ISSN 00405795, Theoretical Foundations of Chemical Engineering, 2010, Vol. 44, No. 4, pp. 536–539. © Pleiades Publishing, Ltd.

, 2010.
Original Russian Text © O.S. Pavlov, S.A. Karsakov, S.Yu. Pavlov, 2009, published in Khimicheskaya Tekhnologiya, 2009, Vol. 10, No. 6, pp. 354–358.

ORGANIC TECHNOLOGIES

2Methyl2Butene Production Using Positional Isomerization

Catalyzed by Sulfonic Acid Cation Exchangers
O. S. Pavlov, S. A. Karsakov, and S. Yu. Pavlov
Chemical Engineering Science and Technology Center, Yaroslavl, Russia
email: olefin@mail.ru
Received September 9, 2008

Abstract—Economically efficient 2methyl2butene production is an essential element of the promising

isoprene manufacturing process using 2methyl2butene epoxidation and the dehydration of the resulting
epoxide. An efficient way of producing 2methyl2butene is isopentane dehydrogenation followed by
2methyl2butene recovery from the resulting C5 fraction by liquidphase isomerization (preferably on sul
fonic acid cation exchangers) and distillation.

Key words: 2methyl2butene, positional isomerization, sulfonic acid cation exchangers, distillation.
DOI: 10.1134/S0040579510040329

Demand for concentrated 2methyl2butene
(2M2B) is largely determined by the problem of manu
facturing cheap isoprene. Isoprene obtained by 2M2B
epoxidation followed by the decomposition of the result
ing oxide is ~2 times cheaper than isoprene synthesized
industrially by twostep isopentane dehydrogenation.
Comparatively inexpensive isopentane dehydrogenation
(with gas separation) and existing equipment can be used
in the former process, as distinct from the previously sug
gested OKSEP process, which is based on isopentane oxi
dation [1], so the reconstruction of the existing facilities
will require quite reasonable capital investments.
Possible raw materials for 2M2B synthesis are C5 frac
tions from the thermal or thermocatalytic conversion of
petroleum hydrocarbons, of which the isopentane–iso
pentene fractions resulting from catalytic isopentane
dehydrogenation are the most convenient. Isopentane
dehydrogenation is performed in the gas phase at ~600°C.
The conversion of isopentane, which turns mainly into
isopentenes, is ~40%. The 2methyl1butene (2M1B) :
2M2B : 3methyl1butene (3M1B) ratio in the product
is approximately 1 : 1.9 : 0.15. The boiling points of the
isopentenes are 31.2, 38.6, and 20.1°C, respectively.
In isoprene production by twostep isopentane dehy
drogenation, converting 2M1B into 2M2B in the C5 frac
tion markedly facilitates the separation of pentane–pen
tene mixtures. At the plants changed to the 2M2B epoxi
dation technology, production of concentrated 2M2B
from the totality of C5 tertalkenes is easily accomplished
by involving the positional isomerization of 2M1B into
2M2B:
CH3 CH3
CH2 C CH2 CH3 CH3 C CH CH3 .
This reaction takes place readily in the presence of sul
fonic acid cation exchanger catalysts at 10–40°C. At these
temperatures, the equilibrium is strongly shifted toward
2M2B, and the lower the temperature, the greater the
shift. Experimental data concerning the equilibrium in
the positional isomerization of 2M1B into 2M2B are
listed in Table 1.
The positional isomerization of 2M1B into 2M2B can
be carried out not only on acidic (sulfonic acid cation
exchanger) catalysts, but, when combined with pentadi
ene hydrogenation, also on nickel, palladium, cobalt,
or platinumcontaining catalysts in the presence of small
amounts of hydrogen. The drawbacks of this method of
catalysis are a comparatively low isomerization rate and a
considerable extent of isopentene hydrogenation into iso
pentane.
Nevertheless, when there are pentadienes (isoprene,
piperylenes) in the C5 fraction, their hydrogenation is
appropriate to prevent the presence of isoprene in isopen
tane recycled for dehydrogenation. This is necessary to
avoid isoprene coking and the deactivation of the dehy
drogenation catalyst and to rule out the presence of pip
erylenes in 2M2B. Piperylenes exert an adverse effect on
2M2B epoxidation and worsen the quality of isoprene
Table 1. Equilibrium reactant concentrations in the isomer
ization of 2M1B into 2M2B at fairly low temperatures
Reactant concentrations (wt %) in equilibrium
Hydro mixtures at various temperatures, °C
carbon
0 20 40 60 80 100
2M1B 4.1 6.2 8.5 10.4 12.7 15.9
(1) 2M2B 95.9 93.8 91.5 89.3 87.3 84.1

536
 2METHYL2BUTENE PRODUCTION USING POSITIONAL ISOMERIZATION
Table 2. Kinetic data for tertpentene and pentadiene conversion
Conversion (%) of various compounds in the C5 fraction at 40°C as a function of time, h
Hydrocarbon sulfonic acid cation exchanger
2 4
2M1B into 2M2B 65.7 80.4
Pentadiene(s) 11.1 27.8
Isopentenes into isopentane – –
Dimerization, % 0.5 0.8
obtained from the epoxide. In view of this, it may be per
tinent to perform the liquidphase hydroisomerization of
C5 fraction components before carrying out the main pro
cess—2M1B isomerization into 2M2B on a sulfonic acid
cation exchanger.
Table 2 presents kinetic data on the conversion of tert
alkenes and alkadienes in a C5 fraction containing 63.7%
pentanes (mainly isopentane): 10.2 wt % 2M2B,
21.1 wt % 2M1B, 1.4 wt % isoprene, and 0.4 wt % pip
erylenes. The catalysts were a sulfonic acid cation
exchanger with a static exchange capacity of SEC =
5.1 mgequiv/g and a Ni/kieselguhr catalyst containing
~20–40% nickel. The proportion of hydrogen in the reac
tion mixture in hydroisomerization was controlled by
maintaining a hydrogen partial pressure of 0.3–0.35 MPa.
Acid catalysts, including sulfonic acid cation exchang
ers, simultaneously catalyze the undesired alkene dimer
ization and oligomerization reactions:
CH3
CH2 C CH2 CH3
iC5H10
2 iC10H20 iC15H30. (2)
CH3 dimers trimers
CH3 C CH CH3
Some researchers attempted the positional isomeriza
tion of concentrated alkenes, but this always led to their
extensive dimerization and oligomerization and to the
deactivation of the sulfonic acid cation exchanger. The
problem of suppressing or minimizing dimerization and
oligomerization can be efficiently solved since the isomer
ization reactions are monomolecular, while reaction (2) is
a bimolecular reaction or a sequence of consecutive
bimolecular reactions. The alkene isomerization selectiv
ity is sufficiently high in the presence of 60–80% alkanes.
This amount of alkanes is present in many fractions
resulting from the thermocatalytic conversion of petro
leum hydrocarbons, including C5 dehydrogenation frac
tions, so the alkenes can be isomerized selectively without
being preconcentrated. If necessary, the alkane concen
tration in the alkenes can be increased by recycling the
isopentane fraction distilled from 2M2B.
The conversion of 2M1B into 2M2B can be enhanced
by distilling the C5 fraction from 2M2B before isomeriza
tion.
THEORETICAL FOUNDATIONS OF CHEMICAL ENGINEERING Vol. 44
537
Ni/kieselguhr
5 2 4 5
82.4 21.0 38.1 44.8
38.9 90.9 ~100 ~100
– 3.0 6.1 7.5
1.0 – – ≤0.05
It is not difficult to isolate 2M2B by distillation, except
for npentane removal from it and 2M2B distillation from
trans1,3pentadiene. The distillation of isopentane from
2M1B and isoprene involves problems because of the
existence of almost tangential zeotropy in the isopen
tane–2M1B and isopentane–isoprene systems [2, 3].
Another difficulty arises from the presence of npentane,
which manifests almost tangential zeotropy with 2M1B.
This makes necessary fairly deep 2M1Bto2M2B
isomerization, and it is desirable to hydrogenize the pen
tadienes in the C5 fraction before isomerization.
3M1B, which has a comparatively low boiling point of
20.1°C, is readily distillable from all pentanes, pentenes,
and pentadienes. This compound might be of interest as a
monomer or comonomer for plastics.
Table 3 presents data characterizing azeotropy and
almost tangential zeotropy in binary systems constituted
by pentanes, isopentanes, and pentadienes.
The figure shows the process flowsheet for obtaining
2M2B and 3M1B from isopentane. This process includes
isopentane dehydrogenation, isolation of the C5 fraction
(which consists largely of isopentane and isopentenes and
contains minor amounts of isoprene, 3M1B, npentane,
npentenes, and 1,3pentadienes) from the contact gas,
isomerization (and, possibly, the hydroisomerization of
2M1B into 2M2B combined with pentadiene hydrogena
tion), distillation, 2M2B reevaporation, and, possibly,
3M1B distillation from recycled isopentane.
The isomerization reactor (IR) is charged with a sul
fonic acid cation exchanger, preferably one with SEC ≥
4.0 mgequiv/g, and the IR temperature is set at 20–
30°C. Predistillation of the C5 fraction in the column C1
for 2M2B removal is possible here. If a hydroisomeriza
tion (HI) reactor is used, it is charged with a hydrogena
tion catalyst (e.g., Ni/kieselguhr) and its temperature is
maintained at 20–35°C. Hydroisomerization reduces the
diene content of the reaction mixture, bringing the iso
prene concentration to ≤0.1% and the piperylene con
centration to ≤0.01%.
Table 4 lists the characteristics of the main streams in
the 2M2B and 3M1B production process that does not
use C5 predistillation in the column C1 the for 2M2B
removal, but separates 3M1B from the recycle stream by
distillation in the column C3. The flow numbering in
Table 4 is the same as in the figure.
No. 4 2010
538 PAVLOV et al.

Table 3. Azeotropy and almost tangential zeotropy data for binary systems constituted by pentanes, isopentanes, and pentadienes
Azeotropy Almost tangential zeotropy
Component 1
Component 2 (bp, °C)
(bp, °C) component 2, wt % bp of azeotrope, °C existence lim α
x 1 → 1 12

3M1B (20.1) Isopentane (27.8) – – – 1.24

Isopentane (27.8) 2M1B (31.2) – – + 1.05
Isopentane (27.8) Isoprene (34.1) – – + 1.04
Isopentane (27.8) 2M2B (38.6) – – – 1.36
Isopentane (27.8) Cyclopentadiene (41.5) – – – 1.20
2M1B (31.2) Isoprene (34.1) – – + 1.05
2M1B (31.2) nPentane (36.1) – – – 1.10
2M1B (31.2) 2M2B (38.6) – – – 1.20
Isoprene (34.1) nPentane (36.1) 26.0 33.8 – 1.11
Isoprene (34.1) 2M2B (38.6) – – – 1.12
Isoprene (34.1) Cyclopentadiene (41.5) – – – 1.14
2M2B (38.6) transPiperylene (42.0) – – – 1.11
2M2B (38.6) cisPiperylene – – – 1.19
2M2B (38.6) Cyclopentadiene (41.5) – – + 1.08
* lim α is the limiting value of relative volatility.
x → 1 12
1

The total conversion of 2M1B into 2M2B is 81.4%
without the column C1 and 93.9% when C1 is employed.
The corresponding 2M2B yields are 90.8 and 93.3% of the
totality of tertpentenes in the starting mixture.
The isopentane consumption in this process is ~1.3–
1.4 t per ton of the resulting 2M2B, and it is possible to
obtain 50 kg of 3M1B per ton of 2M2B.
An advantage of this process is that it allows the first
stage of isoprene production from isopentane to be recon
structed without changing the isopentane dehydrogena
tion and gas separation (C5 recovery) units. It is also
unnecessary to modify the isopentane–isopentene
extractive distillation unit, whose equipment can be used
in obtaining 2M2B, the isopentane fraction to be recycled
for dehydrogenation, and, possibly, 3M1B.

Isopentane+ 15 16
Off gas C4 C3
4b
Comp 9
Recovery C 4a
5
of the
C5 fraction 4 H2
14a
(recycle)
14
3 C6+ 6
7
Hydrocarbons 8 IR C2 H2O
C1 HI
DU 4c
12
H2

Isopentane 2 5 10 11 Ev
1 2M2B HM
12a 13
Dimers

Production of 2M2B and 3M1B from isopentane: DU = dehydrogenation unit; Comp = compressor; HI = hydroisomerization; IR =
isomerization reactor using a sulfonic acid cation exchanger; C1, C2, and C3 are distillation columns; Ev = evaporator; HM = heating
medium; 1–16 are flow numbers.

JOURNAL OF CTHEORETICAL FOUNDATIONS OF CHEMICAL ENGINEERING Vol. 44 No. 4 2010

 2METHYL2BUTENE PRODUCTION USING POSITIONAL ISOMERIZATION 539

Table 4. Characteristics of the main streams in the production of 2M2B and, possibly, 3M1B from isopentane
Composition of streams, wt %
Component
no. 1 no. 2 no. 4 (7) no. 8–9 no. 10 no. 11 no. 12 no. 14 (14 a) no. 15 no. 16
Isopentane 99.5 ~96.95 67.0 ~68.5 ~68.6 – – 94.1 95.75 2.0
nPentane 0.5 0.6 0.7 0.8 0.8 1.3 1.3 0.7 0.7 –
3M1B – 0.3 1.4 1.4 1.4 – – 1.9 ≤0.05 ~98.0
nPentenes – 0.4 0.7 0.7 0.7 0.5 0.5 0.6 0.8 –
2M1B – 0.4 9.4 6.9 2.0 – – 2.2 2.2 –
2M2B – 0.05 18.2 21.6 26.4 97.8 98.5 0.4 0.4 ≤0.02
Isoprene – – 2.3 ≤0.01 ≤0.08 – – ≤0.1 ≤0.1 –
Piperylenes – – 0.3 ≤0.01 ≤0.01 ≤0.05 ≤0.05 – – –
Dimers – – – – 0.1 0.4 – – – –
Flow rate, kg/h 1100 3246 2984 2984 2984 796 793 2188 2146 ~42

This will sharply reduce the total capital investment
necessary for changing the manufacture of isoprene from
isopentane from twostep isopentane dehydrogenation to
2M2B epoxidation followed by epoxide dehydration.
CONCLUSIONS
Combining the sulfonic acid cation exchanger–cata
lyzed liquidphase isomerization of 2M1B into 2M2B in
the isopentane–isopentene fraction (isopentane dehy
drogenation product) with sharp distillation provides a
fairly simple method of obtaining 2M2B and utilizes
nearly the entire potential of the tertpentenes in this frac
tion. The resulting 2M2B meets the requirements
imposed by the epoxidation reaction and subsequent
epoxide dehydration into isoprene.
REFERENCES
1. Pavlov, S.Yu. and Surovtsev, A.A., Outlook for the
Manufacture Isoprene and Polyisoprene Rubber, Khim.
Prom–st., 1997, no. 7, pp. 12–19.
2. Spravochnik neftekhimika (Petroleum Chemist’s Hand
book), Ogorodnikov, S.K., Ed., Leningrad: Khimiya,
1978, vol. 2, pp. 82–83.
3. Pavlov, S.Yu., Vydelenie i ochistka monomerov dlya sin
teticheskogo kauchuka (Recovery and Purification of
Monomers for Synthetic Rubber), Leningrad:
Khimiya, 1987, pp. 11–14.

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