Article

pubs.acs.org/IECR

Alkylation Kinetics of Isobutane by C4 Olefins Using Sulfuric Acid as

Catalyst
Weizhen Sun, Yi Shi, Jie Chen, Zhenhao Xi, and Ling Zhao*
State-Key Laboratory of Chemical Engineering, East China University of Science and Technology, Shanghai 200237, China
*
S Supporting Information

ABSTRACT: The alkylation kinetics of isobutane with butene using sulfuric acid as catalyst was investigated by batch
experiments in the conditions of industrial interest. More than 16 alkylates were identified and quantified by GC-MS. On the
basis of the classic carbonium ion mechanism, the kinetic model was established, which can predict the concentration change of
three groups of key alkylates including trimethylpentanes (TMPs), undesirable dimethylhexanes (DMHs), and heavy ends
(HEs). The agreement between experimental and model calculated data was quite satisfactory. The rate constants were found to
be constant with the varied temperatures (276.2 to 285.2 K) except those accounting for the addition of H+ to isobutene and its
reversible reaction. An anti-Arrhenius behavior was observed for the addition reaction of H+ to isobutene, in which the
corresponding rate constant falls with the increasing temperatures. The kinetic model was confirmed by the simulation of the
industrial alkylation reactor. Hopefully, the kinetic model developed in this work will be useful to the design and optimization of
novel alkylation reactors.

1. INTRODUCTION isobutane with olefins, much classical literature had been

In early 1990s, the USA refiners had to start changing their
strategy on gasoline composition to meet the mandatory CAA
(Clean Air Act) specifications.1 Since that time, gasoline was
forced to move in a more environmentally friendly direction,
such as reducing volatility, limitations in the aromatic content,
increased amount of oxygenates, reduction of olefins and sulfur,
and elimination of lead. As a desirable blending component,
without olefins or aromatics, alkylate exclusively contains
isoalkanes with high octane number. Since its commercial
production in the last century, alkylate had been the most ideal
blending component for a typical refinery gasoline pool. Nearly
70% of the world’s alkylate production is from North America,
and over 20% is produced from Europe.2 It was believed that
alkylate will continue to be a desirable blending component as
long as cars are operated on high octane gasoline.3
The alkylation reaction producing alkylates combines
isobutane with light C3−C5 olefins in the presence of a strong
acid catalyst. Currently, the only processes of commercial
importance use either sulfuric or hydrofluoric acid as catalysts.4
Although the number of established alkylation units using
sulfuric acid is almost as much as that using hydrofluoric acid,
more new alkylation plants built worldwide chose sulfuric acid
as catalyst in the recent past years.5 One of the reasons is that
hydrofluoric acid is a highly toxic liquid, and released into the
atmosphere, it forms aerosol, which drifts downwind for several
kilometers.6 Actually, both acids suffer from certain drawbacks,
but it is not the intent of this work to review in detail the pros
and cons of sulfuric acid versus hydrofluoric acid but to address
the alkylation kinetics using sulfuric acid as a catalyst.
It is well-known that the study on reaction kinetics is of
fundamental importance not only to the design and
optimization of a ripe chemical reactor but also to the
development of a novel one. Also, it is helpful in understanding
the reaction mechanism. As to the alkylation mechanism of
published,7−11 in which the formation pathway of the majority
of key components and intermediates in alkylate were well
formulated although different publications would have different
descriptions regarding some specific steps. However, to the best
of our knowledge, there was little literature focusing on the
alkylation kinetics of isobutane with butene in sulfuric acid to
address the formation of several key alkylates such as
trimethylpentanes (TMPs), dimethylhexanes (DMHs), and
heavy ends (HEs). Using uniform hydrocarbon drops and short
contact time, the sulfuric acid catalyzed reaction of isobutane
with 1-butene, as well as the oligomerization of 1-butene, was
investigated, in which only two key reactions were consid-
ered,12 but other important reaction steps in view of the
presence of several dozen isoparaffins in commercial produced
alkylates are far from being understood.13 The two-step process
for the alkylation of isobutane with C4 olefins was investigated,
but the rate constants were not given.10
In this work, the alkylation kinetics of isobutane with butene
using sulfuric acid as catalyst was measured under the condition
of industrial interest. The kinetic model was established on the
basis of the carbonium ion mechanism, in which three families
of key isoparaffins were considered including TMPs, DMHs,
and HEs.
2. EXPERIMENTAL SECTION
The experiments were carried out in a batch setup with a glass
reactor with the volume of 1 L. To keep isobutane and olefin in
Special Issue: NASCRE 3
Received: February 4, 2013
Revised: April 2, 2013
Accepted: April 3, 2013

© XXXX American Chemical Society A dx.doi.org/10.1021/ie400415p | Ind. Eng. Chem. Res. XXXX, XXX, XXX−XXX
Industrial & Engineering Chemistry Research Article

Figure 1. Schematic diagram of experimental setup: 1, cylinder for mixed C4; 2, cylinder for N2; 3, dryer; 4, filter; 5, mass flow meter for liquid; 6,
refrigerator; 7, mass flow meter for gas; 8, low temperature salt water; 9, reactor; 10, baffles; 11, sampling cylinder.

liquid phase, the operating pressure was set to be 0.5 MPa. One different components are very close to 1.0 with respect to the
refrigerant system was employed to obtain cycling salt water, same standard substance benzene on FID detector. The
which was used to keep the entire reactor and the hydrocarbons maximum relative analysis deviation was less than 5%, which
into and out of the reactor at constant temperature ranging shown in Table 1. More detailed descriptions about GC-MS
from 276.2 to 285.2 K. Inside, the reactor baffles and stirring can be found in the Supporting Information.
apparatus were installed, which can be adjusted within 3000
rpm. For a typical experiment, first, the weighed sulfuric acid Table 1. Reproducibility of Analysis Method
was put into the reactor, and then, the nitrogen (N2) was
mass content, %
introduced to remove air in the reactor, after which the
pressure was set to be 0.5 MPa. Next, the refrigerant system alkylate relative
number components sample 1 sample 2 average, % deviation
started to work to keep the material inside the reactor at the set
temperature. When the temperature inside the reactor reached 1 isopentane 1.491 1.374 1.433 0.041
the set temperature, the weighed mixture of isobutane and 2 2,3- 3.475 3.286 3.380 0.028
dimethylbutane
olefin with certain molar ratio was quickly introduced into the 3 3-methylpentane 0.427 0.403 0.415 0.030
bottom of the reactor. Almost at the same time, the agitator 4 2,4- 2.936 2.758 2.847 0.031
started to work to ensure the good dispersing of hydrocarbon dimethylpentane
upon contacting the sulfuric acid. According to the alkylation 5 2,2,3- 0.348 0.345 0.347 0.004
reaction progress, the sampling interval was shorter initially and trimethylbutane
then longer in the later period. In all of the experiments, the 6 2-methylhexane 0.207 0.227 0.217 −0.046
7 2,3- 1.744 1.692 1.718 0.015
temperature inside the reactor was recorded and controlled to dimethylpentane
ensure it was within a set range. The schematic diagram of the 8 3-methylhexane 0.152 0.162 0.157 −0.029
experimental setup was shown in Figure 1. 9 isooctane 21.843 21.348 21.595 0.011
The gas chromatography−mass spectrometry (GC-MS) was 10 2,5- 4.054 3.982 4.018 0.009
adopted to identify and quantify more than 16 alkylate dimethylhexane
components. A typical chromatogram of alkylate components 11 2,2,3- 2.395 2.377 2.386 0.004
trimethylpentane
is shown in Figure 2. The area normalization method was
12 2,4- 1.100 1.105 1.102 −0.002
employed in this work, since all of the correction factors of dimethylhexane
13 2,3,4- 9.507 9.276 9.391 0.012
trimethylpentane
14 3,3- 12.174 11.904 12.039 0.011
dimethylhexane
15 2,3- 0.272 0.287 0.280 −0.027
dimethylhexane
16 2,2,5- 10.083 9.976 10.030 0.005
trimethylhexane

The intrinsic chemical reaction of alkylation is very fast,

leading to a strong mass transfer limitation of olefin into the
reaction region when the mass transfer rate is not big enough.14
The experiments showed that when exceeding above 2500 rpm
the increasing stirring speeds have no influence on the
Figure 2. Chromatogram of all alkylate components. alkylation rate, which demonstrates the elimination of mass
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Industrial & Engineering Chemistry Research Article

Figure 3. Diagram of the reaction pathways network.

transfer limitation. Thus, all of the investigations of alkylation TMP+ + iC4 = → TMP + C=C(CH3)−C+ (6)
kinetics with varied temperatures were performed with the
stirring speeds of 2800 rpm.
C=C(CH3)−C+ + iC4 =
3. KINETIC MODEL → C=C(CH3)−C−C−(CH3)C+−C (7)
It is well accepted that the alkylation of isobutane with olefins
follows the classic carbonium ion mechanism. Initially the tert- Through suitable hydrogen and proton transfer reactions, the
butyl cation is produced by this reaction: unsaturated cation ion forms a DMH molecule. Another
possible pathway to give DMHs is through the addition of 1-
k1
iC4 = + H+ → iC4 + (1) butene to iC4+,11
k5
where iC4= is isobutene and iC4+ represents tert-butyl cation. iC4 + + 1‐butene → DMHs+ (8)
Actually, regardless of whether the feed butene is either 1-
butene or 2-butene, it tends to give iC4= through fast Similar to TMPs+, the DMHs+ are saturated through the
isomerization, which occurs especially in the presence of hydride abstraction from isobutane, giving an iC4+ meanwhile,
sulfuric acid.15 The transform between different butenes k6
proceeds by the following equilibrium reaction, DMHs+ + iC4 → DMHs + iC4 + (9)
K1 K2
1 − C4 H8 ⇄ 2 − C4 H8 ⇄ iC4 = According to the experimental data in this work, it was verified
(2)
that the formation of DMHs is most likely through the latter
Interestingly, it is found that even when isobutane alkylated pathway, that is, the addition of 1-butene to iC4+.
with olefins rather than butenes, the trimethylpentanes are still By reactions involving olefins, heavy ends (HEs) are
generated by so-called self-alkylation. The key step for self- produced, which are primarily polymerization reactions.15
alkylation is the formation of isobutene, which in fact is a The polymerization of C4 olefins proceeds by the addition of
reversible reaction of the reaction 1:1 iC4= or 2-butene to TMPs+ or DMHs+,
k2
iC4 + → iC4 = + H+ (3) TMPs+ (or DMHs+) + iC4 = (or 2‐butene) → iC12+
(10)
The tert-butyl cation adds to an olefin to produce the
corresponding C8 carbonium cation. For example, when the The iC12 would further add iC4 or 2-butene to give iC16+.
+ =

tert-butyl cation reacts to iC4= or 2-butene, the trimethylpen-
tanes will be formed,
k3
iC4 + + 2‐butene (or iC4 =) → TMPs+ (4)
where TMPs is the abbreviation of trimethylpentanes. These
C8 carbonium cations tend to isomerize via methyl shifts and
hydride transfer reaction to form several isomer cations.4 For
simplification, in this work, all these C8 cations are regarded as
one pseudo component TMP+. By rapid hydride transfer with
isobutane, each TMP+ changes to the corresponding TMP
component, regenerating the iC4+ to keep on the chain
propagation.
k4
TMP+ + iC4 → TMP + iC4 + (5)
For simplification, in this work, we regard iC12+ and iC16+ as the
pseudo components iCm+. When these polymer cations iCm+
are contacted with isobutane, the HEs is formed, along with the
production of iC4+,
k7
iCm+ + iC4 → iCm + iC4 + (11)
As one of the five groups in alkylated hydrocarbon products,
the light ends (LEs) include C5−C7 isoparaffins. The
production of LEs is believed to come from the fragmentation
of large isoalkyl cations.9 Due to the strong oxidizing capacity of
concentrated sulfuric acid, the isoalkyl cation will be generated
again from HEs as follows,
iCm + H+ → iCm+ (12)

where iC4 stands for isobutane. The source of undesirable These heavy isoalkyl cations are fragmentated following the
dimethylhexanes (DMHs) with low octane numbers has several β-scission rule, leading to smaller isoalkyl cations and olefins.1
possible pathways. One was believed from the addition of iC4= k8
and allylic carbocation, which is the result of a hydride ion iCm+ ⇄ iCx + + iCy =
abstraction from the allylic position of an olefin molecule.10 k9 (13)

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Industrial & Engineering Chemistry Research Article

Figure 4. Concentration profile of key components in alkylation of isobutane with butene. Temperature: (a) 276.2 K, (b) 279.2 K, (c) 282.2 K, (d)
285.2 K. Symbols: experimental data; Line: calculated values by kinetic model.

Isoalkyl cations generated by fragmentation (iCx+) and c1‐C4H8 = α*cC4H8 (15)

protonation of olefins (iCy=) are thought to be the major
precursors of LEs. Through the hydride ion transfer, these c 2‐C4H8 = β*cC4H8 (16)
isoalkyl cations change into the corresponding LEs.
According to the experimental observation in this work, the ciC4= = (1 − α − β)*cC4H8 (17)
degradation of DMH was found to be obvious. It may be
ascribed to the formation of DMH+ from the oxidation of where α and β represent 1/(K1 + K1*K2 + 1), K1/(K1 + K1*K2
DMH, which is further fragmentated into small LE through + 1) respectively.
scission reaction.16 To simplify this multistage reaction, one Following the above reaction steps and assumptions, the
single reaction step is used in this work, kinetic model can be formulated readily as follows,
k10 dc1
DMH → LE (14) = −(1 − α − β)k1c1 − (1 − α)k3c1c3 − αk5c1c3
dt
The diagram of the whole reaction pathway network was shown − (1 − α)k7c1c 2c4 + k2c 3 (18)
in Figure 3.
The alkylation products are composed of more than two dc 2
dozen branched−chain paraffinic hydrocarbons. Both TMPs = −k4c 2c4 − k6c 2c5 − (1 − α)k7c1c 2c4
dt (19)
and DMHs have multiple isomers. HE, as well as LE, also refers
to one family of isoparaffins with close molecular weight. dc 3
Including those carbonium components, there will be more = (1 − α − β)k1c1 + k4c 2c4 + k6c 2c5 − k4c1c3
dt
than three dozen species in this system. However, only three or
four groups of components can be measured due to the limit of − αk5c1c3 − k2c 3 + (1 − α)k 7c1c 2c4 (20)
analysis method and the faster transform between various
species. To avoid the over fit or over parametrization, the dc4
= (1 − α)k3c1c3 − k4c 2c4 − (1 − α)k7c1c 2c4
number of involved species and pathway should be simplified as dt (21)
much as possible. So first, some species with similar properties
are treated as one pseudo component, such as TMPs (or dc5
= αk5c1c3 − k6c 2c5
DMHs) mentioned above. HE, as well as LE, is regarded as one dt (22)
single component, respectively, because of close molecular
weight. Second, some steps are assumed to be instantaneous, dc6
= k4c 2c4
such as reactions 10 and 12, and the reaction 2 is assumed to be dt (23)
under chemical equilibrium control. Accordingly, the concen-
tration distribution for these three butenes can be calculated, dc 7
= k6c 2c5 − k10c 7
respectively, on the basis of the total concentration of butene, dt (24)

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Industrial & Engineering Chemistry Research
dc 8
= (1 − α)k7c1c 2c4 + k9c 9c10 − k8c 8
dt
dc 9
= k8c 8 − k9c 9c10
dt
dc10
= k8c 8 − k9c 9c10
dt
These ordinary differential equations (ODEs) are completed
with specifications of the following initial conditions at time t =
0,
c1 = c10 ; c2 = c20; c3 = 0; c4 = 0; c5 = 0;
c6 = 0; c 7 = 0; c8 = 0; c 9 = 0; c10 = 0
In eqs 18 to 28, the relationship between the numbers of 1
through 10 and the corresponding species is as follows: 1,
butene; 2, iC4; 3, iC4+; 4, TMP+; 5, DMH+; 6, TMP; 7, DMH;
8, HE; 9, iCx+; 10, iCy=.
4. RESULTS AND DISCUSSION
The concentration profiles of three groups of key components
in alkylation of isobutane with butene were plotted in Figure 4.
It shows that all of three species have dramatic changes within 2
min. Initially, the HEs go up sharply and then come down
shortly. This demonstrates that the alkylation of isobutane with
butene is a very fast reaction. Almost after 5 min, each of the
species reaches to a platform individually, although the DMHs
still continue to go down slightly.
To fit the experiments and estimate k1 through k10 in eqs
18−28, the nonlinear least-squares fitting method was
employed by the following object function,
m −231.5 kJ/mol, which indicates that this is a strong exothermic
obj = ∑ (ciexp − cical)2
i=1
where cexp
and ccal
represent the experimental and calculated
i i
values of ith component, respectively, and m is the number of
experimental data. An lsnonlin function in Matlab was used for
the regress of the set of k1 through k10. Equations 18−28 were
resolved by the Runge−Kutta method in each iteration. Before
the fitting was performed, the values of α and β should be
determined first; that is, the equilibrium constants in reaction 2
should be computed. According to thermodynamics, K1 and K2
are the functions of temperature and can be calculated on the
basis of the Gibbs free energy variation of reaction 2. As we
know, the ASPEN Plus software is a useful tool in chemical
process modeling and has a reliable thermodynamic database.
The RGibbs module in ASPEN Plus was used to obtain the
average values of K1 and K2 at the temperatures between 276.2
and 285.2 K, which is 28.39 and 6.433, respectively.
Accordingly, the values of α and β can be calculated to be
0.004718 and 0.1340, respectively.
Preliminary fitting results show that with the variation of
temperature most of the rate constants change a little, except k1
and k2. It indicates that those reaction steps corresponding to
the rate constants of k3 through k10 have small or even no
activation energy. A similar finding has been reported by
Langley et al. in the alkylation kinetics of isobutane with
propylene.17 In this work, these rate constants including k3
through k10 are assumed to be constant with varied temper-
atures in the range from 276.2 to 285.2 K. One of the
advantages of such an assumption is to reduce the adjustable
Article
parameters and make the estimated rate constants more
definite. So, in the refitting of experimental data, the values
(25)
of k3 through k10 are kept fixed with temperatures, and the only
adjustable parameters are k1 and k2. The fitting results are
(26) shown in Figure 4, compared with the experiments. It can be
seen that the agreement between experimental and calculated
data is quite satisfactory. In particular, the dramatic change of
(27) HEs in short time is captured successfully by the model.
The estimated k1 through k10 are listed in Table 2 with 95%
confidence intervals. We can see that most of the confidence
intervals are one magnitude smaller than the corresponding
parameters except k3 and k6, which confirms the reliability of
the estimated rate constants. However, an anti-Arrhenius
behavior can be found for k1; that is, the value of k1 falls as
(28) the temperature increases. In fact, this phenomenon is not
unusual or abnormal for hydrocarbon reaction with the
presence of free radical molecules.18 The observations of anti-
Arrhenius kinetics are usually ascribed to an entropic
contribution to the free energy of activation. This anti-
Arrhenius behavior is believed to be caused by a decrease of
the equilibrium constant of a multistep reaction.19
The Arrhenius relationships of k1 and k2 are obtained by
plotting ln(ki) against 1/T shown in Figures 5 and 6,
respectively, both of which have good linear relationships.
The activation energies of k1 and k2 are computed to be −58.3
and 173.2 kJ/mol, and the corresponding pre-exponential
factors are 5.23 × 10−11 and 6.87 × 1031 min−1 respectively.
According to the fundamental principle of physical chemistry,
in a reversible reaction, the difference of activation energy
between the forward and backward reaction should be equal to
the heat of the reaction. So, in this sense, the heat of reaction
for the addition of H+ to the iC4= can be calculated to be
reaction.
(29) Using uniform hydrocarbon drops, L. Lee et al. studied the
sulfuric acid catalyzed reaction of isobutane with 1-butene and
the 1-butene oligomerization.12 Kinetic constants for a
simplified model were calculated, in which only the primary
reactions were considered. When using sulfuric acid of 98%, the
rate constants for alkylation of isobutane with 1-butene and 1-
butene oligomerization at 298 K were calculated to be 2.25 ×
108 and 9.5 × 108 cm3/mol/s, respectively. However, in this
work, there are no such reaction steps exactly corresponding to
those in the literature.12 This is because the kinetic model in
this work was developed on the basis of the carbonium ion
reaction mechanism which used elementary steps, while L. Lee
et al. dealt with the alkylation and oligomerization reactions by
the empirical method on the basis of power exponent. Even so,
it is found that one elementary step in our model is similar to
the alkylation reaction of isobutane with 1-butene, which is the
addition of 1-butene to iC4+ (eq 8). The rate constant for this
step was estimated to be 1.26 × 104 kg/mol/min, which equals
1.17 × 105 cm3/mol/s. It seems much smaller than the
alkylation reaction rate constant of isobutane with 1-butene
reported by L. Lee et al., but it should be noted that our
experiments were carried out at the temperatures from 276.2 to
285.2 K, which are 13 to 22 K smaller than that reported by L.
Lee et al. (298 K). According to L. Albright et al.’s work,10 at
the temperature of 259 K, the alkylation reaction rate slowed
down dramatically, in which “hour” was used as the unit of
time. Thus, taking into consideration the sensibility of
alkylation reaction to temperature, the difference of the rate
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Industrial & Engineering Chemistry Research Article

2.61 ± 0.85
k10, 10−2
min−1
kg·mol−1·min−1
5.48 ± 0.82
k9

0.63 ± 0.06
min−1
k8

Figure 5. Arrhenius relationship between k1 and 1/T.

kg2·mol−2·min−1
88.46 ± 6.78
k7
kg·mol−1·min−1
4.36 ± 2.48
k6, 103
kg·mol−1·min−1
1.26 ± 0.42

Figure 6. Arrhenius relationship between k2 and 1/T.

k5, 104

constant of isobutane alkylation reaction with 1-butene

between L. Lee et al.’s and ours should be reasonable.
In L. Albright et al.’s work,10 an S-shaped curve of alkylation
yield versus time for a batch run can be noticed. The author
kg·mol−1·min−1
1.03 ± 0.22

believed that the increasing rates of alkylate formation during

the initial stages were ascribed to the increasing acidity of the
k4
Table 2. Estimated Rate Constants with 95% Confidence Intervals

acid phase because acid was regenerated, but this S-shaped

curve can be easily understood if we illustrate this phenomenon
from the point of view of reaction mechanism. In this work, eq
1 is a chain initiation step. By the subsequent addition of iC4+
kg·mol−1·min−1
8.33 ± 1.86

and olefin, the precursor of alkylates are generated. Thus, in the

k3, 102

initial stage, the alkylation rate increases due to the continuous

accumulation of the concentration of iC4+. At the last period,
the alkylation rate slows down with the decrease of olefin
concentration. This is similar to the free radical chain reaction
of hydrocarbon, in which the existence of induction period is
0.06
0.20
0.38
0.56

very common in the oxidation of hydrocarbon, especially at low

min−1
k2

±
±
±
±

temperature.
0.15
0.45
1.00
1.59

To confirm the reliability of the kinetic model developed in

this work, we simulated the alkylation reactor operated at
industrial conditions. Table 3 listed some basic conditions of
0.72
0.57
0.50
0.71

the typical industrial alkylation reactor. The industrial alkylation

min−1
k1

±
±
±
±
6.37
5.06
4.15
2.79

Table 3. Operating Conditions for Industrial Alkylation

Reactor
A/H, m3/m3a I/O, mol/molb temperature, K pressure, MPa
temperature

1.1:1 8:1 279 0.45

276.2
279.2
282.2
285.2
K

a
Ratio of sulfuric acid to hydrocarbon (isobutane + olefin) based on
volume. bRatio of isobutane to olefin based on mole.

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Industrial & Engineering Chemistry Research
reactor of isobutane with olefin is a well mixed flow reactor.1
For this type of reactor, the material balance equation can be
written as follows:
xi 0 − xi = τ *( −ri) (30)
where xi0and xi stand for the inlet and outlet concentration of
ith component in alkylates with the unit of mol/kg and τ and
−ri represent the mean residence time of sulfuric acid in reactor
and formation or consumption rate of the ith component with
the unit of min and mol/kg/min. In the eq 30, −ri is
determined by the kinetic model in this work and xi0 is
calculated through the operating conditions listed in Table 3.
Thus, xi can be solved only if τ is given.
The conversion of olefin and alkylate yield versus mean
residence time is shown in Figures 7 and 8, respectively. It can
Figure 7. Conversion of olefin versus mean residence time.
Figure 8. Alkylate yield versus mean residence time.
be seen that the conversion of olefin will be greater than 99.5%
when the mean residence time (τ) is above 10 min, but the
yield of alkylate is under 200% even when τ reaches 20 min.
Usually, the alkylate yield is required to be more than 200%, so
the τ should be kept greater than about 21 min according to
Figure 8. It also indicates that when τ exceeds 30 min the
alkylate yield will approach its theoretical value (203.6%). It
was reported that in the industrial unit the mean residence time
ranges from 20 to 30 min.1,20
Clearly, the simulation results show that the kinetic model
developed in this work can predict the mean residence time of
the industrial alkylation reactor successfully. As we all know, the
mean residence time determines the reactor size when the scale
of production is known and vice versa. Thus, using the kinetic
model developed in this work, we will be allowed to design and
optimize the novel alkylation reactors.
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Article
5. CONCLUSIONS
The alkylation kinetics of isobutane with butene was measured
in the condition of industrial interest. The kinetic model was
established on the basis of the classic carbonium ion
mechanism. The agreement between experiments and model
fitting is quite satisfactory. Except the addition of H+ to
isobutene and its reversible reaction, other reaction steps’ rate
constants were found not to change with the varied
temperatures from 276.2 to 285.2 K. An anti-Arrhenius
behavior was observed for the addition of H+ to isobutene.
Both of them also can be found in other hydrocarbon reactions.
By the kinetic model, the successful simulation of industrial
alkylation reactor was achieved. We hope that the alkylation
kinetics reported in this work will be useful for the reactor
design and optimization of isobutane alkylation with butene.
■
*
ASSOCIATED CONTENT
S Supporting Information
Mass spectrogram of key alkylates and retention time of
alkylate products in GC. This information is available free of
charge via the Internet at http://pubs.acs.org/.
■ AUTHOR INFORMATION
Corresponding Author
*Tel.: +86 21 64253175. Fax: +86 21 64253528. E-mail:
zhaoling@ecust.edu.cn.
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
The authors gratefully acknowledge the financial support from
the Joint Funds of the National Natural Science Foundation of
China (U1162202), the Fundamental Research Funds for the
Central Universities, the China Postdoctoral Science Founda-
tion (2012M512055), and the 111 Project (B08021).
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