a series of
papers in the 1960’s (Ziegler, 1961; Albright and Smith,
1968). The oligomerization or growth of ethylene uses metal
alkyl catalysts, usually triethylaluminum. Ethylene adds to
triethylaluminurn by insertion between the aluminum atom
and one of the alkyl groups until a selected alkyl size is
reached. For example one possible reaction is:
......................................... (1)
Reaction ( I ) is known to be bimolecular (with respect to
each of three active sites) with an overall order of two
(Ziegler et al., 1960). It is important to note that reaction ( I )
is one example of what might occur when two moles of
ethylene are reacted with one mole of triethylaluminum
(TEA). An equally possible reaction might have one mole of
ethylene add to one active site while the other mole of
ethylene adds to another. It has been shown, however, that
the reactivity of the alkyl-aluminum bond toward ethylene is
affected very little by the length of the alkyl chain. There-
fore, the length of each alkyl chain is determined by proba-

818 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING, VOLUME 62, DECEMBER 1984
 ETHYLENE GROWTH
DISPLACEMENT
F:EED t .
I ' REACTOR I
I '
CATALYST
r
OLEFINS + CATALYST
t
, C ~ A +OLEFIN
C PRODUCT
t
CATALYST RESIDUES
Figure 1 - Schematic flowsheet of one-step oligomerization
process.
bilistic considerations. The average chain length or molecu-
lar weight of the alkyl group is a function of the amount of
ethylene added and the reaction temperature. The more
ethylene added and/or the higher the temperature, the
, C2Hs
A1 - CHZCH2CH2CH2C2HS + C2H4 --*
, C2Hs
A1 - C2H5 + CbH12
' C2HS
There are two basic processes for the oligomerization of
ethylene; they are the so-called One-Step and the Two-step
processes. In the One-Step Process, shown schematically in
Figure 1, only catalytic amounts of aluminum alkyl are
used. Typical reaction conditions for the One-Step Process
are 176-287°C and 14-28 MPa. Under these conditions
both displacement and chain growth are favoured. The prod-
uct distribution obtained by the One-Step Process is given
by the mathematical correlation (Ziegler, 1961):
X ( P ) = P [ B / ( I + B ) ] ....................... (3)
where X(P) is the fraction of olefins having 2(P + 1) car-
bons and B is a function of operating conditions.
In the Two-step Process, shown schematically in Figure
2, each aluminum bond produces one olefin on each pass
through the chain growth reactor. The reactor yields alkyls
having a molecular weight distribution according to the
Poisson equation (Ziegler, 1961):
X(P) = n P e - " / f ! ........................... (4)
where n = moles ethylene added/moles aluminum bonds.
The alkyls are displaced from the aluminum by a lower
olefin in a displacement reactor and then separated from the
aluminum alkyls, which are returned to the growth reactor.
Typical reaction conditions for the growth reactor are
93-121°C, 10-21 MPa and for the displacement reactor
are 260-315"C, 0.7-2 MPa.
Objectives
There are two main objectives of this work:
1. To obtain kinetic data for the alpha-olefin aluminum
alkyl displacement reaction.
THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING, VOLUME 62, DECEMBER
ALUMINUM ALKYLS
t
LDISPLACING
OLEFIN MAKEUP
Figure 2 - Schematic flowsheet of two-step oligomerization
process.
higher the average molecular weight.
Once the alkyl is grown it may then be converted to the
corresponding olefin by displacement with a lower olefin
(often ethylene) as follows:
............................................. (2)
2. To simulate the operation of a bench scale alpha-olefin
reactor using ASPEN (Gallier et a]. , 1980) for the pur-
pose of preliminary plant design.
The kinetic data for the growth reaction have already been
determined and published by Albright and Smith (1968).
Those for the displacement reaction are not available in the
literature and were obtained here using a 150 cm3CSTR and
a 1 cm3 plug flow reactor.
A 175 cm3 bench scale reactor was built, operated, and
simulated using ASPEN. The ASPEN simulator requires
kinetic data to simulate a plug flow reactor. Literature
values for the growth reaction and experimental values,
obtained in this study, for the displacement reaction were
used to simulate the bench scale reactor (Albright and
Smith, 1968). Scale-up and design of a full scale reactor
system are obvious future objectives. The bench scale reac-
tor design and operation as well as the ASPEN simulation
results are presented.
Experimental
DISPLACEMENT
REACTION KINETICS
Kinetic experiments were performed to determine the rate
constant expression for the displacement reaction. Experi-
ments were carried out in a 150 cm3 CSTR (for low
temperatures), and a 1 cm3 plug flow reactor (for high
temperatures). Two different displacement reactions were
studied. At low temperatures the displacement of tribu-
tylaluminum by octene was investigated and at high tem-
peratures the displacement of trioctylaluminum by hexene
was studied.
The 150 cm3 CSTR reactor system consisted of a
1984 819
 TABLE1 TABLE2
Reactor Operating Conditions Displacement Reaction Rate Constants in 150 cm7 CSTR
I cm3 175 cm' T Holdup Butene Butane
kinetic bench scale (OK) (S) Q % % k (m'/kmol.s)
reactor reactor
406.15 480.0 0.055 0.293 0.017 3.55 X lo-'
Preheated temperature ("C) 279-302 413.35 475.2 0.095 0.276 0.024 6.55 x 10 '
Reactor temperature ("C) 245 -273.5 110- 130 418.45 413.4 0.149 0.205 0.036 1.10 x I U 4
Reactor pressure (MPa) 9.7- 10.2 10 422.45 471.0 0.184 0.258 0.058 1.43 X 10.'
Reactor holdup (s) 1.54-3.2 343- 387 428.95 468.0 0.286 0.232 0.093 2.59 x 10
Molar ratio:
olefin/aluminum alkyl 23- I40
Molar ratio:
ethylene/aluminum bonds* 0.16- I .83 gas chromatograph with a capillary column. The on-line
results were used only to monitor the progress of the reac-
*There are 3 aluminum bonds per mole of aluminum alkyl
tion. The off-line results are reported here.
The I cm3 reactor system consisted of a carbon steel
PELARGONIC ACID reactor composed of a mixing section and a reactor section.
The reactor section was 5.4 cm long and 0.47 cm in di-
ameter. Trioctylaluminum (AlOct,) was fed into the mixing
34.5kPo N2 section at ambient temperature where it was mixed with
BLANKET hexene-1 which was heated to 30-40°C above the reactor
CATALYST FEED operating temperature. The reactor operating conditions are
ETHYLENE FEED presented in Table I . The reactor effluent was analyzed
AIR DRIVEN on-line and off-line as previously described.
STIRRER
ELECTRIC BENCHSCALE
-
PR E H EATER REACTOR

The bench scale reactor experiments were performed in a

175 cm3 plug flow reactor, shown in Figure 3, which con-
sisted of a coil of 3/8-in. dia. carbon steel tubing 622 cm

-
long with an 1.D. of 0.6 cm. The coil was immersed in a
HEATING OIL constant temperature oil bath. Ethylene, preheated to
(ESSOTHERM N l W C , was mixed with aluminum alkyl at the inlet of the
reactor. Two catalyst feeds were used in these experiments.
tributylaluminum and trihexylaluminum. The operating
086cmI D conditions of the bench scale reactor are presented in
622cm CA Table 1. The reactor effluent was analyzed as previously
STEEL CO

ELECTRIC HEATERS
z
1
described.

Experimental results

DISPLACEMENT
REACTION KINETICS
Figure 3 - Diagram of bench scale reactor system.
In order to determine the kinetic rate constant for the
displacement reaction, Equation (5)

stirred autoclave 6.3 cm in diameter and 4.8 cm in height. ko

The reactor was injected with octene-l (10 cm'/min @
99.1 wt.%), tributylaluminum (6 cm3/min @ 85 mmol/L in
an n-heptane solvent), and n-heptane (6 cm3/min @
99 mole %). This resulted in a steady state reactor concen-
tration of 2896 mmol/L of olefins and 23.2 mmol/L of
aluminum alkyls. The reactor was operated at various tem-
peratures from I33 to I55"C, and at a pressure of 10 MPa.
The reactor effluent was reacted with pelargonic acid in
order to liberate the alkyl group from the aluminum alkyls
in the form of alkanes. Otherwise the aluminurn alkyls pre-
cipitate out on the gas chromatograph column packing. The
detection and analysis of the alkanes is an indication of the
presence of the corresponding aluminum alkyl. The effluent
was then analyzed on-line using a Varian Model 3700 gas
chromatograph with a 5486 mm by 0.318 mm SS column
with 9.3% OVlOl on 100/120 Chromosorb W, in combina-
tion with a Valco high pressure sampling valve. Samples
were further analyzed off-line using a Varian Vista Series
Al(CnH2nt 113 + 3CmH~w 3CnH2n
k-D
+ AI(C,nH2,n+1)3. . . . . . . . . . . . . . . . . . . . . . , .. . . (5)
it was assumed that the rate constants were the same for all
aluminum alkyl-olefin reactions, thus kD = k - D . This is a
common assumption required due to the complexity of the
system (Albright and Smith, 1968). The kinetic data are
summarized in Tables 2 and 3. A non-linear regression
analysis was carried out to obtain the parameters for the
Arrhenius equation. The SAS (Statistical Analysis System),
library subroutine NLIN (using the Marquardt non-linear
least squares method) was employed in the analysis. The
NLIN (Non-LINear) routine requires as inputs the rate
constants, temperatures, parameter estimates (the pre-
experimental factor and the activation energy) and the form
of the Arrhenius equation. The routine then simultaneously
adjusts the two parameters to minimize the residual sum of
squares. The experimental data, along with the Arrhenius

820 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING, VOLUME 62, DECEMBER 1984
 TABLE3
Displacement Reaction Rate Constants in 1 cm' Plug Flow Reactor
T Holdup Hexene Hexane
(OK) (S) Q 70 % k (m'/kmol * s)

518.15 2.13 0.87 54.2 8.1 0.2850

517.65 2.09 0.92 57.1 4.9 0.0975
524.95 2.12 0.90 60.4 6.2 0.0913
525. I5 2.72 0.92 44.6 3.7 0.1310
523 S O 1.92 0.98 78.4 1.2 0.2520
523.30 2.13 0.978 68.5 1.6 0.2900
531.10 2.02 0.97 67.9 2.16 0.5 150
545.30 2.00 0.97 67.9 2.10 0.61 10
540.70 1.54 0.97 67.9 1.99 0.7750

0 0.2 0.4 0.6 0.8 I 1.2 1.4 1.6 1.8 2

N , ETHYLENE MOLES PER 113 MOLES TRIBUTYL ALUMINUM

Figure 5 - Yield butene as a function of average moles of ethyl-

ene added to each mole aluminum bonds with aluminum tributyl
feed.

2) The displacement reaction:

+ 3C,,Hz,,
AI(C,,H~,,+I), F= 3C,,H2,1
kD

k-D

+ Al(C,,,H2,,,+i),. . . . . . . . . . . . . . . . . . . . . . . . . . . ( 5 )
( n = 2, 4, 6, 8, ...)
( m = n + 2, n 4, n + + 6, n + 8, ....)
In this work, n and rn in Equation (5) were limited to 14
and 16, respectively. Using even numbered alkyl groups,
this produces 56 possible reactions. The kinetics for the
displacement reaction were determined here; the Arrhenius
i expression for the displacement reaction is:
kD = (1.667)( 10l2)exp [ -( 1.2988 X 108)/RT] . . . (8)
The experimental results from the bench scale reactor are
19 20 21 22 23 24 25 26
plotted in Figures 5 to 9.
RECIPROCAL TEMPERATURE, I / T x lo4,( O K - ' )

Figure 4 - Arrhenius plot for displacement reaction.
non-linear regression line is plotted in Figure 4. Discussion
of all results is contained in the Discussion of Results
section.
BENCHSCALE REACTOR
The bench scale reactor was simulated using the ASPEN
plug flow reactor model. Two types of reactions occur:
1) Chain growth reaction:
kG
AKCnH2,tlh + 3CzH.4 +A ~ ( C ~ + Z H .~. ~. .+. .A(6)
( n = 2, 4, 6, 8, ....)
For the current work, n was limited to 16. This gives a
total of 8 reactions. Kinetics for this reaction were taken
from the work by Albright and Smith (1968). The Arrhenius
expression for the growth reaction is:
kc = (8.6)(lO5) exp [-(6.279 x 107)/R7'] . . . . . . . (7)
ASPEN simulation
The ASPEN plug flow reactor model RPLUG was used to
simulate the operation of the bench scale reactor. The use of
RPLUG requires kinetic data for a kinetic model, either
user-supplied or a built-in power law model. In this work,
the built-in power law model was used; the information
required by the user for RPLUG is summarized below:
- reactor temperature and pressure (and profiles if
required)
- reactor length and diameter
- reaction stoichiometry
- pre-exponential factor
- activation energy
- exponential constants
The reactor was operated under isothermal and isobaric
conditions, and therefore no temperature or pressure profiles
were required. The reactor size was specified as 622 cm
long and 0.6 cm in diameter. The stoichiometric coeffi-
cients, vitrfor each of the 64 possible reactions (8 growth
reactions, 56 displacement reactions), were specified. The
pre-exponential factor, K,, and the activation energy, E,,
were specified for the growth and displacement reactions by

THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING, VOLUME 62, DECEMBER 1984 82 I

 --
- THEORETICAL I -THEORETICAL
-z
-
80 0 EXPERIMENTAL
-z 80 0 EXPERIMENTAL

--
E"
z 60
0 0

.
t-
V 0
a 0
K

\\- K.= 1.667 x 10l4 0

," 20
-1 K K = 1.667 x 10''

0 0.2 0.4 0.6 0.8 I 1.2 1.4 1.6 1.8 2 0 0.2 0.4 0.6 0.8 I 1.2 1.4 1.6 1.8 2
N, ETHYLENE MOLES PER 113 MOLES TRIBUTYL ALUMINUM N, ETMYLENE MOLES PER 113 MOLES TRIHEXYL ALUMINUM

Figure 6 - Yield hexene as a function of average moles of ethyl- Figure 8 - Yield hexene as a function of average moles of ethyl-
ene added to each mole of aluminum bonds with aluminum tributyl ene added to each mole of aluminum bonds with aluminum trihexyl
feed. feed.

-z
-
too

80
__ THEORETICAL
0 EXPERIMENTAL
-z
-
100

80
_-0
THEORETICAL
EXPERIMENTAL

-P- -z-E 60
z 60
0 -t-0
lt-J V
a 0
a
K
LL

1
40 40
m m 6 7 x 10"
V V
-I -I
K K = 1.667 x 10" a
2 +
0
+ 20

0 0.2 04 0.6 0.8 I 1.2 1.4 1.6 1.8 2 0 0.2 0.4 0.6 0.8 I 1.2 1.4 1.6 1.8 2
N, ETHYLENE MOLES PER 113 MOLES TRIWJTYL ALUMINUM N, ETHYLENE MOLES PER 113 MOLES TRIHEXYL ALUMINUM

Figure 7 - Yield octene as a function of average moles of ethyl- Figure 9 - Yield octene as a function of average moles of ethyl-
ene added to each mole of aluminum bonds with aluminum tributyl ene added to each mole of aluminum bonds with aluminum trihexyl
feed. feed.

Equations (5) and ( 6 ) , respectively. The exponential con- likely that a system of 17 simultaneous equations repre-
stants ark were assumed to be unity, reflecting bi-molecular senting 64 chemical reactions would exhibit stiffness with
reactions. certain species being produced or consumed at rates signifi-
The amount of each chemical species was calculated as a cantly different than others. The ASPEN predictions for the
function of position in the reactor, z , by: yields of the bench scale reactor are plotted in Figures 5
to 9.
dF,/dz = Ar, . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . (9)
The reaction rate of component i , r,, is calculated using the Discussion of results
power law model, Equation (10).
Nr N<
The discussion of results focusses on the appropriateness
ri = F C v i k ~exp
k= I
, , (- &/m) n
i= I
. ....
c l u # ~. . (10)
of the results, the trends, and sources of errors. Before
proceeding further we feel it necessary to emphasize the
complexity of the system studied. The reaction system con-
where F is the total molal flow rate. sists of 64 simultaneouschemical reactions (8 for the growth
Equation (9) is solved for Fi = f ( z ) using a method reaction and 56 for the displacement reaction) involving 17
proposed by Gear (1971). This method has been widely chemical species. Displacement kinetics were obtained by
accepted for stiff systems of differential equations. Al- using feeds of octene- 1 and tributylaluminum in a 150 cm3
though the equations have not been tested for stiffness, it is CSTR and hexene-1 and trioctylaluminum in a I cm3 plug

822 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING, VOLUME 62, DECEMBER 1984
flow reactor. The kinetics (growth reaction from Albright
and Smith (1968), and the displacement reaction from this
work) were then used in the ASPEN plug flow reactor model
to simulate a bench scale reactor using feeds of ethylene
and tributylaluminum and ethylene and trihexylaluminum in
a 175 cm’ plug flow reactor. In other words, four different
feed systems in three different reactors were used.
In Figure 4 the agreement between the best fit line and the
experimental data is good, especially at low temperatures.
At higher temperatures there is more scatter which is due in
part to the fact that a different reactor was used to generate
the high temperature data. The low temperature results were
obtained from the 150 cm’ CSTR while the high temperature
results were obtained from the 1 cm3 plug glow reactor. A
significant difference exists between the hold-up in the two
reactors; in the CSTR the hold-up was about 410 s and in the
plug-flow reactor about I .75 s. As a result, the 1 cm3 plug
flow reactor was somewhat more difficult to control. Small
absolute errors in flow rates are reflected in relatively large
errors in hold-up and ultimately in the reaction rate. In the
calculation of the reaction rate constant, k,, second order
kinetics were assumed. The fact that the resultant Arrhenius
plot is straight suggests that this assumption is valid.
Figure 5 is a plot of the total C, fraction (olefins and
alkanes) in the effluent of the bench scale reactor as a func-
tion of the amount of ethylene added to the reactor. When
no ethylene is added, no chemical reaction takes place and
the effluent is identical to the feed (butene + tributyl-
aluminum), i.e., a 100% C4 fraction. As more ethylene is
added, more of the tributylaluminum is grown to high alu-
minum alkyls by the chain growth reaction of Equation (4),
and the total C4fraction decreases. The trend of decreasing
C4 fraction with increased addition of ethylene is predicted
by the power law model and supported (with the exception
of one data point) by experimental measurements. The ap-
parent bias in the experimental data (all of the points lie
above the predicted curve) is discussed below. The dashed
curves on each plot (representing predictions based on dis-
placement reaction rates 100 times greater than those ob-
served experimentally) are also discussed below with refer-
ence to the bias.
Figures 6 and 7 are plots of the c6 and C8 fractions as
functions of the amount of ethylene added. In both cases the
initial concentrations, when no ethylene has been added, are
zero. This is reasonable since when n = 0 no chain growth
occurs and only tributylaluminum (C,) is present in the
reactor. As n increases, the chain growth reaction begins
and some tributylaluminum (C,) growth to produce tri-
hexylaluminum (c6) and trioctylaluminum (CE), etc. As
more ethylene is added, more trihexylaluminum is produced
which in turn produces more trioctylaluminum. Eventually
the concentration of trihexylaluminum reaches a maximum
and begins to decrease as the rate of its consumption (to
produce trioctylaluminum) exceeds its rate of production
(from tributylaluminum). Again this trend is exhibited by
experimental measurement; however, a bias exists in the
data (they are all scattered below the theoretical curve).
Figures 8 and 9 represent the C6 and CEfractions in the
effluent of the bench scale reactor when using a tri-
hexylaluminum catalyst (instead of tributylaluminum).
Figure 8 shows the C6 fraction decreasing from 100% at
n = 0. This is analogous to the behaviour exhibited in Figure
5 . The experimental data support the trend predicted by the
power law model and although a slight bias is observed, a
better fit of the data was achieved. The main reason for the
THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING, VOLUME 62, DECEMBER 1984
improved fit may be the fact that more than twice as many
experimental data points were taken in Figure 8. Figure 9
represents the CE fraction as a function of n using a tri-
hexylaluminum catalyst. At n = 0 the mole percent CE
fraction is zero because no growth had taken place. As the
amount of ethylene added is increased the higher the Cs
fraction until a maximum is reached, at which point the rate
of production equals the rate of consumption (to produce
higher alkyls). Here again the experimental data support the
trend but exhibit considerable scatter and definite bias.
There is a considerable amount of scatter in the bench
scale reactor data. This scatter may be primarily attributed
to error in the product analysis. The calibration factors for
the G.C. analysis are very sensitive to column pressure,
temperature, and injection sample size. The aluminum alkyl
deactivation products cause considerable problem in the
sampling system with the gradual buildup of residue, this
despite product stream filtration prior to sampling. A further
complication in sample analysis is the low product con-
centrations, typically of the order 3 X to 2.5 X
mmol/L. Feed flows, concentration, and ethylene con-
sumption are considered to be accurate.
The major source of uncertainty in the determination of
reaction rate constants is the error in concentration mea-
surements (Hill, 1977). Attempts to improve the accuracy of
the rate constants should focus on trying to improve the
accuracy of concentration measurements. Bensen ( 1960)
has shown that for an analytical error of about 2%, the level
of uncertainty in the resulting k value is about 15%. Our
analytical errors have been estimated to be about 10%;this
translates into about a 75% level of uncertainty in each
estimated k. Reaction kinetics were determined over a rela-
tively large temperature range from 110 to 272°C; this re-
sulted in a range of k from 3.55 X to 0.775 m3/
kmo1.s. Despite the high level of uncertainty in each esti-
mate of k, the rate constants of displacement are signifi-
cantly less than those for the growth reaction. Furthermore,
the wide range of experimental k values allowed for a
good estimation of the Arrhenius constants. The estimated
Arrhenius constants are thus adequate for the present reactor
simulation.
The apparent shift or bias of the experimental data points
from the model may be due to greater than expected dis-
placement, catalyzed by nickel residue. The problem of
nickel contamination was particularly evident in earlier ex-
perimental work when some of the reactor feed lines and
solvent storage facilities were 316 SS. Replacement of 316
S S by carbon steel greatly reduced the displacement, as
measured by the ratio of alkane to alkene. Recall that al-
kanes were produced when aluminum alkyls were reacted
with pelargonic acid; alkanes are therefore indicative of
displacement. However, a few 316 S S fittings (e.g.
couplings and valves) are still present in the system. To
demonstrate the effect that an increased displacement reac-
tion rate would have on the theoretical predictions, the pre-
exponential factor, Kk,was increased by a factor of 100from
Kk= 1.1667 x 1Oi2tOKk= 1.667 x 1Oi4m3/kmol.S.The
results are shown by the dashed lines in Figures 5 to 9. The
predicted trend is as expected. The goodness of fit between
the data and the theoretical curve still leaves something to be
desired in certain cases. An improved fit may be possible
with better data, by using a different model, or by deter-
mining the values of Kk and Ek for each reaction individu-
ally. Since the purpose of this work was to obtain informa-
tion on the kinetics of the displacement reaction for the
823
purposes of preliminary plant design, this additional work
was not performed.
Statistical analysis of the bench scale reactor model indi-
cates that in the case of the bench scale reactor with tributyl-
aluminum catalyst, the model was significant at a 10%sig-
nificance level. For growth with trihexylaluminum catalyst,
the model was significant at a 1.O% significance level. The
difference in the significance levels with the two sets of data
may be partly attributed to the difference in the number of
data points used in the analysis. This analysis indicates that
the errors are primarily experimental errors and not due to
the model. It is important to note that we are using a the-
oretical model (the power law model, Equation (10)). We
did not use an empirical model to fit the data.
It is important to stress that with all the complications and
experimental difficulties of this system the predicted results
are satisfactory from an industiral point of view, and can be
used as the basis for at least preliminary design.
Conclusions
I . The kinetics for the displacement reaction of the alpha
olefin-aluminum alkyl system have been estimated.
2. A bench scale plug flow reactor in which growth and
displacement reactions took place was simulated using
ASPEN. The power-law kinetic model appears to be an
adequate model of the system of 64 simultaneous chem-
ical reactions. Most of the deviation of the data from the
model is due to experimental error.
3 . Further work is required to obtain better experimental
data of this process. With improved data an accurate
evaluation of the adequacy of the power law model can
be made.
4. ASPEN, using a GEAR stiff integration routine, was
able to successfully integrate a system of 17 simulta-
neous (and likely stiff) differential equations.
5 . Nickel impurities likely catalyzed the displacement reac-
tion in the bench scale reactor and were responsible for
the bias in the experimental results with respect to the
model predictions. ASPEN correctly predicted the bias
trend when the displacement reaction rate was increased.
6. The fact that multiplying the displacement rates by I00
had a modest effect-on the simulation suggests that the
rate coefficients need not be known very accurately.
Changes in the activation energy will naturally have a
greater effect than similar changes in the pre-exponential
factor.
Acknowledgements
This work was supported under an NSERC Operating Grant
(P. L. Douglas) and a grant from Du Pont Canada Inc. The authors
824 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING, VOLUME 62, DECEMBER 1984
wish to express their gratitude for the active participation of Du
Pont Canada Inc. in this study.
Nomenclature
A = cross sectional area of plug flow reactor (m’)
o , ~ = exponential constant in Power Law
B = function of reaction conditions, Equation (3)
c, = concentration of component i (kmol/m’)
El = activation energy for power law expression (J/kmol)
F = mole flow (kmol/h)
k = rate constant for bench scale reactor (m’/kmol* s)
k, = displacement rate constant (m’/kmol - s )
Kk = pre-exponential constant (m’/kmol a s )
kG = growth reaction rate constant (m’/kmol.s)
n = moles ethylene added/mole aluminum bonds
N, = number of chemical reactions
N, = number of chemical species
P = number of ethylenes added
Q = conversion of aluminum alkyl
R = gas constant (8314.39 J/kmol OK)
r, = reaction rate ( s c ’ )
T = temperature ( O K )
X(P) = fraction of olefin having 2(P + I ) carbons
v , ~ = stoichiometric coefficient for component i in reaction k
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Manuscript received December 2, 1983; revised manuscript re-
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