1-Butene and 2-Butenes Production Using the

Positional Isomerization of Butenes Catalyzed

by Sulfonic Acid Cation Exchangers
Abstract—Pure 1-butene and 2-butenes can be efficiently obtained from butane–butene fractions by
com- bining the positional isomerization of n-butenes on sulfonic acid cation exchanger catalysts with
sharp distil- lation. At 50–60°C, an equilibrium 2-butenes : 1-butene ratio of ~25 : 1 is attained. The 2-
butenes, which are comparatively high-boiling compounds, can be sufficiently completely separated
from detrimental impurities (1,3-butadiene and isobutene), 1-butene, and isobutane by distillation. The
back isomerization of the puri- fied 2-butenes into 1-butene with continuous removal of the latter as
distillate affords pure 1-butene at a rel- atively low cost.
1-Butene is an efficient monomer for obtaining distillation because of the formation of numerous
high- quality plastics, and demand for this compound azeo- tropes and almost tangential zeotropes [2] (Table
is increasing rapidly. 2-Butenes are of considerable 1).
interest as the starting compounds for the synthesis of
It follows from phase equilibrium and azeotropy
1,3-butadi- ene via epoxidation followed by epoxide data that distillation can separate 2-butenes from
dehydration and for obtaining methyl ethyl ketone, isobutane, isobutene, 1-butene, and 1,3-butadiene. n-
sec-butanol, and some other compounds. The Butane can be removed only partially because it forms
industrial synthesis of 1-butene by ethylene an azeotrope with trans-2-butene and shows almost
dimerization on organometallic catalysts is com- tangential zeotropy with cis-2-butene.
plicated and expensive [1]. A much more attractive Pure 1-butene is very difficult to separate from the
alter- native is the synthesis of 1-butene and 2-butenes C4 fraction by distillation because it forms an
from C4 fractions obtained by the thermal and azeotrope with isobutene and exhibits almost
thermocatalytic conversion (pyrolysis, catalytic tangential zeotropy with 1,3-butadiene—strictly
dehydrogenation, and catalytic cracking) of petroleum controlled impurities in 1-butene polymerization.
hydrocarbons. These fractions contain comparable Furthermore, 1-butene displays almost tangential
amounts of 1-butene and 2-butenes, their ratio ranging zeotropy with isobutane.
between 1.5 : 1 and 1 : 2. These isomers are difficult Isolation of 1-butene needs a complicated
to separate by conventional technology typically including hydrogenation of
impurity 1,3-butadi-

Table 1. Azeotropy and almost tangential zeotropy in systems formed by 1-butene, 2-butenes, and 1,3-butadiene

Proportion of component 2 Azeotrope pressure, * lim α12

Component 1 Component 2 in the azeotrope, wt % kPa x1 → 1

Isobutane 1-Butene Almost tangential zeotrope 1.05

Isobutane 1-Butene 25.0 475 –
1-Butene 1,3-Butadiene Nearly tangential zeotrope 1.09
n-Butane trans-2-Butene 28.0 381 –
n-Butane cis-2-Butene Almost tangential zeotrope 1.02
trans-2-Butene cis-2-Butene Almost tangential zeotrope 1.06
* lim α12 is the limiting value of relative volatility.
x1 → 1

531
532
Table 2. Equilibrium concentrations of 1- and 2-butene at comparatively low temperatures
Hydrocarbon bp, °C
0 20
1-Butene –6.3 1.8
trans-2-Butene +0.9 72.2
cis-2-Butene +3.7 26.0
ene, removal of isobutene (e.g., via reacting it with an
alcohol to obtain an alkyl tert-alkyl ether), and
removal of
isobutane and n-butane by extractive distillation with a
polar agent or by sharp distillation with loss of part of the
target product.
We have developed technology making the
separation and purification of butenes much easier.
With this tech- nology, nearly all of the n-butenes of
the C4 fraction can be involved in the production of
either 2-butenes or, more importantly, 1-butene. This
technology combines liquid- phase positional
isomerization at modest temperatures with sharp
distillation.
The following reactions take place in the positional
isomerization of n-butenes:
trans-2-butene
1-butene
cis-2-butene (1)
In the presence of a sulfonic acid cation exchanger,
the
positional isomerization of n-butenes proceeds fairly
readily at 50–60°C. The equilibrium in reaction (1) is
strongly shifted toward 2-alkenes, and the lower the
tem- perature, the greater the shift. Experimental data
con- cerning the equilibrium in the positional
isomerization of n-butenes are presented in Table 2.
The separation of concentrated 2-butenes from
butane–n-butene fractions (BBFs) by sharp distillation
is favored by the fact that the boiling points of 2-
butenes are higher than those of the other butenes,
butanes, and 1,3-butadiene.
The technological importance of 1-butene
conversion into 2-butenes is not limited to the isolation
of pure 2-butenes. This reaction is also used to
improve the qual- ity of the alkylation product
resulting from the interaction of isobutane with n-
butenes contained in catalytic crack- ing factions and
to enhance the output capacity and eco- nomic
efficiency of the separation of butanes and butenes by
extractive distillation.
In distillation, part of the n-butane (10–20%) finds
itself in the 2-butene fraction. n-Butane does not exert
any adverse effect on 2-butene conversion catalysts
and can be removed after the conversion of 2-butenes
into the desired products.
Acid catalysts, including sulfonic acid cation
exchang- ers, can simultaneously catalyze alkene
dimerization and oligomerization reactions:
PAVLOV et al.
Concentration in equilibrium mixtures (wt %) at T, °C
40 60 80 100 150
2.5 3.3 4.1 5.0 6.0 9.8
69.8 65.9 62.5 59.0 55.9 49.4
27.7 30.8 33.4 36.0 38.1 40.8
⎧1-Butene ⎫
2⎨ ⎬ iC 8 H 16 iC12H24. (2)
iC8H16
⎩2-Butene ⎭ dimers trimers
These reactions are undesirable in alkene production.
Some researchers attempted the positional
isomerization of concentrated alkenes, but this led to
extensive alkene dimerization and oligomerization and
to the deactivation of the sulfonic acid cation
exchanger. This problem can readily be solved since
the isomerization reactions are monomolecular, while
the dimerization and oligomeriza- tion reactions (2)
are, respectively, a bimolecular reaction and a
sequence of consecutive bimolecular reactions. Alk-
ene isomerization proceeds with a sufficiently high
selec- tivity in the presence of 65–80% alkanes. This
amount of alkanes is present in many fractions
resulting from the thermocatalytic conversion of
petroleum hydrocarbons (catalytic cracking and n-
butane dehydrogenation frac-
tions), so it is unnecessary to preconcentrate these frac-
tions prior to selective isomerization. Conversely, in order
to raise the alkane concentration in the conversion of low-
alkane C4 fractions, such as pyrolysis BBF, it is appropri-
ate to dilute the feed with the unreacted butane fraction
or introduce a comparatively high-boiling alkane solvent.
It is often required to rule out the presence of 1,3-
buta- diene in the products distilled from the desired
2-butenes. This may be necessary for further
processing of these products, e.g., dehydrogenation. In
this case, it is perti- nent to carry out liquid-phase 1,3-
butadiene hydrogena- tion in the C4 fraction before
isomerization. Hydrogena- tion catalysts, including
supported Ni- and Pd-contain- ing ones,
simultaneously cause the positional iso- merization of
butenes in the presence of hydrogen. It was
demonstrated that isomerization on these catalysts pro-
ceeds more slowly than isomerization on sulfonic acid
cation exchangers and, besides, use of these catalysts
in deep isomerization is irrational because of the
inevitable hydrogenation of butenes into butanes to
an extent of
~10% or above. The conditions for the Ni- and Pd-cata-
lyzed processes should be optimal for alkadiene
hydroge- nation. The extent of 1-butene isomerization
into 2-butenes will then be 25–35% of the extent
allowed by the chemical equilibrium.
The kinetics of 1-butene and 1,3-butadiene conver-
sion on sulfonic acid cation exchangers and
hydrogena- tion catalysts is illustrated here by the
conversion of a C4 fraction containing ~70% butanes,
14% 1-butene, 14.5% 2-butenes, and 1.3% 1,3-
 1-BUTENE AND 2-BUTENES PRODUCTION 533
butadiene (Table 3). The sul-

THEORETICAL FOUNDATIONS OF CHEMICAL ENGINEERING Vol. 44 No. 4 2010

Table 3. Kinetic data for 1-butene and 1,3-butadiene conversion
Conversion of the C4 fraction (%) on different catalysts
sulfonic acid cation exchanger (20%), kieselguhr-supported Ni (20%), 60°C,
Hydrocarbon 60°C, process duration (h) process duration (h)
2 4 5 2 4 5
1-Butene 72.1 88.6 91.5 69.0 90.7 92.8
Butadienes 15.0 30.8 38.5 89.0 96.2 ~100
Butenes into n-butane – – – 8.4 17.2 21.4
including n-butenes and 0.4 0.8 1.0 – – 0.05
butadienes dimerization

fonic acid cation exchanger had a static exchange
capacity of SEC = 5.1 mg-equiv/g.
For deeper 1-butene conversion into 2-butenes, the
2-butenes present in BBF can be separated out by
distilla- tion.
The conversion of 1-butene into 2-butenes is 90–91%
without BBF predistillation for the removal of 2-butenes
and ~96% when predistillation is used.
Isomerization for Improving the Quality of the
Catalytic Cracking Alkylate
Raising the 2-butenes : 1-butene ratio in the stream
to be alkylated (reacted with isobutane) increases the
pro- portion of trimethylpentanes in the alkylation
product and increases its research octane number
(RON) by 1.5– 3 points. This effect is most
pronounced in alkylation pro- cesses using HF.
For 1-butene isomerization into 2-butenes on
sulfonic acid cation exchangers in C4 fractions from
catalytic cracking, it is convenient that industrial n-
butenes + isob- utane alkylation is conducted at a 6-
to 10-fold excess of isobutane and the unreacted
isobutane is recycled for combining with the C4
catalytic cracking fraction after isobutene removal
from it. The concentration of butanes in the mixed
stream is 80–85%, which is very favorable for 1-
butene isomerization into 2-butenes without butene
dimerization and oligomerization.
Figure 1 shows the block scheme of the alkylation
pro- cess involving preisomerization.
Isomerization for Enhancing the Output
Capacity and Economic Efficiency of BBF
Separation
by Extractive Distillation
In the separation of butanes from n-butenes in
BBF by extractive distillation (with acetonitrile, N,N-
dimethyl- formamide (DMF), or another polar
extractant), the n-butane–1-butene pair is the most
difficult to split (key pair). Inversion and further
separation of volatilities are required to draw n-butane
(higher boiling component, bp = –0.5°C) as distillate
and 1-nutene (lower boiling component, bp = –6.9°C)
as bottoms.
At an extractant (acetonitrile, DMF) concentration
of 70 wt %, the relative volatility α12 of this pair is
1.25. After the conversion of most of the 1-nutene into
2-butenes (their boiling points at 0.1 MPa are +0.9°C
for trans-2- butene and +3.7°C for cis-2-butene), the
n-butane– trans-2-butene pair becomes the key pair
(α12 = 1.56 under the same conditions). The block
scheme of this process is presented in Fig. 2.
The extractive distillation unit may be preceded by
a simple adiabatic reactor with a sulfonic acid cation
exchanger, which requires minimal energy input. This
will increase the output capacity of the extractive
distillation unit by a factor of 2 and reduce the energy
consumed by this unit by a factor of 1.5–2.5 (both the
extractant recycle rate and the reflux ratio will be
decreased). This method makes it possible to carry
out, with sufficient efficiency, extractive distillation
using less expensive (even if less selective) extractants
that do not form ammonia or amine impurities or
azeotropes with C4 hydrocarbons, such as methyl ethyl
ketone.

Light Butanes Butanes

Isobutane hydrocarbons
Butane
H2
Hydroiso- merization
Isomerization on sulfonic acid cation exchanger Isomerization on the cation exchanger
Extractive (Is) (with desorption)
distillation
Alkylation and separation
BBF Hydroiso-
BBF merization
(HI)
Acid+ Dimers
Alkylation gasoline

Fig. 1. Block scheme of the positional isomerization

process combined with the production of cracking alkylate. Fig. 2. Process using isomerization for raising the output rate
of extractive distillation.
THEORETICAL FOUNDATIONS OF CHEMICAL ENGINEERING Vol. 44 No. 4 2010
 IR-1
BBF
C-1
IS
2-Butenes
Fig. 3. Production of 2-butenes and pure 1-butene from BBF via positional isomerization and distillation: IR-1 = isomerization
reactor converting 1-butene into 2-butenes (possibly preceded by hydroisomerization); IR-2 = isomerization reactor converting 2-
butenes into 1-butene; C-1, C-2, and C-3 = distillation columns; IS = inert solvent.
Obtaining Concentrated 2-Butenes
A concentrated 2-butene mixture can be isolated
directly from BBF by sharp distillation as bottoms
con- taining some n-butane. However, 1-butene
present in this product cannot be involved in 2-butenes
production. Attaining the maximum possible
involvement of 1-butene in the production of pure 2-
butenes is very beneficial for obtaining 1-butene by
the back isomerization of 2-butenes and for 1,3-
butadiene synthesis via 2-butenes epoxidation
followed the decomposition of the resulting epoxide.
In order to utilize nearly all of the n-butenes’
potential in 2-butenes production, 1-butene is
isomerized into 2-butenes in BBF and the product is
distilled, as is shown in the left part of Fig. 3 (IR-1, C-
1). For more complete 1,3-butadiene removal, liquid-
phase hydroisomerization (HI) may be carried out
before isomerization on the sul- fonic acid cation
exchanger (IR-1). If necessary, the isobutene and 1,3-
butadiene concentrations in 2-butenes can be reduced
to <0.001%.
The IR-1 temperature is 50–60°C. The catalyst can
be any sulfonic acid cation exchanger, preferably fine-
grained one with SEC > 3.0 mg-equiv/g (preferably
>4.0 mg-equiv/g). If an HI reactor is employed, its
tem- perature is set at ~60°C and any suitable
hydrogenation catalyst, such as Ni/kieselguhr and
Pd/Al2O3, is used here. The conversion of 1-butene
into 2-butenes is 91– 96%. The resulting 2-butenes
contain n-butane (10– 20%) as an impurity.
1-Butene Production
1-Butene is a valuable monomer for high-quality
plastics.
The foreign industrial process for recovery of pure
1-butene from BBF is complicated and does not
allow the 2-butenes contained in BBF to be converted
into this valuable monomer. 1-Butene forms an
azeotrope with isobutene and shows almost tangential
zeotropy with 1,3-butadiene (in excess 1-butene, α12 =
1.09) and isobu-
1-Butene+
Light hydrocarbons
1-Butene
IS
IR-2 C-2
C-3
n-Butane
IS
Impurities Impurities
tane (in excess 1-butene, α12 = 1.05). The process
includes chemical removal of impurities detrimental to
1-butene polymerization. 1,3-Butdiene is removed by
total hydrogenation, which suffers from loss of part of
the n-butenes because of their conversion into n-
butane. Isobutene is removed via the addition reaction
with a C1– C4 alcohol followed by distilling off the 1-
butene-contain- ing hydrocarbon mixture and its
washing. Isobutane is removed by extractive
distillation or by ultrasharp distilla- tion, an energy-
intensive process, in which part of the 1- butene is
lost.
Use of positional isomerization makes it possible to
obtain comparatively cheap 1-butene by 1-butene
isomerization into 2-butenes in BBF followed by the
removal of isobutane, isobutene, and 1,3-butadiene
from the product by sharp distillation, back
isomerization of 2-butenes into 1-butene, and
separation of the latter by distillation.
This technological solution may seem paradoxical.
In fact, this process is the simplest and the most
efficient. It allows nearly all of the BBF n-butenes to
be involved in the production of pure 1-butene. In
addition, 1,3-butadi- ene, isobutene, and isobutane can
be removed by ordinary distillation owing to the fact
that the 2-butenes, which are relatively high-boiling
compounds, do not form azeo- tropes or almost
tangential zeotropes with these impuri- ties. The 1,3-
butadiene and isobutene contents of com- mercial 1-
butene are the same as those of 2-butenes (<0.001%).
1-Butene obtained by isomerization in IR-2
followed by distillation may contain 10–20% n-
butane, depending on the n-butane content of the 2-
butenes leaving IR-2. If necessary, 1-butene (1) can
then be separated from n-butane (2) by sharp
distillation (α12 in excess 1-butene is 1.1) or,
preferably, distillation in the presence of a higher
boiling alkane, such as n-pentane of isopentane (this
raises α12 to ≈1.3).
The block scheme of this process is presented in Fig. 3.
A more heat-resistant sulfonic acid cation
exchanger (e.g., Amberlyst 36 or DS) and a higher
temperature of
120–150°C are used inIR-2. The conversion of 2-
butenes into 1-butene is 8–13% per pass. Due to the
recycling of the liquid bottoms from the bottom
section of C-2 into IR-2, the total conversion of 2-
butenes into 1-butene in the process is 99–100%.
The distillate obtained in C-2 contains 80–90% 1-
butene and 10–20% n-butane. If necessary, the 1,3-
butadiene and isobutene content can be reduced to
<0.001%. Distillation in C-3 affords a distillate
containing 98–99% 1-butene. One ton of BBF
containing 30–50% n-butenes gives 0.27–0.45 t of 1-
butene, which is 2– 3 times more than is obtained
without positional isomer- ization.
An alternative way of producing 1-butene from 2-
butenes is by reactive distillation.
The 1-butene production technology described here is
profitable since the cost of the resulting 1-butene is
16000–17?000 rubles per ton, while its market price is
>50?000 rubles per ton. The raw material for this
process (BBF) is available in quantity, and the process
itself is fairly simple. At a production rate of 100?000
t/yr, the annual benefit will be > 3 billion rubles.
The outlook for 1-butene realization in Russia and
abroad is quite favorable, particularly because of the
development of the production of poly(1-butene), a
plas- tic far superior to polyethylene and
polypropylene.
The 1-butene polymerization technology is similar
to the stereoregular polymerization of 1,3-butadiene
and
isoprene in the presence of TiCl4. Therefore, plants
suffer- ing from 1,3-butadiene and isoprene shortage
in Russia (Efremov, Yaroslavl) can be changed to
poly(1-butene) production.
CONCLUSIONS
Combining the 1-butene 2-butenes positional
isomerization and distillation provides an efficient
way of obtaining pure 2-butenes and pure 1-butene
from BBFs. The efficient catalysts for this process are
sulfonic acid cation exchangers, which are used at 50–
60°C in 2-butene production and at 120–150°C in 1-
butene pro- duction from 2-butenes.
REFERENCES
1. Spravochnik neftekhimika (Petroleum Chemist’s Hand- book),
Ogorodnikov, S.K., Ed., Leningrad: Khimiya, 1978, vol. 2, pp.
82–83.
2. Pavlov, S.Yu., Vydelenie i ochistka monomerov dlya
sin- teticheskogo kauchuka (Recovery and
Purification of Monomers for Synthetic Rubber),
Leningrad: Khi- miya, 1987, pp. 11–14.
3. Bobylev, B.N., Farberov, M.I., and Epshtein, D.N., 1-
Butene Isomerization into 2-Butene, Neftekhimiya,
1974, no. 14, pp. 33–37.
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