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Processes for the production of higher linear α-

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DOI: 10.1134/S0965544110040055

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ISSN 09655441, Petroleum Chemistry, 2010, Vol. 50, No. 4, pp. 283–289. © Pleiades Publishing, Ltd., 2010.
Original Russian Text © G.P. Belov, P.E. Matkovsky, 2010, published in Neftekhimiya, 2010, Vol. 50, No. 4, pp. 296–302.

Processes for the Production of Higher Linear αOlefins

G. P. Belov and P. E. Matkovsky
Institute of Chemical Physics Problems, Russian Academy of Sciences, Chernogolovka, Moscow Region, Russia
email: gbelov@cat.icp.ac.ru
Received January 29, 2009

Abstract—The results of scientific investigations and industrial developments in the field of the selective and
statistical oligomerization of ethylene to obtain higher linear αolefins are generalized.
DOI: 10.1134/S0965544110040055

One of the strategic trends in petrochemistry is the
development of processes for the production and con
version of higher olefins, including linear αolefins
(LAOs) obtained through the oligomerization of eth
ylene. Ethylene is the principal raw material of the
petrochemical industry that is used mainly to produce
polyethylene. The scale of the production of ethylene
has approached 100 million tons per year and contin
ues to grow higher. The solution to the problems of the
manufacture of linear αolefins has been facilitated by
advances in the chemistry of metalloorganic com
pounds.
The development and widescale implementation
of processes for the production and conversion of eth
ylene and propylene have led to the emergence of the
chemistry and technology of higher αolefins from С4
to С40. It is possible to distinguish the following main
industrial methods [1]:
(1) Vaporphase thermocracking of nparaffins at a
temperature of 550–650°С, a pressure of 0.07–
2.8 MPa, and a residence time of 2–10 s in the reac
tion zone.
(2) Hightemperature dehydrogenation of nparaf
fins.
(3) Hightemperature oligomerization of ethylene.
This can be effected in one of the following two ways:
—a twostage process wherein the chain growth in
AlR3 takes place at a temperature of 100–140°С and an
ethylene vapor pressure of 20–25 MPa and the extrac
tion of the resultant αolefins occurs at a temperature
of 260–310°С and a pressure of 1–2 MPa; or
—a singlestage process wherein both of the above
stages are combined and conducted at a temperature
of 190–220°С and a pressure of 23–25 MPa.
(4) Lowtemperature (30–120°С) statistical oligo
merization of ethylene in the presence of complex
metalloorganic catalysts containing titanium [2], zir
conium [3], palladium [4], nickel [5], cobalt [6], iron
[7], or chromium [8].
The worldwide growth rate of LAO production
between 1980 and 1990 amounted to 10–15 wt % per
year, and from 1990 to 2000 the annual increase in
LAO production came to 4.5–5% wt %. The total
amount of LAOs manufactured worldwide came to
2.6 million tons in 1999, 3.5 million tons in 2003, and
4.2 million tons in 2005. The worldwide production of
the most essential αolefins in 2006, the average
annual demand for them over the next 10–15 years,
and their main sources are presented in Table 1.

Table 1. Worldwide consumption of αolefins [9]

Linear aolefins (LAOs) 1Butene 1Hexene

Demand as of 2006, million 4.3 1.1 0.650

tons

Average annual increase in de 3.5 5.3 4.7

mand (2006–2020), %

LAO source αolefins Statistical ethylene oligomer Selective ethylene dimeriza Selective ethylene trimeriza
ization, 90% tion, 35% tion, ≤10%

283
284 BELOV, MATKOVSKY
The main application fields of LAOs in the chemi
cal and petrochemical industries are the productions
of ethylene and propylene—αolefin copolymers,
polybutene and polyhexene, 40%; higher alcohols,
19%; starting raw materials for the manufacture of all
season lowfreezing ecologically pure polyolefin oils
for automotive, aviation, and many other types of
modern machinery, and surfactants (including domes
tic washing agents), 14%; and heat carriers, plasticiz
ers, lubricants, additives, waxes, and many other sub
stances, 27%.
Worthy of special consideration is the problem
of the production and primary conversion of higher
βolefins (cis and trans2butenes, hexenes, octenes,
decenes), isobutylene, and also complex pyrolytic
fractions of petroleum products containing the above
mentioned olefins.
ETHYLENE OLIGOMERIZATION
Ethylene oligomerization processes can tentatively
be subdivided into selective and statistical ones. The
former embrace reactions and processes wherein indi
vidual LAOs are formed selectively, and the latter,
those which yield mixtures of LAO homologs from С2
to С40.
In this context, classed with selective processes are
those of the selective oligomerization of ethylene into
butene1 and hexene1, frequently referred to as eth
ylene di and trimerization. Catalysts will apparently
be found in the near future for the selective tetramer
ization of ethylene into octene1 (a 60% selectivity has
already been attained for octene1 [10] and ethylene
pentamerization to give decene1). Presented below
are generalizations of the scientific advances and
industrial developments in the field of ethylene oligo
merization.
SELECTIVE OLIGOMERIZATION
Production of Butene1
In the 1970s–1990s, a great amount of scientific
and applied investigations were carried out at the Insti
tute of Chemical Physics Problems, Russian Academy
of Sciences, and a number of applied research institu
tions on the selective ethylene oligomerization into
butene1 in nonpolar (nheptane, toluene, butene1,
butane–hexene fraction) and polar (ethyl chloride,
ethers) media, including:
—detailed studies of the kinetic laws governing the
dimerization of ethylene on the catalyst system
Ti(OR)4 ⎯AlR3, the nature of the intermediate com
pounds, and their role in the dimerization of ethylene
into butene1 [11–18];
—the elucidation of the composition of the active
centers and their action mechanisms [19–21];
—studies on the effect of various factors on the
kinetics and selectivity of ethylene dimerization into
butene1 [22–28];
—the development of a mathematical model for
the ethylene dimerization reaction [29];
– the search for modifiers for the principal
catalyst system to improve the selectivity of the pro
cess [33–39];
—the search for the optimal process conditions in
experimental facilities and the development of the
principal process sequence for commercial production
[34–38].
Based on the results obtained in these investiga
tions, over 30 author’s certificates and patents were
granted in the USSR, United States, France, Ger
many, and other countries.
A commercial version of the highselectivity syn
thesis of butene1 of polymerization purity was real
ized for the first time in 1982–1983 at OAO
Stavropolpolimer (Budennovcsk) and OAO Kazan
orgsintez (Kazan). The dimerization process was con
ducted on the catalyst system Ti(OС4Н9)4–AlR3–
modifier (an electron donor compound) in a column
type hollow reactor at a temperature of 65–90°С and
a pressure of 0.5–0.8 MPa. Hexenes were used as
absorbents. Formed during the course of ethylene
dimerization are butene1, 3methylpentene1,
2ethylbutene1, hexene1, and a small amount of a
polymer. The concentration of these components
depends on various factors and can range over fairly
wide limits (% by mass): butene1, 90–95; hexene1,
0.3–0.6; 3methylpentene1, 1.5–3; 2ethylbutene1,
3⎯6; and polymer, 0.001–0.04.
A logical development of the scientific research and
experimental industrial works performed at the Insti
tute of Chemical Physics Problems, Russian Academy
of Sciences, in cooperation with OAO
Stavropolpolimer and OAO Kazanorgsintez was the
purchase by the French Petroleum Institute of a
license from Russia for the process of the selective eth
ylene dimerization into butene1 in the early 1980s.
Having patented their own modification of the tita
nium catalyst in France, this institute started actively
promoting the process of the selective dimerization of
ethylene into butene1 under the trade name Alfabutol
as far back as the mid1980s. The process is conducted
at a temperature of 55°С and a pressure of 2.5 MPa in
a butene1 medium on the catalyst system
Ti(OС4Н9)4–Al(C2H5)3–modifier (an electron donor
compound). Currently, there are 24 plants operating
all over the world to produce some 25% of the butene1
consumed worldwide for the synthesis of ethylene
butene1 copolymers.
The butene1 production plants built in Russia in
the early 1980s are still operational, and in 2008 a new
plant was built by OAO Kazanorgsintez to produce
20.5 thousand tons of butene1 per year by an
improved production process allowing for operation at
PETROLEUM CHEMISTRY Vol. 50 No. 4 2010
 PROCESSES FOR THE PRODUCTION OF HIGHER LINEAR αOLEFINS
II
I 1
Fig. 1. Block diagram of the novel butene1 production process at OAO Kazanorgsintez: 1, reactor; 2, cooler; 3, catalyst extrac
tion section; 4, ethylene extraction column; 5, betene1 extraction column; and 6, solvent recycle. I, ethylene; II, catalyst; IV,
butene1; and V, C6 fraction.
a temperature of 40–70°С and a pressure of 2–3 MPa
using as a solvent both the hexene fraction formed dur
ing the synthesis of butene1 and butene1 proper
(Fig. 1).
Production of Hexene1
Currently, around 150 patents concerning the pro
duction of hexene1 by the selective trimerization of
ethylene [39] have been published in international
published data. The process developed by the Philips
Petroleum Company for the selective ethylene trimer
ization into hexene1 was implemented on the indus
trial scale in 2003 in Qatar (a production plant for
47 thousand tons of hexene1 per year) [40]. At the
root of the process were the patents taken out during
the course of the development of the process in 1993–
1999 [41–49]. The research activities of the company
enabled them to formulate the main criteria for the
selection of the catalyst system and to develop catalyst
preparation technologies and the production pro
cesses appropriate for the trimerization of ethylene at
a working pressure of 5.5 MPa in the reactor and a
temperature of 110°С. To increase the productivity of
hexene1 works, the company recommends installing
several reactors in parallel, each comprising a long
ringshaped tube or a group of Ushaped tubes con
nected in series and immersed in a boiling medium
(water or a hydrocarbon) to withdraw the heat evolved
during the reaction with the goal of generating low
pressure steam. Fresh ethylene entering the reactor
together with the recycled ethylene flow is compressed
to 5.5 MPa and heated to 100°С. The concentrated
catalyst solution—a Cr(III) complex in a recycled
cyclohexane solution prepared beforehand—is fed
into the reactor by means of a dosing pump.
PETROLEUM CHEMISTRY Vol. 50 No. 4
285
IV
4 5
V
3 III
The gas–liquid phase comprising a mixture of
cyclohexane, unreacted ethylene. hexene1, octene1,
decene1, branched α and βolefins, the catalyst, and
some amount of byproducts (mainly a polymer) comes
from the reactor to the evaporator, whence the major
part of the unreacted ethylene goes to the recycle,
while the olefin mixture goes to the separation stage.
Production of Octene1
The most promising method to obtain octene1 is
the selective tetramerization of ethylene, which
became feasible thanks to the discovery of novel cata
lysts based on chromium complexes with
R2PNR1PR2type diphosphinamine ligands. Some
of these complexes are used in the trimerization of
ethylene into hexene1. The selectivity attained for
octene1 amounts to 60–70%; up to 25% of the
byproducts formed are made up of hexene1 and ole
fins from C10 to C14 [50]. The Sasol company that in
the past few years actively searched for highactivity
chromium complexes with phosphorus or nitrogen
containing bi and tridentate ligands intend to con
struct a plant in 2011–2013 to produce 100 thousand
tons of octene1 (predominantly) and hexene1 per
year [51].
STATISTICAL OLIGOMERIZATION
Investigations in the field of the statistical oligo
merization of ethylene can tentatively be subdivided
into two stages. The first stage starts with the investiga
tions by Ziegler et al. [52] into the reactions of ethyl
ene combination with trialkylaluminum at the Al–C
bond, followed by the thermal destruction of the
“growing” АlR3 molecule and the extraction of the
higher αolefin or its expulsion from АlR3 by ethylene.
2010
286 BELOV, MATKOVSKY

Table 2. Industrial statistical ethylene oligomerization processes

Process Working pressure,

Company Catalyst system Temperature, °C Olefin composition
name MPa

Ineos Ethyl AlR3–modifier 100–120 C4–C30+ 10–12

BP Amoco AlR3 130–140 C4–C18 19

Chevron Gulfene Al–organic compound + 40–100 C4–C30+ 3–6

Phillips Nicomplex

Idemitsu Zr + Alorganic compound 100–150 C4–C20

(mixture) + thiophene deriva
tive

Shell Shop Nicomplex 50–120 C6–C30+ 2–15

IFPAxens AlphaSelect Zr + Alorganic compound + 40–150 C4–C10 0.5–15

modifier

UOP Linear1 Nicomplex 30–80 C4–C10 6–14

SabicLinde αSablin Zr + Alorganic compound 60–100 C4–C18 2–3

The second stage is characterized by studies on the use
of complex catalysts based on metals of alternate
valence that were started practically simultaneously in
Germany [53], France [54], and the USSR [55] in the
mid1960s.
The investigations already done and being con
ducted at present have resulted in the development of
various industrial processes for obtaining higher linear
αolefins (С4–С30+), whose main characteristics are
presented in Table 2.
Judging from the data of Table 2, the AlphaSelect,
Linear1, and αSablin processes show the highest
selectivity.
The further development of the Alfabutol process
yielded a process for the production of highpurity lin
ear αolefins with an even number of carbon atoms,
from C4 to C10. The process was named AlphaSelect
[9] (IFPAxens Co., France). It involves ethylene oli
gomerization in an aromatic solvent medium in the
presence of a highly active and selective zirconium
containing catalyst and provides for the high purity of
the αolefins produced. The masspercent distribu
tion of the αolefins in the mixture is as follows:
butene1, 33–43; hexene1, 30–32; octene1, 17–21;
and decene1, 9–14.
An important stage in the Linear1 process (UOP,
United States [39, 56]) using a homogeneous phos
phine nickel catalyst is the removal and recirculation
of the catalyst. In this respect, the Linear1 process is
advantageous: although the catalyst and ethylene are
both soluble in the polar solvent, the LAO products are
but little soluble in it (Fig. 2). The LAO yield in the
Linear1 process is practically 100%. The formation of
heavy polymers, typical of many oligomerization pro
cesses, is minimized here by the choice of conditions
facilitating the formation of light LAOs.
The scientific fundamentals of the αSablin pro
cess were worked out in the 1970s–1990s at the Insti
tute of Chemical Physics Problems of the Russian
Academy of Sciences [57–64]. The LAO synthesis
reaction is conducted at a temperature of 60–100°С
and a pressure of 2–3 MPa; the catalyst is a homoge
neous twocomponent system based on a zirco
nium(IV)aluminumorganic compound. In 1998,
Linde (Germany) acquired from the Institute of
Chemical Physics Problems of the Russian Academy
of Sciences the exclusive right for the utilization of this

PETROLEUM CHEMISTRY Vol. 50 No. 4 2010

 PROCESSES FOR THE PRODUCTION OF HIGHER LINEAR αOLEFINS
Ethylene recycle
Solvent
Catalyst Reactor
Separator
Catalyst recycle
Fig. 2. Block diagram of the Linear1 process.
process and constructed, in cooperation with the
Sabic, a pilot plant with 50 t/year in output in the Al
Jubail industrial city in 2000. The construction of their
industrial plant with an annual output of 150 thousand
tons of LAOs from C4 to C20 was completed in 2009.
CONCLUSIONS
The analysis of the scientific investigations into the
oligomerization of ethylene to obtain linear αolefins
and the implemented processes for their industrial
production shows that the main line of these investiga
tions is the search for and development of such catalyst
systems that would make it possible to obtain the
desired higher αolefins of high (the socalled poly
merization) purity, and with maximum selectivity at
that. Classed with such systems today are the tita
niumcontaining catalyst system used in the Alfabutol
selective process for the production of butene1
through ethylene dimerization and the zirconium
containing system used in the αSablin ethylene oligo
merization process. The scientific fundamentals of
both of these processes were developed at the Institute
of Chemical Physics Problems, Russian Academy of
Sciences, in cooperation with a number of applied
research institutions.
ACKNOWLEDGMENTS
This work was supported by the Russian Founda
tion for Basic Research (project no. 070300108a).
PETROLEUM CHEMISTRY Vol. 50 No. 4 2010
287
Preliminary
ethylene Ethylene
purification
Fractionation
of light Butene1
LAOs/C2 fractions
Separation
Solvent Solvent
extraction
Hexene1
Products Octene1
fractionation Decene1
C12 ⎯C18 LAOs
C18 + LAOs
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