Professional Documents
Culture Documents
Alkylation
4.3.1 Introduction
The alkylation reaction is the addition of an alkyl
group to any hydrocarbon. In the petroleum
industry, however, the term alkylation is used for
the reaction of low molecular weight olefins with a
light isoparaffin to form a liquid hydrocarbon. The
alkylation process was commercialized during the
second half of the 1930s to convert the light
hydrocarbons in the Fluid Catalytic Cracking
(FCC) off-gases into more useful, liquid products.
During the Second World War, it experienced a
tremendous growth due to the need for high-octane
aviation fuel. From 1950 to 1970, the world
capacity remained relatively flat due to the
comparative cost of other gasoline blending
components. The lead phase-down in many
countries and additional environmental regulations
after the 1970s increased the demand for alkylate
as a blending stock for motor gasoline.
In addition, the phase-out of MTBE (methyl
tert-butyl ether) in some US states has further
increased the need for high-octane clean streams. At
the beginning of the millennium, 13% of the US
gasoline marked was alkylate. In fact, alkylate is a
high-octane blend-stock (RON, Research Octane
Number, 93-98; MON, Motor Octane Number, 90-95)
free of undesirable components such as sulphur,
benzene and other aromatics. It is mostly made up of
C4 cut
Wide cut
C
3
1-C
4
2-C
4
i-C
4
C
5
C3
n-C4
i-C4
i-C5
others
6.7
17.7
8.2
9.3
18.9
18.5
6.0
7.3
1.1
5.2
3.7
7.8
10.2
7.8
37.4
19.3
7.3
6.5
0.5
0.6
181
CH2 CH3
CH
CH3
CH3
CH3
isobutene
isobutane
CH3
CH3
CH2
CH3
CH
CH3
CH3
2,2,4-trimethylpentane
CH3
CH2
CH
CH2 CH3
CH
CH
CH3
CH
CH3
CH3
1-butene
CH2
CH3
CH3 HC
CH2
CH2
CH3
CH3
isobutane
CH2
CH3
CH3
CH3
CH3
CH
CH3
CH3
CH3
CH3 CH3
CH2
2,2-dimethylhexane
CH3
CH
CH2 CH3
CH
CH2 CH3
CH
C
CH3
CH3
CH3
CH3
propylene
CH3
isobutane
CH
CH3
CH2
CH2
CH2
CH3
CH3
CH3
CH3
CH
CH2
2,2-dimethylpentane
182
CH3
CH3
CH3
CH3
CH3
CH3
CH3
CH3
C
CH3
CH3 HC
CH3
CH3
CH3
CH3
CH3
CH2
CH2
CH3 CH3
C
CH3
CH3
CH3
ENCYCLOPAEDIA OF HYDROCARBONS
ALKYLATION
(Marcilly, 2003)
PROPERTY
HF
H2SO4
Molecular weight
Boiling temperature (C)
Melting temperature (C)
Specific weight (d415)
Viscosity (cP)
Hammett acidity (Ho)*
20.01
19.4
82.8
0.99
0.256 (0C)
10
98.08
290
10.4
1.84
33 (15C)
11.1
C3H8
isobutane
CH3
CH3
CH
CH3
CH2
CH3
CH3
propane
trimethylpentane
183
Table 3. Yield and octane number of the product from H2SO4 alkylation process
Type of feed
Yield (vol C5/vol olefin)
i-C4 consumption (vol/vol olefins)
Catalyst consumption (kg/t C5)
MON
RON
Propylene
Butenes
Amylenes
1.45-1.78
1.27-1.32
137-171
88-90
89-92
1.74
1.14
51-102
92-94
94-98
1.57
1
102-171
88-90
90-92
Table 4. Yield and octane number of the product from HF alkylation process
Type of feed
C
3
1-C
4
2-C
4
i-C
4
C
3 C4
1.76
1.36
92
90
1.73
1.1
94.4
91.6
1.77
1.14
97.8
94.6
1.78
1.28
95.9
93.4
1.79
1.28
93.7
90.8
C
5
1.63
1
91.5
90
184
ENCYCLOPAEDIA OF HYDROCARBONS
ALKYLATION
alkylation reactor.
to settler
coolant
pressure
relief
acid
hydrocarbon
feed
driver
drain
coolant
185
n-butane product
compressor
accumulator
economizer
i-C4
propane
product
olefin feed
isobutane feed
fresh acid
spent acid
alkylate
product
The ExxonMobil cascade process uses the autorefrigeration system to remove the heat of reaction and
to maintain the low reaction temperature (4-5C)
needed for alkylation. The reactor is a horizontal vessel
containing a number of compartments with mixers in
each stage to emulsify the hydrocarbon-acid mixture.
The reaction is held at low pressure and the heat of
reaction is eliminated by evaporating an isobutane
stream directly fed into one end of the reactor. The acid
is fed on the same end and moves together with the
isobutane by overflowing from one compartment to the
other. The olefin feed is split and added into each
compartment. It is not necessary to maintain a high
pressure in the reactor to prevent vaporization of light
hydrocarbons: the pressure varies from about 1.5 bar in
the first stage (richer in isobutane) to about 0.5 bar in
the last stage. Usually, the reactor contains a settling
186
ENCYCLOPAEDIA OF HYDROCARBONS
ALKYLATION
compressor
spent
caustic
depropanizer
propane
waste
water
reactor
M
M
water
washing
waste
water
butane
debutanizer
i-C4
caustic
washing
coalescer
recycle refrigerant
deisobutanizer
fresh
caustic
water
washing
caustic
washing
economizer
KO drum
water
settler
recycle acid
make-up
acid
spent
acid
olefin
feed
spent water
caustic
waste
water
alkylate
make-up
isobutane
187
hydrocarbon product
settler
riser
reactor
acid
hydrocarbon
feed
acid
cooler
cooling
water
188
ENCYCLOPAEDIA OF HYDROCARBONS
ALKYLATION
acid from
depropanizer section
reactor settler
main
fractionator
recycle acid
acid
recontactor
acid standpipe
reactor
riser
acid
make-up
cooling
water
acid
tank
acid eductor
acid
rerun
column
acid
cooler
depropanizer feed
steam
mixer
nozzle
stripping
i-C 4
ASO
recycle isobutane
steam
butane to
KOH treater
olefin
feed
isobutane
isobutane from
depropanizer section
Other processes
189
acid
regenerator
alumina
treater
acid
recycle
reactor
olefin
feed
cooling
water
settler
i-C4 recycle
isostripper
HF stripper
KOH
treater
i-C4
make-up
KOH
treater
KOH
treater
to depropanizer
alkylate
n-butane
Fig. 6. Typical scheme of a UOP HF-alkylation unit fed with C4 cuts (Detrick et al., 2004).
light
ends
Alkylene
reactor
LPG
i-C4/H2
catalyst
reactivation
zone
olefin
feed
alkylate
H2
hot
reactivation
vessel
isobutane recycle
190
ENCYCLOPAEDIA OF HYDROCARBONS
ALKYLATION
191
References
DAMICO V. et al. (2006) Consider new methods to dedottleneck
clean alkylate production, Hydrocarbon Processing,
February, 65-70.
Detrick K.A. et al. (2004) UOP HF alkylation technology,
in: Meyers R.A. (editor in chief) Handbook of petroleum
refining processes, New York, McGraw-Hill, Chapter 1.33.
Gary J.H., Handwerk G.E. (1975) Petroleum refining.
Technology and economics, New York, Marcel Dekker, 152.
Graves D.C. (2004) Stratco effluent refrigerated H2SO4
alkylation process, in: Meyers R.A. (editor in chief)
Handbook of petroleum refining processes, New York,
McGraw-Hill, Chapter 1.11.
192
Carlo Giavarini
Dipartimento di Ingegneria Chimica, dei Materiali,
delle Materie Prime e Metallurgia
Universit degli Studi di Roma La Sapienza
Roma, Italy
ENCYCLOPAEDIA OF HYDROCARBONS