1828 Ind. Eng. Chem. Res.

2008, 47, 1828-1834

Synthetic Jet Fuel Production by Combined Propene Oligomerization and

Aromatic Alkylation over Solid Phosphoric Acid
Tebogo M. Sakuneka,* Arno de Klerk, Reinier J. J. Nel, and Andrew D. Pienaar
Fischer-Tropsch Refinery Catalysis, Sasol Technology Research and DeVelopment,
P.O. Box 1, Sasolburg 1947, South Africa

The oligomerization of propene, as well as the alkylation of benzene and toluene with propene, was evaluated
at 160-240 °C, 3.8 MPa, and aromatic to olefin ratios of 1:6 to 6:1 using solid phosphoric acid (SPA) as a
catalyst. It was found that steric effects were more important than electronic effects in determining alkylation
rate and selectivity. Monoalkylation was favored even at the lowest aromatic to olefin ratio, and the isomer
distribution of dialkylated aromatics remained constant irrespective of the conversion or operating conditions.
No transalkylation or alkylbenzene isomerization activity was observed. It was shown that olefin oligomerization
and aromatic alkylation could be combined in a single SPA catalyzed reaction system to produce a synthetic
jet fuel that meets Jet A-1 specifications.

Introduction
Propene is the most abundant unsaturated hydrocarbon that
is obtained from high-temperature Fischer-Tropsch (HTFT)
synthesis, with more than 10% of the total organic product being
propene.1 It is desirable to recover the propene for the production
of high value chemicals, such as polypropylene, but this is not
always practical. Fischer-Tropsch based coal-to-liquids (CTL)
and gas-to-liquids (GTL) plants are normally located close to
coal and gas reserves. The coal and gas reserves may be in
remote locations that are far from propene consumers, which
are typically associated with petrochemical facilities. Crude oil
refineries may encounter a similar problem, in which case the
propene is used within the refinery to produce transportation
fuels. Indeed, as much as 40% of the propene produced by Figure 1. Main products from a combined solid phosphoric acid catalyzed
residue upgrading during crude oil refining is not recovered and process for the alkylation of benzene and toluene with propene and the
oligomerization of propene.
is used for motor-gasoline production by aliphatic alkylation
(60%) and olefin oligomerization (40%) processes.2 However,
it is not desirable to use aliphatic alkylation in a Fischer-
used as a fully synthetic jet fuel. On a conceptual level such a
Tropsch refinery, since it increases the refinery complexity and
process would have to produce a highly isomerized product to
its environmental footprint.3 It is preferable to make use of olefin
meet the freezing point specification and be able to either
oligomerization, with both solid phosphoric acid (SPA) and
produce some aromatics, or alkylate aromatics from another
zeolite (ZSM-5) based processes being commercially used in
source in the refinery. Of the commercially available technolo-
HTFT refineries.4,5
gies it was found that only a ZSM-5 based process could
A reevaluation of propene as a building block for the
produce aromatics and branched aliphatics from propene. Its
production of synthetic jet fuel was sparked by an interest in
applicability to jet fuel production is unfortunately limited, since
Fischer-Tropsch technology as a means to produce jet fuel
only a small fraction of product distills in the kerosene boiling
meeting military requirements,6,7 called Battlefield Use Fuel of
range.9 Patent literature suggested that aromatic alkylation in
the Future (BUFF). The key properties of such a fuel is a
maximum freezing point of -47 °C, a minimum flash point of combination with oligomerization was in principle a possibil-
60 °C, and a maximum viscosity of 8 cSt at -20 °C. The United ity,10 but no commercial processes were found that combined
States Department of Defense indicated that the minimum these two transformations to produce jet fuel. It was nevertheless
density requirement of Jet A-1 (775 kg‚m-3) is of secondary noted that oligomerization occurred as a side reaction during
importance, but it was realized that at least some aromatics are aromatic alkylation and that it should, in principle, be possible
needed to provide elastomer compatibility. These fuel properties to devise a combined process. The three main catalyst types
can be achieved by blending Fischer-Tropsch and crude oil used for the alkylation benzene and toluene with propene are
derived kerosenes.8 Yet, to make Fischer-Tropsch a truly MCM-22, β-zeolite, and SPA.11-13 Of these, only SPA is used
strategic technology, it must be possible to produce a fully commercially for olefin oligomerization. On closer inspection
synthetic jet fuel that meets all BUFF requirements. it was found that SPA had other advantages. The carbon number
Using propene as the main building block, a process was distribution during SPA catalyzed propene oligomerization is
sought to produce kerosene that would have the potential to be limited,14 resulting in a kerosene-rich product, especially during
tetramer mode of operation.15 SPA also has a higher selectivity
* To whom correspondence should be addressed. Tel.: +27 16 960- to monoalkylated aromatics during aromatic alkylation with
4925. Fax: +27 11 522-8288. E-mail: tebogo.sakuneka@sasol.com. propene than zeolite catalysts, such as MCM-22.13
10.1021/ie0710566 CCC: $40.75 © 2008 American Chemical Society
Published on Web 02/22/2008

Figure 2. Effect of aromatic to olefin ratio on the alkylation rate of benzene
with propene over SPA at 3.8 MPa in a batch reactor at 160 (9), 180 (b),
and 220 °C ([).
Figure 3. Effect of benzene to propene ratio on the propene oligomerization
rate over SPA at 3.8 MPa in a batch reactor at 160 (9), 180 (b), and
220 °C ([).
In this paper we investigate the possibility of using SPA as
a catalyst to carry out aromatic alkylation and olefin oligomer-
ization with propene in a single process (Figure 1) to produce
mainly jet fuel. The study focuses on the catalysis to prove the
concept and does not deal extensively with the fuel properties
of the product.
Experimental Section
Materials. The catalyst used for the alkylation/oligomeriza-
tion studies was a commercial C84-3 solid phosphoric acid
(SPA) obtained from Süd-Chemie Sasol Catalysts, manufactured
in Sasolburg, South Africa. Characterization data for this catalyst
have been reported previously.16 A batch of this SPA catalyst,
which was obtained as extrudates, was crushed to a particle
size of <150 µm and stored in a desiccator to minimize any
possible differences in catalyst hydration between the different
experiments. All the experiments were conducted using this
batch of catalyst. Crushing of the catalyst was an attempt to
minimize any possible mass transfer limitations.
The propene feed used was obtained from Sasol Monomers
Division in Sasolburg, South Africa. The purity of this material
was determined by gas chromatographic analysis and found to
be 96.16% propene with the balance being ethane (1.88%),
ethene (0.14%), propane (1.43%), C6 hydrocarbons (0.10%),
and C7 hydrocarbons (0.29%). Benzene (+99.7%) was obtained
from NT Laboratory supplies, and toluene (99%), p-cymene (4-
methyl-1-isopropylbenzene, 99%), and the n-tetradecane (+99%)
solvent used were obtained from Aldrich. Nitrogen (99.999%)
was obtained from Afrox. All the chemicals were used without
any pretreatment.
Ind. Eng. Chem. Res., Vol. 47, No. 6, 2008 1829
Figure 4. Effect of aromatic to olefin ratio on the alkylation rate of toluene
with propene over SPA at 3.8 MPa in a batch reactor at 160 (9), 180 (b),
and 220 °C ([).
Figure 5. Effect of toluene to propene ratio on the propene oligomerization
rate over SPA at 3.8 MPa in a batch reactor at 160 (9), 180 (b), and
220 °C ([).
Procedure. The reactions were conducted using stainless steel
autoclave batch reactors with a capacity of 150 mL, and a
detailed description of the reactor setup has been reported
previously.16 The inertness of the reactor was confirmed by
conducting a blank reaction experiment at 220 °C, whereby only
propene and the aromatic feed were charged into the reactor
without any SPA catalyst. No oligomerization or alkylation
reaction products were detected in the product from the blank
experiment.
In a typical catalytic experiment, the reactor was preloaded
with the catalyst (0.3 g), a magnetic stirrer bar, aromatic feed,
and the n-tetradecane solvent and was leak-tested with nitrogen
at 5.0 MPa. The pressure was then reduced to about 0.5 MPa
and the reactor heated to the desired temperature, upon which
the propene feed was introduced via a nitrogen-pressurized
system and the pressure adjusted to 3.8 MPa. Sampling was
also carried out as described previously16 and analyzed as
outlined below.
To quantify and identify the different components in the
product samples, a gas chromatograph equipped with a flame
ionization detector (GC-FID, Agilent 6890N) and gas chroma-
tography-mass spectrometry (GC-MS, Agilent 6890N +
5973N) were used, respectively. For component separation, both
instruments were fitted with HP Pona methylsiloxane columns,
50 m × 200 µm × 0.5 µm. The temperature program started at
40 °C with a hold time of 5 min, followed by a temperature
ramp of 4 °C/min to 120 °C and then to 300 °C at 20 °C/min.
A response factor of 1.00 was used for all the alkylbenzenes,
but for benzene a factor of 1.12 was used. This is in line with
work reported in the literature.16,17
1830 Ind. Eng. Chem. Res., Vol. 47, No. 6, 2008

Table 1. Product Selectivity at ∼10% Benzene Conversion in the Presence of Propene over SPA at 3.8 MPa in a Batch Reactora
product selectivity (%)
temp (°C) benzene:propene (mol/mol) benzene conversion (%) cumene DIPB C6 olefins C9 olefins C12 olefins
160 6:1 3.1 88.6 0.6 3.2 7.1 0.5
1:1 11.9 84.2 2.3 8.8 4.5 0.2
1:6 10.1 53.1 1.9 28.2 16.3 0.5
180 6:1 11.7 84.2 2.3 8.8 4.5 0.2
1:1 13.6 82.3 2.4 9.8 5.3 0.2
1:6 14.2 49.7 4.6 22.4 22.8 0.5
200 6:1 11.6 96.3 2.2 1.1 0.2 0.2
1:1 13.2 83.4 4.1 8.1 4.3 0.1
1:6 9.0 59.4 3.7 21.2 15.1 0.6
220 6:1 12.8 91.2 2.7 3.4 2.6 0.1
1:1 10.3 83.4 4.5 7.5 4.4 0.2
1:6 9.0 60.7 5.2 17.2 16.5 0.4
240 1:1 10.5 88.0 5.7 4.2 1.9 0.2
a The diisopropylbenzene (DIPB) isomers were identified and occurred in the same ratio in all experiments.

Table 2. Product Selectivity at ∼10% Toluene Conversion in the Presence of Propene over SPA at 3.8 MPa in a Batch Reactora
product selectivity (%)
temp (°C) toluene:propene (mol/mol) toluene conversion (%) o-cymene m-cymene p-cymene DIPT C6 olefins C9 olefins
160 5:1 4.5 21.9 10.3 12.3 1.4 54.1 0
1:1 9.1 39.7 18.5 25.4 3.0 9.4 4.0
1:6 6.3 24.7 11.5 17.2 2.5 29.5 14.6
180 1:1 9.7 41.4 20.0 24.4 3.3 7.9 3.0
220 5:1 8.8 43.2 21.7 25.6 2.9 4.2 2.4
1:1 8.4 39.5 20.0 23.9 3.9 11.6 1.1
1:6 10.3 27.9 14.2 17.2 6.4 13.6 19.9
a The individual diisopropyltoluene (DIPT) isomers were not identified.

The alkylation and oligomerization rates were calculated from
the alkylated products and the C6, C9, and C12 oligomer products,
respectively. Effort was made to identify the alkyl aromatics
by using standards, as well as GC-MS with selective ion
extraction. However, not all species could be identified, and
some products were lumped together based on product class.
For example, the different olefin oligomers were grouped
together according to carbon number and were not individually
identified. As the unreacted aromatic and the propene flashed
during sampling, the reacted amounts were back-calculated from
these different product components. The method used to
calculate the initial rates reported in this paper has been
described in a previous study.16
Results
Alkylation of Benzene with Propene. It is an established
commercial practice to use a high aromatics to olefin ratio,
typically 6:1 to 8:1, to limit propene oligomerization during the
alkylation of benzene with propene.12 Even at such a high
dilution of the propene, the selectivity of propene to oligomers
is still in the order of 8-9%.18 When jet fuel is targeted as
product, both oligomerization and alkylation are desirable
reactions and operation at lower aromatic to olefin ratios can
be considered, which was investigated experimentally.
When the SPA catalyst was used, however, the benzene
alkylation rate (Figure 2) and propene oligomerization rate
(Figure 3) responded differently to changes in aromatic to olefin
ratio and temperature. Increasing the aromatic to olefin ratio
from 6:1 to 1:1 resulted in an increase in both the alkylation
rate and the oligomerization rate. It should also be noted that
the alkylation rate was always higher than the oligomerization
rate over this range of aromatic to olefin molar ratios. Also noted
from Figure 2 is that, irrespective of the reaction temperature,
the alkylation rate passed through a maximum at a 1:1 ratio,
while Figure 3 shows that the oligomerization rate increased
with increasing olefin concentration. A slight difference in both
the oligomerization and the alkylation rates was observed at
temperatures between 160 and 180 °C. At 200 °C and higher,
a sharp increase in the oligomerization rate was observed for
propene-rich mixtures (Figure 3).
Differences in alkylation and oligomerization rates not only
affected the ratio of alkylbenzenes to oligomeric olefins, but
also affected the product selectivity within these categories
(Table 1). The most notable difference was in the relative
abundance of C6, C9, and C12 olefins. As can be expected, the
selectivity to these olefins was more pronounced at higher
temperatures and under conditions where the feed was olefin-
rich. Irrespective of the temperature, the formation of these
olefins was almost always in the order C6 g C9 > C12. Although
not reported in Table 1, less than 0.1% C15 oligomers was
observed and no material heavier than C15 olefins were detected
in the product. Predictably, the ratio of mono- to dialkylated
benzene showed a decrease in monoalkylation with increasing
temperature, and the same trend was observed with increasing
olefin feed concentration, especially at feed ratios of 1:1 to 1:6
of benzene to propene. Although the total amount of the
dialkylated benzene products formed varied at different condi-
tions, the isomer ratio of the three dialkylated benzene species
remained constant: 1,2-diisopropylbenzene (23%), 1,3-diiso-
propylbenzene (37%), and 1,4-diisopropylbenzene (40%). No
n-propylbenzene was detected in any of the products.
Alkylation of Toluene with Propene. Toluene was expected
to react in an analogous way to benzene, but it was not clear
whether steric or electronic effects would dominate reaction
selectivity. The methyl group increases the steric bulk of the
molecule and could hinder alkylation, but the methyl group also
has an inductive effect on the aromatic ring,19 increasing the
nucleophilicity of toluene compared to benzene. The alkylation
of toluene with propene was investigated experimentally at
aromatic to olefin feed ratios similar to the study with benzene,
but only in the temperature range 160-220 °C.
 Ind. Eng. Chem. Res., Vol. 47, No. 6, 2008 1831

Table 3. Product Selectivity during Propene Conversion over SPA at 180 °C and 3.8 MPa in a Batch Reactor
selectivity (%)
time (h) conversion (%) C6 olefins C9 olefins C12 olefins
0 <1 6 56 38
0.5 2 63 33 4
1.0 5 61 37 2
1.5 7 56 43 1
2.0 12 53 46 1

Table 4. Jet A-1 Specifications and Properties of the Kerosene Range Hydrogenated Oligomers from Olefin Oligomerization over SPA
(Isoparaffinic Kerosene), As Well As Calculated Mixtures Thereof with Alkylated Aromatics (91% Cumene and 9% Diisopropylbenzene)
IPK blend with IPK blend with
fuel properties Jet A-1 specifications hydrogenated oligomers (IPK)31 8% alkylbenzenes 24% alkylbenzenes
heat of combustion (MJ‚kg-1), min 42.8 44 43.8 43.3
freezing point (°C), max -47 < -65 < -65 < -65
flash point (°C), min 38 53 52.5 51.5
density at 20 °C (kg‚m-3) 771-836 765 773 789
viscosity at -20 °C (cSt), max 8 3.2 ∼3 ∼3
aromatic content (vol %) 8-25 0.5 8.5 24.4
naphthalene content (vol %), max 3 0 0 0
sulfur content (mass %), max 0.3 <0.001 <0.001 <0.001
mecaptan content (mass %), max 0.003 <0.001 <0.001 <0.001
acidity (mg of KOH/g), max 0.1 0.004
smoke point (mm), min (no.) 25 42
distillation (°C)
IBP - 174 152 152
T10, max 205 181 175 152
T20, max - 182
T50, max - 188
T90, max - 210
final boiling point, max 300 232 232 232

The alkylation rate (Figure 4) and oligomerization rate (Figure
5) observed during the experiments were plotted as a function
of toluene to propene feed ratio. Trends similar to those observed
with benzene alkylation were observed with toluene alkylation.
The alkylation rate (Figure 4) goes through a maximum as the
feed ratio is varied from an olefin-lean environment to an olefin-
rich environment, and under such conditions the oligomerization
rate (Figure 5) increases with an increasing concentration of
olefins.
Neither temperature nor toluene to propene ratio affected the
ratio of cymene isomers (Table 2), which remained constant at
o-cymene (48%), m-cymene (23%), and p-cymene (29%). No
n-propyltoluene was detected in any of the products. Dialky-
lation to produce diisopropyltoluene (DIPT) increased with
propene concentration and temperature, although the overall
selectivity to alkylation products decreased. Oligomerization
yielded mostly C6 olefins (dimer), except under propene-rich
conditions, when the C9 olefins (trimer) became more abundant.
Less than 1% C12 and heavier olefins were found in the product.
Nonintegral multiples of propene were not seen, expect in the
product from propene-rich reaction at 220 °C, where some C7-
C8 olefins were detected.
Oligomerization of Propene. The oligomerization selectivity
pattern observed during the alkylation of benzene and toluene
with propene (Tables 1 and 2) was not the same as expected
from other studies.20,21 A remarkably high C6 olefin (dimer)
selectivity was found, while in other propene oligomerization
studies the C9 olefin (trimer) had been the dominant oligomer.
To check whether this was just a solvent effect due to the
n-tetradecane, as noted in the alkylation studies with 1-pentene,16
an experiment was carried out with propene in the absence of
benzene and toluene (Table 3).
The initial selectivity of propene oligomerization resembled
that expected from the literature, but the selectivity changed
considerably to yield a product rich in C6 olefins. As time
progressed, the ratio of C6 to C9 olefins changed in the direction
of the C9 olefins, but it was clear that the n-tetradecane solvent
influenced the selectivity behavior. The observed oligomeriza-
tion selectivity pattern was similar to that found during the
alkylation experiments.
Transalkylation of Cymene. The high monoalkylation
selectivity of SPA reported in the literature13 was confirmed
by the present work (Tables 1 and 2). To establish the
contribution of transalkylation and isomerization to the product
distribution, p-cymene was heated to 180 °C in the presence of
SPA catalyst at 3.8 MPa, following a procedure similar to that
used for the other experiments. Product samples collected over
a period of 6 h indicated that no change in the cymene isomer
distribution took place and no other products were formed.
Discussion
Product Selectivity. Propene reacts with phosphoric acid to
form a propyl phosphoric acid ester (or carbocation equivalent)
or propyl phosphate,22 which then undergoes nucleophilic attack
by another olefin molecule (oligomerization) or by an aromatic
species (alkylation). Since SPA does not have a constraining
pore structure, as is the case with small- and medium-pore
zeolites, an Eley-Rideal mechanism (and not the Langmuir-
Hinselwood) governs the alkylation reaction.23-25 The rate of
either reaction, alkylation or oligomerization, will to a great
extent be determined by the feed ratio and temperature. In
addition to the different oligomerization products formed by
the reaction of propene with itself and already formed oligomers,
various alkylated aromatic products were detected in the product
stream. In the experiments using benzene as the aromatic, the
alkylated benzenes were mainly cumene and the three diiso-
propylbenzene isomers. In the experiments with toluene as the
aromatic, the main alkyl aromatics were o-, m-, and p-cymenes,
as well as the trialkylated diisopropyltoluene.
No n-propylbenzene or n-propyltoluene was detected in the
products of any of the experiments. Using a continuous fixed
1832 Ind. Eng. Chem. Res., Vol. 47, No. 6, 2008
Figure 6. Ideal system illustrating the effect of different benzene to propene ratios on the reaction probability, assuming similar adsorption constants. Both
alkylation (A) and oligomerization (O) require propene to be the adsorbed species, and no reaction takes place if benzene is the adsorbed species. There is
competition between the benzene and propene for the protonic sites, and in practice benzene and propene have dissimilar adsorption constants.
bed reactor system, Cavani and co-workers26 reported only parts
per million levels of n-propylbenzene in the product stream using
an SPA catalyst under reaction conditions similar to those
employed in this study. Similar findings were reported for
benzene alkylation by pentenes and hexenes over SPA, namely
that no n-alkylbenzenes were detected.16,27 However, high
selectivities to n-propylbenzene formation have been reported
to occur at temperatures of 300 °C using H-ZSM-5 zeolite
catalysts.28,29 Zeolites that have strong acid sites are known to
catalyze isomerization and transalkylation of alkyl aromatics.30
It is therefore not surprising that no n-propyl aromatics were
detected in our experiments, because the acid sites of the SPA
catalyst are not strong enough to catalyze these reactions, as
demonstrated by the experiments with p-cymene, where no
evidence of isomerization or transalkylation was found.
Alkyl groups on an aromatic ring are ortho-para-directing,
but steric hindrance may result in para prevalence. The
difference in the dialkylation selectivity between diisopropyl-
benzene (to the para position) and cymene (to the ortho position)
can therefore be attributed to steric hindrance; that is, the propyl
group on cumene is more bulky than the methyl group of the
toluene species. This results in increased dialkylation on the
para position, instead of the ortho position. The ortho-para-
directing influence of the alkyl groups was nevertheless found
to be weak, with the observed selectivity to the meta isomer
being more than 10%.
The low alkylation rate at high aromatic to olefin ratio as
well as at low aromatic to olefin ratio can be explained in terms
of the probability of interaction of the aromatic with the olefin
on the acid sites. This can be illustrated by calculating the
reaction probabilities of an ideal system, assuming the same
adsorption constant for propene and benzene (although there is
a difference in practice)23 and assuming that all potentially
productive reactions will lead to either alkylation or oligomer-
ization (Figure 6). This follows the trends seen in the experi-
mental data (Figures 2 and 3).
The high electron density on an aromatic ring makes it a good
nucleophile capable of an interaction with a positively charged
species, which in the present system is either a carbocation or
an acid site. When the aromatic interacts with a carbocation,
alkylation can take place. However, when the aromatic interacts
with an acid site, the aromatic becomes a temporary poison to
that acid site, as no “real protonation” will occur. This is due
to the stability of the π-electron system of the aromatic ring,
which is more stable than the π-electron system of olefins that
can readily be protonated. This difference in stability makes
aromatics less reactive than olefins, as shown by Siffert and
co-workers,23 who reported that the adsorption of propene on
protonated zeolites is much stronger than the adsorption on
benzene.
Figure 7. Comparison of alkylation (9) and oligomerization (b) rates of
propene with benzene (solid symbols) and toluene (open symbols) in a 1:1
molar ratio over SPA at 3.8 MPa in a batch reactor.
A comparison between the oligomerization and alkylation
reaction rates (Figure 7) shows that the benzene alkylation rate
is higher than the toluene alkylation rate. However, the electron
density of toluene is higher than that of benzene due to the
electron-donating methyl group attached to the toluene ring,
thereby making it the better nucleophile of the two. The
observations therefore seem to be contrary to expectation, which
indicates that steric effects are more important than electronic
effects during alkylation over SPA.
The oligomerization reactions in the presence of the two
aromatics (Figure 7) exhibited similar behavior. The oligomer-
ization reaction rate in the presence of benzene is higher than
the oligomerization reaction rate in the presence of toluene. In
this instance the observations followed the expected trend.
Toluene, being a stronger nucleophile than benzene, had a
stronger interaction with the acid sites and it lowered the
oligomerization rate more than benzene by being a stronger
temporary catalyst poison.
Commercial Implications. The hydrogenated kerosene boil-
ing range product from olefin oligomerization over SPA consists
mostly of branched paraffins, giving it properties that are
desirable for jet fuel (Table 4).31 It can also be used for diesel
fuel, but it has a cetane number of less than 35.14 From Table
4 it can be seen that the kerosene-range hydrogenated oligomers
meet specifications except for the aromatics content and density
that are too low.
The aromatic feed materials considered in this study, namely
benzene and toluene, are both motor-gasoline components. The
propene alkylation products, with the exception of cumene,
which has a boiling point of 152 °C, are all kerosene boiling
range products. The cumene can nevertheless be included in
jet fuel, since its flash point (44 °C) meets the specification,
but it is also a good motor-gasoline component, with a high
research octane number (RON ) 113) and a high motor octane

Figure 8. Solid phosphoric acid catalyzed combined oligomerization and
alkylation process that includes recycling of unconverted aromatics and light
olefins to produce mainly jet fuel.
number (MON ) 99.3).32 However, if the kerosene is considered
for application as BUFF, the flash point specification increases
to 60 °C and it is less desirable to include cumene in the fuel.
The same holds true for the monoalkylated products from
toluene. Although the boiling points of o-cymene (178 °C),
m-cymene (175 °C), and p-cymene (177 °C) are at the light
end of the kerosene boiling range, their flash points are less
than 60 °C. However, they too have high octane numbers and
can be used in motor gasoline. The application, Jet A-1 or
BUFF, therefore determines whether the monoalkylated products
can be included in the kerosene, or whether they can be used
as motor gasoline. It should be noted that the BUFF flash point
specification not only affects the alkyl aromatics that can be
included, but also requires the hydrogenated oligomers (Table
4) to be cut differently.
It has been shown (Tables 1 and 2) that when benzene or
toluene is used as co-feed with the propene in a 1:6 ratio, the
product contains a high monoalkylated to dialkylated aromatic
ratio (about 10:1), despite the high olefin content of the feed.
This ratio has been used to calculate the properties of a mixture
of the hydrogenated oligomerization product and the aromatic
product from benzene alkylation with propene (Table 4). Blends
within the aromatic content specification range of jet fuel meet
all the Jet A-1 specifications.
It is possible to operate industrial reactors in such a way that
the unconverted aromatic fraction can be separated from the
product and returned to the reactor as a recycle stream (Figure
8). Such an operation, where part of the naphtha-range product
is recycled, is practiced commercially.14 Catalytic distillation
can also be employed for continuous separation of feed and
product,33 but it requires a more active catalyst than SPA, such
as β-zeolite.
It should therefore in principle be possible to combine SPA
catalyzed olefin oligomerization and aromatic alkylation in a
single process operating at low aromatic to olefin ratios. The
product from such a process would be suitable for use as either
a motor-gasoline blending component or synthetic jet fuel. It
may even be possible to use the heavier part of the kerosene
fraction as BUFF.
Another important aspect to consider is the impact of the
suggested process modification on the catalyst lifetime. This is
especially important for SPA, because SPA is not regenerated
and reused like its zeolite-based counterparts. Under commercial
operating conditions for olefin oligomerization, the catalyst
lifetime is typically on the order of 475-620 kg of product/kg
of catalyst.34 However, despite its limited catalyst lifetime, SPA
is arguably a more environmentally friendly catalyst than zeolite-
based catalysts. SPA is manufactured using only natural
substances, namely phosphoric acid and kieselguhr,34,35 and after
Ind. Eng. Chem. Res., Vol. 47, No. 6, 2008 1833
use, it can be neutralized with ammonia to produce ammonium
phosphate fertilizer for the agricultural industry, instead of
becoming solid waste. Although the present study was not
designed to evaluate the effect of aromatics co-feeding on SPA
catalyst stability, similar SPA deactivation rates were observed
during reaction at low aromatics to olefin ratio and olefin
oligomerization without co-feeding aromatics in a related study
conducted in our laboratories. As a matter of fact, co-feeding
of 0.5-5 mass % aromatics has been claimed to be beneficial
for the SPA catalyst lifetime due to increased removal of heavy
oligomers from the catalyst surface during operation.36
Conclusions
It was demonstrated that it is possible to combine propene
oligomerization and the alkylation of benzene and toluene with
propene in a single reaction system using a solid phosphoric
acid catalyst. Alkylation proceeded even at a 1:6 aromatic to
olefin molar ratio, and this finds application in the production
of a motor-gasoline blending component or a fully synthetic
jet fuel that meets Jet A-1 specifications. The following specific
observations were made:
(a) SPA favored monoalkylation even at low aromatic to
olefin ratio, with the selectivity ratio of monoalkylated to
dialkylated aromatics being 10:1 or better.
(b) In the reaction system steric effects were more important
than electronic effects. This could be seen by the higher
reactivity of benzene for alkylation than toluene. Aromatic
substitution was also controlled by steric effects, with alkyl
groups being only weakly ortho- and para-directing, with a
selectivity of more than 10% to the meta isomers. The high
o-cymene selectivity, but low 1,2-diisopropylbenzene selectivity,
that was observed was due to the smaller steric bulk of the
methyl group compared to the isopropyl group.
(c) The disubstituted aromatics were identified, and it was
found that the isomer distribution was not affected by the
operating conditions. During benzene alkylation with propene,
the selectivity ratio was 1,2-diisopropylbenzene (23%), 1,3-
diisopropylbenzene (37%), and 1,4-diisopropylbenzene (40%).
During toluene alkylation with propene, the selectivity ratio was
o-cymene (48%), m-cymene (23%), and p-cymene (29%).
(d) SPA is not a strong enough acid to catalyze transalkylation
or the interconversion of alkyl aromatic isomers.
Acknowledgment
All work was carried out at the facilities of Sasol Technology
Research and Development, and permission to publish this work
is appreciated. The contribution of André van Eeden (FTRC
0709) is also gratefully acknowledged.
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ReceiVed for reView August 3, 2007
ReVised manuscript receiVed December 3, 2007
Accepted December 5, 2007
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