329

ALKENE

OLIGOMERIZATION

C.T. O'Connor
Department
Rondebosch

and M. Kojima

of Chemical Engineering,
7700, South Africa

University

of Cape Town,

Private

Bag,

SUMMARY
This

paper

kinetics

of

catalysts

is

catalysts,

reviews

the

the

reaction

discussed.

especially

oligomerization

and

the

use

Particular
zeolites,

of alkenes.

of

both

attention
and

The

thermodynamics

homogeneous
is

given

homogeneous

and

to

and

and

heterogeneous

the

use

of

heterogeneous

acid

nickel

catalysts.

INTRODUCTION
The

oligomerization

of alkenes

is an

important

represents

a route to the production

of, inter

medicines,

dyes, resins,

lubricants

generally

refers to the preparation

few monomer

units

as opposed

high molecular

weight

to oligomerize

olefins,

classes

are usually

homogeneous

and

catalysts,

processes

largely

the

fuels.

dimerization

Supported

variety

their

molecular

of

dimers
weight

0920-5861/90/$07.35

for

use

linear

nickel

catalysts,

processes.

in processes

designed
in the
alkenes

of

the production

Alkene

for

of ethene

synthesis

catalysts

to convert

weight

petrochemical

industry

as

well

for

example,

in

the

use,

for

0 1990 Elsevier Science Publishers

B.V.

high

to
into

octane

a feedstock

found

weight

acid

need

hand are used

to produce
have

alkenes

of

low molecular

as a

are acid
over

by

on the other

the

to 1-butene

Homogeneous

catalysts

primarily

of
used

The first two

oligomerization

molecular

catalysts

either

of catalysts

and the last mentioned

motivated
low

plasticizers,

of only a relatively

implies

of heterogeneous

been

and

Oligomerization

and free radical.

catalysts

catalysts.
has

consisting
which

anionic

classes

conversion

or for the dimerization

application
to

nickel

zeolites,

for

quality

as

gasoline
for

supported

especially

distillate

viz., cationic,

The two main

fuels,

are three main classes

used as heterogeneous

reaction

and additives.

of molecules

There

motor

alia,

to polymerization

products.

catalyst.

catalysts

develop

detergents,

industrial

widespread
alkenes

as

both

into

high

detergent

and

330
plasticizer
mainly

industry.

highly

reactions,

In this

paper

offset

separation
the

advantage

by

and

will be reviewed

in their

activity

the

ability

to

and selectivity

difficulties

produce
for such

associated

with

the

process.

thermodynamics

first

lies

Their excellent

is often

catalyst

be discussed

reaction

main

linear products.

however,

accompanying

will

Their

then

the

as follows

and

kinetics

use

of

each

of alkene
class

oligomerization

of catalyst

for

this

- Acid catalysts
- Zeolites
- Non-zeolitic
- Heterogeneous
- Homogeneous

nickel

catalysts

nickel catalysts

- Transition

metal catalysts

THERMODYNAMICS
There

acid catalysts

AND KINETICS

is relatively

of isomers of alkenes
is not surprising

OF ALKENE
little

data

with molecular

using

on dimerization

on

individual

the

Benson

in

the

thermodynamics

method

thermodynamically

models

been

has been proposed

groups

equal, different
is assumed

some

oligomerization

of
of

catalyst

(ref.

7).

catalyst

in

fixed

dimerization

Langmuir-Hinshelwood

for exclusion

the

he has

of a catalyst

selectivities

analysing

shown

such as

with

promoted

kinetics

a model

rate

those
of

of

the

A lumped

to

metallic

with propene

be

this model

are

been

over

mass

sodium

adsorption

was

model

used

to

which
the
acid

a Ni(S%)-Zeolite

controlled.

modelled

controlling

be

if it

for

phosphoric

transfer

by

a 30-

reactions

assumed

kinetic

has

supported

dimerization

found

path for

from those obtained

process
on

alkene

followed

molecular

constants

are obtained

of

reaction

Using

for all possible

mixtures

was

the

oligomerization,

are equal.

of I-butene

reactor

expression

example,

to C,H1,

from the group calculation

firstly,

providing

constants

rate

over

in

If bimolecular

complexities

bed

for

co-polymerization.

propene-butene
The

focused
published

to form (ref. 4).

of isomer groups

that the cracking

circumvents

Propene

6).

amounts

Recently,

have
has
this

actual

and finally

(ref.

thermodynamic

Alberty

by comparing

involving,

step mechanism

group

has extended

(ref. 5) have proposed

ZSM-5

cracking

isomer

1).

This

12.7 x 10' isomers

oligomerization

(ref.

properties

proposed

isomerization,

of

3).

of

the selective

allowing

et al.

over

use

of

and butene

(ref.

unlikely

have

Tabak

conversion

the

properties

than that of hexenes.

an estimated

up to C,H,, (ref. 2) and

oligomerization

oligomerization.
propene

necessitated

to deduce

isomers considered
Various

on the thermodynamic

greater

has

species
group

alkene

predicted
those

weights

of propene

that it may be possible

ZSM-5

OLIGOMERIZATION

data available

since there are, for example,

This
Of C*s alkenes.
properties.
Reviews of
mainly

other than nickel

using

(refs. 8,9).

331
An

d-parameter

model

heterogeneous
selectivity
study

of

proposed

adsorbed

and

kinetics

a free

monomer
and

proposed

(ref.

propene,
Various

catalysts

A similar

distribution

are considered
of products

form

Nix,

both

via

between

also

been

oligomerization

13,14).

and isomerization

an

reactions

has

of alkene

in a
resin,

between

viz., reaction

over

(refs.

ll),

and parallel

mechanism,

using

acid

place
to

over
of

(ref.

proposed

intermediate

have been proposed

and chain termination

Haag

taking

for the kinetics

butene

advantage

a sulphonic

and free monomer)

a cyclic

models

10).
over

were

and

the

reaction

however

dimer

via

(ref.

viz.,

Trimers

propene

which

dimerization

mechanism,

(adsorbed

of

in

demonstrated

isobutene

monomer.

12).

a Schulz-Flory

proposed

and free dimer).

free

homogeneous

growth

was

of

reactions

adsorbed

co-dimerization

been

Langmuir-Rideal

consecutive

using

the

has

relationships

the

(adsorbed

for

catalyst

When

only

processes

chain

ignored,

is predicted.

ACID CATALYSTS
Zeolites
Although
active

for

a number

alkene

industrial

route

(ref.

has

17)

silica
operated
0.5

been

ratio

in the distillate

number

375'C

and

olefinic
Table

using

reported

at

present

gasoline

with

1 shows typical

fixed

of over 55.

a research

production
octane

properties

35

In the gasoline

number

be

kept

This

with

alumina.

4-10

MPa,

WHSV

with

mode

of the gasoline-range

When

fuels

very

of 92 is formed

in

refinery

typically

wt%

can be distillate

can

fuels

(refs. 15-17).

190-31OC,

bed,

being

promising

in a Mobil

zeolites,

with

as

most

into liquid

by Mobil

pore

product

the

equipment

extruded

(viz.,

distillate

product

medium

and

of the

hydrogenation

MPa),

scale

literature

far

alkenes

pioneered

type

70

mode

as 80 mass%

after

0.4-3

of

in the
by

of.Tight

commercial

use of ZSM-5

molar

- l), as much

cetane

are

is the MOGD process

tested

and makes

alumina

zeolites

for the oligomerization

terms of flexibility
process

of

oligomerization,

(viz.,
low

285-

and

C,,

in good yield.

and diesel-range

material.
While

ethene

conversion
pressures

can

be

employed

conditions,

is

the

relatively

greatly

enhanced

in the gasoline

gasoline

to

distillate

ratio

in

over

the reactant.
in refs.

it at low pressure

5,

index

being

Some of the findings

20

and

21.

In

Conditioning

distillate
temperatures

Depending
the

product

between

index of the lubricant

larger
related

particular,

with

decreasing

to the MOGD
boiling

point

mode,
and

on the

fresh HZSM-5

and at a temperature

the viscosity

increase

higher
18).

0.12 and over 100 (ref. 17).

the viscosity

the

the

(ref.

alkenes

to increase

at

in

mode

between

been found

unreactive

may

its
lower

reaction

be

varied

by passing

light

200 and 3OO'C

product

(ref.

molecular

process

weight

has
19),
of

are summarized

distributions

of

the

332
TABLE

MOGD Product

Quality

Distillate
Hydrogenated

Raw

Specific

gravity

Bromine

0.78

0.79

no.

Aromatic,

79

4.0

vol. %

3.0

lC

Pour point,
Viscosity,
Cetane

15'/15'

(-50

(-50

33

56

cs 9 40-C

2.5

no. (Engine)

Sulfur, wt. %

(0.002

CO.002

90% B-P.,

333

343

'C

Gasoline

Specific

gravity

15'/15'

0.73

Octane

92

R+O

92

MtO

79

products

from

that

reactants

the

distillate

various

olefins

through

mode, the product

methyl

branch

fairly

independent

effect

of

carbon

light

go

per

five
of

limiting

number

hydrogenated

the

in

the

propene

been

atoms

initial

extent

of

to be similar,
stage

100% olefinic

(ref.

5),

reactant

of

the

(ref.

branching

neighbourhood

oligomerization

found

intermediate

is essentially

carbon
the

have

a common

is

suggesting
In the

20).

with approximately

degree
21).

of
The

particularly

10.

products

(ref.

Detailed

branching

one
being

shape

selective

evident

above

identifications

up to C, have been published

a
of

(ref.

22).
The reaction
is loaded

onto

can be carried

ZSM-5

For this purpose

has no activity
achieved
ethene
lowers

at

out at much lower temperatures

of

the crystallite

Ionic Ni-exchanged
and a reaction

by means

HZSM-5

enhancing

conversion
the reaction

as

size of ZSM-5

between
effect

opposed

over

or

100 and 450'C

for propene,

to

unmodified

temperature

3OO'C

which

HZSM-5.

necessary

if Ni and/or Zn

impregnation

should

can be used to oligomerize

temperature

IOO'C

ion-exchange

(refs.

23-27).

than

0.1 Am.

be smaller

ethene

(ref. 23).

at less than 2.9 MPa

The presence

of Ni

but high conversion

of ethene

is the

temperature

required

Treating

Ni-ZSM-5

for alkene

with

oligomerization

is
for

Et,Al,Cl,
(ref. 28).

333
If

Ni is reduced,

the catalyst

been found to reduce

Zn

If
dimerizing

is

in the

5O'C

(ref.

reported

phase,
Zn

dimer

(ref.

reaction

Hz,

catalyst

to

gives

in

activity

extent the activity

from trace

Al

ZSM-12

with

Near

40-5O'C

40

optimum

4.1

example,

comprises

for

80

is

trimer

Pd,

alumina,

is not

clear

for

active

and
the

Fe

or
in

(ref. 29).

active

Ni-REY

while

to what

that

a liquid

more

Cr

all the

to the silicalite

is

= 0.6,

the

V and

and

is evidence

with

far

0.6%

at WHSV

Cu,

at high pressure

>

with

regenerate

alkene

feed
for

amorphous
product

(ref.

propene
silica-

of

propene

and tetramer.

converting

light

olefins

over HZSM-48

5 - 7 MPa and WHSV = 0.3

and ZSM-5 are reported

to

gasoline,

have been reported

- 4 (ref. 31).

by

At 23O'C,

to give essentially

the same

point fractions.

offretite,

et

ratio

unreactive
boralite
at 3OO'C.

al.

(ref.

HY, H-mordenite

pressure

reaction

HZSM-5,
and

range hydrocarbons

200 - 260-C,

Occelli

alumina

There

higher

increasing

references

in
it

contacted

HZSM-12

mainly

conditions

2.7 MPa and 0.3 WHSV, ZSM-48

high

when

MPa,

conditions

and lubricant

to be

boiling

bound

from the binder

ratio

15O'C

Co,

activity

has

Purging

to

the

be reduced

by

25).

shown

with

has low

has higher

in the above

in silicalite.

and

at

for

these

over HZSM-12

The

from Al leaching

and

hence

Zn-ZSM-5

(ref.

been

are

than

and

increased

is claimed,

silica-alumina

and

than,

Under

distillate
Mobil

between

oligomerization

reaction

that

examples

silicalites

present

size

has

less

in principle

be

the

trimer

Silicalite

feed

plays a role in alkene oligomerization

oligomerization

alumina.

arises

can

maintain

with Zn has also been

Ni-ZSM-5

silicalites

be noted

has

predominantly

more

content,

can

phase,

24)

Loading

given

of

initially

ferrosilicate

30).

the

Al

a gaseous

lifetime

(ref.

of

(ref. 25).
low

crystallite

vapour

It should

samples

of

with

catalyst

degrees.

poor activity.

oligomerization

but

water

temperatures

impregnated

and aromatics

decreasing

water

varying

result

is in the liquid

The

and

N, or

silicalite

and

which

production

oligomerization

as

selectivity,

pressure

flowing

the

becomes

conditions

pressures

in

to aliphatics

27).

HZSM-5

Silicalite

for alkene

When the feed

greater

activity

at high

Co-feeding

(ref. 23).

Ni,

reaction

results

faster deactivation.

activity

to

under

e.g.,

alone

of alkenes

(ref. 26).

addition

propene

liquid

transfer

conversion

and

for

to be active

hydrogen

in

27).

significantly

very rapidly.

the rate of deactivation

loaded

catalyst

feed

deactivates

and

compared

and omega,

propene

oligomerization.

of

at

78,

showed

containing
The

32)

little

MPa

Although

and

activity

was

activity

all extruded

1.0
below

WHSV

of H-omega

and

increased

from

to

20 wt%

their
the

HZSM-5,

sepiolite,

ZSM-5

catalyst
Under

boralite,
for

had

was

unusually

similar

silica

conditions

, achieving complete conversion

H-offretite
200

of

with

3OO'C.

860 p.p.m. Al was more active

activity

temperature

4.8

the

increased

350-C

and

steadily

from

150

to

as the
25O'C,

334

respectively. HY was active at 4O'C; HM converted little propene below 25O'C,

presumabfy because reactant and/or products are too strongly adsorbed at low
temperatures. After the reaction the BET surface areas of boralite and ZSM-5
were halved while those of the other zeolites were reduced nearly 15-fold. The
degree of branching of the liquid product as calculated from 'H and 13C NMR
spectra increased in the order boralite < offretite < ZSM-5 = HM < HY < omega
(ref. 33).
The effect of varying the NH,/Na content in NH,NaY on the oligomerization
of butenes at 5 MPa has been examined (ref. 34).

The activity decreased with

increasing Na content but the product spectrum was independent of 4: exchange.

Ion-exchangingNaY with Ni gave two temperature regions corresponding to maximum
activity for ethene oligomerization at 3.5 MPa, one near 12O'C and the other
above 300C (ref. 35).

At f20'C the product followed

Schulz-Flory

statistics.

The catalyst deactivated rapidly under conditions which gave high distillate
yield.
The effect of varying NH,/Na content on the oligomeritation of butenes
over NH,Na-mordenite at 2OO'C and 5 MPa has also been investigated (ref. 36).
Above about 50% NH,+, the increase in activity was much less than the increase
in the amount of acidity. The product distribution was fairly independent of %
exchange. The activity

was low after calcination at 6OO'C, probably due to the

presence of Lewis sites (ref. 37) which result in large diffusional resistance.
Highly dealuminated mordenite has been

tested

for the conversion of

propene, butenes and hexenes at high pressure (ref. 38).

At 1 WHSV and near

ZOO'C, the IFP polydiesel process gives a near complete conversion with a cetane
number after hydrogenation of 39 in the oligomerization of propene, a cetane
number of 30.5 for butenes, 39 for a mixture of C,/C,/C,,and 51 for I-hexene.
Under these conditions, the diesel yield (b155.C) exceeds 80% for all the
reactants except in the case of 1-hexene where it is 75%.

Ni on dealuminated

mordenite has also been shown to be reactive for alkene oligomerization with
long lifetime (ref. 39). Further examples of the conversion of alkenes over
metal loaded zeolites with a particular focus on dimerization are given in ref.
40.
The reaction of ethene, propene and butenes over
atmospheric pressure has been
spectroscopy (refs. 41-43).

acid zeolites at

investigated using infrared and UV

At

visible

room temperature, oligomer products were

detected over HY, HM and HZSM-5 calcined at 5OO'C (ref. 41).

highly branched product was formed over HY.

In particular,

At elevated temperatures, the

oligomers were transformed into coke over HY, to aromatics over HZSM-5, and
first to aromatics, then to coke over HM.

When calcination was carried out at

65O'C, a temeprature at which a large fraction of acid sites would be Lewis

sites, much less coke formation was observed.

Poisoning of strong Bronsted

335
sites eliminated

coke or aromatic

formation

and allowed

only oligomerization

to

proceed.
The

role

investigated
acidity

by

content,

sites

poisoning
was

In particular,
the

Bronsted

and Lewis

catalyst

(ref.

involved

in

of

the

46%

For

to

of

sites

sites

Lewis

ethene

over

or

sites

on

although

in dealuminated

HM

been

the

increasing

NaHY

with

over

Lewis
were

of ethene

has

the amount

changing

with

oligomerization

and oligomerization

NaHY

and varying

increase

seen to be active,

Bronsted

in the protonation

strongest

shown

poisoning

inactive.

oligomerization

at 730 or 83O'C

clearly

sites were

44).

butene

By calcining

activity

rendered

active

Lewis

pyridine

the

acidity.

of

(ref. 41).

of
NH,'

Lewis

77%

NH,'

HZSM-5,

both

sites were more

also

seen

at room

to

be

temperature

(ref. 43).
The oligomerization
type molecular
sieves

sieves

shown

and 0.2-0.3

to

catalyst

increase

MPa,

propene

fuel was

conversion,

propane

of the acid
increases

process

is varied

from

increases

from

to the tetramer

93

and

as a diluent

97%

and

a flow reactor,

distribution

rate

divinylbenzene

on

pore

water

was

reduced

the

by V.N.

used in about thirty

into gasoline.

average
product

reaction

is

Ipatieff

in

plants worldwide

As the concentration
of propene

molecular

weight

fraction

shifting

conditions

resins

Haag,

a macroreticular

to oligomers

of

the

product

from the trimer

are 200'C and 3 MPa.

of products

of

for the oligomerization

using

a sulphonated

pore structure

distribution

product

copolymers

conversions

33% dimer,

by overall

a mixture

At

indicating

of alkenes

for isobutene

formation

conversion
was

of butenes

at temperatures

were obtained

57% trimer

2460

over

oligomerization

and

10% tetramer,

(ref. 11).
g

of -lOO'C,

At 60-C

liquid/g

a range

has

styrene-divinylbenzene

has shown that at 16'C, 1 MPa and LHSV = 180 the conversion

of

in

This

and co-dimerization.

exchange

11,4B).

acid catalysts

kieselguhr.

reported

(109%) there is a wider distribution

being governed

oligomerization

the

Typical

(ref. 47).

89% and the product

the

is currently

139 to 151, the major

(refs.

with

supported

originally

of propene/butene

The use of cation

copolymer

of non-zeolitic

acid

and was

amounts of cracking

reported

maximum

Medium

to C,, fractions.

produced

from 92 to 109% the conversion

to

acid strength

significant

applications

phosphoric

This process

for the oligomerization

3600

while

(ref. 45).
propene

little distillate

uses

as the Catpoly

1935 (ref. 46).

been

converted

aluminophosphate-

acid catalvsts

oligomerization

higher

non-zeolitic

by Long et al.

31, 34 and MAPO-11

One of the most widespread

known

over

activity.

Non-zeolitic

alkene

olefins

has been reported

such as SAPO-11,

At 37O'C

of light

of

when the functionalization

was
this

and LHSV =

cat-h.

sulphonated

1.5 MPa

in

and WHSV

In

the

styrene-

1.7,

was 100% (ref. 49).

336
There are limitations, however, in using these catalysts due to their poor
thermal

stability

above

sulfonation (ref. 50).

overcome

by

attaching

previously activated silica and

by

subsequent

13O'C.

trimethoxybenzyl silane to

This

may

be

In the oligomerization of isobutene at 13O'C this

catalyst achieved a similar selectivity to that reported in ref. 11 but higher

conversions (97% as opposed to 58%).

At 13O'C the catalytic activity decreased

by 50% over 120 h due to a partial loss of sulphonic groups and deactivation of
the remaining groups, presumably by esterification.
Fletcher et al. (ref. 51) have studied the oligomerization of propene over
the dioctahedrai clay, synthetic mica-montmorillonite, at 6 MPa.

They found

that in the presence of Lewis acid sites high conversions and long lifetimes
were obtained.

When moisture was present a temperature runaway occurred and

rapid deactivation ensued.

This was thought to be due to the conversion of

Lewis to Bronsted sites by rehydration with the latter sites resulting in higher
activity.

The higher activity also increased the formation of high molecular

weight products which led to deactivation due to "coke" formation.

The main

products at 171-C and 1.6 WHSV were the trimer, tetramer, pentamer and hexamer
(all -20 mass%).
HETEROGENEOUS NICKEL CATALYSTS
Although heterogeneous nickel catalysts have been extensively reported for
use

as alkene oligomerization catalysts most of this literature predates 1980.

Nickel supported on various aluminosilicates is widely used

especially for the

dimerization of ethene, propene and butene (refs. 23,27,52-55). These supports

include silica-alumina, silica, layered alumina-silicates and zeolites such as
mordenite, Zeolite-Y, and ZSM-5.
been discussed.

The use of zeolites as supports has already

Ethene and propene can be oligomerized over a nickel oxide-

silica-alumina catalyst prepared by mixing a solution of sodium silicate with a

solution of aluminium and nickel nitrates (ref. 52).
ratio was

The

Al/(Al t Si) atomic

0.05 and the nickel content ranged from 0 to 8 atomic %.

An optimum

of 3 atom% Ni was observed for ethene oligomerization. This corresponded to the

optimum acidity of the catalyst at different nickel loadings.

The selectivity

to butene isomers was related to the Al/Ni ratio rather than to Al or Ni

content.

The major product in the oligomerization of propene over a similar

catalyst,(3 atom% Ni, 3 atom% Al, 94 atom% Si prepared by coprecipitation) were

dimers, predominantly 2methylpentene.

The dimerizing site is proposed to be a

combined low valent nickel and acid site (ref. 56).

Espinota et al. (refs. 57"

59) have carried out studies of ethene oligomerization over nickel-exchanged

amorphous silica-alumina.
SiO,/Al,O,molar ratio of 50.

The catalyst contained 0.27 mass% Ni and had a

Reactions carried out at 1.1 MPa and 3OO'C showed

that the major product was the dimer.

The oligomerization activity of the

337
catalyst

was found to be proportional

in nickel
more

loading

dimer.

alumina

was

oligomerization

using

found

mainly

led to an increase

The

precipitation

obtained
nickel

impregnation,

using

as that

found

active.

dimerizing

on its own produced

mainly

the

catalytic

and

Al,O,/SiO, olefin
the

alumino

layer

active

silicate

coordinatively

type

unsaturated

nickel

participation

Bercik

et

comprising

al.

63,64)

(Ni-SMM)

and acidity

(mainly

had

trimer

and

SMM

tetramer)

(ref.

initially

ethene was converted

the Ni2' exchanged

silica-alumina,
The nickel
poisoned

site was

was

monoxide

leaching

case

Ni-SMM

Bronsted

the

active

further

Gamma-

(ref. 66).

to

formed.

on

4 MPa

filling

method

prepare

that

alumina

and silica-alumina

NiO-

suggested

that

into

al.

mica-

propene

and

in surface

oligomerization

lifetime

and

67-69)

in the

activity

found

that

at ZO'C over

case

of nickel-

ion/Bronsted

dimerization

enhanced

area

and zinc into SMM by

nickel

activity.
by

(ref. 71) have observed

in

was

(ref. 70).

nickel

resulted

site.

activity

catalytic

reduced

nickel

the

layer of the synthetic

when reacted

the

with

substituted

propene

as

general

ions

of Ni'(CO), complexes

removing
et

in

for oligomerization.

(refs.

proposed,

nickel

treatment,

incorporated

cobalt

a combined

matrix

and

for oligomerizing

to n-butene

of

and

nickel

in an increase

at 130'C

the

studies

thermal

nickel

co-workers

They

of

The
which

silicate

used

catalyst

Robschlager

an

carbon
in the

enhanced

of the hydrogen.

impregnated

with

(refs. 72,73).
a

or

have been

increase

by

has

was

support

NiO,/SiO,

unsaturated

for

hydrogen

reduction

or eta-alumina

at 6O'C,

He

layer

of nickel,

and

improved

were

pressure.

Dimerization

due to the formation

acidity dl(e to oxidation

and butene

61,62).

to be a Ni+ ion since

in flowing

that

of

selectivity

site was

same

were

selectively

proposed

of Ni-SMM

activity

Sohn

montmorillonite.

that

by CO treatment

Reduction

of

66).

products

After

resulted

on

of

silica-

deposition

out extensive

into the octahedral

but did

to

at the

nickel

shown

and

effect

the

respectively.

The incorporation

little

relative

This

have

clay

of -90X,

series

is a very active catalyst

dioctahedral

(ref. 65).

ion-exchange

(refs.

supported

The nickel was incorporated

layered-lattice

coordinatively

nickel

homogeneous

has carried

such as montmorillonite

(refs.

montmorillonite
butene.

of

on

(ref. 60) and the last mentioned

of

ions

ions in the neighbourhood.

of clays

Wendt

structures,

aluminium

structure

and

supported

on the silica-alumina

exhibited

by

and the production

nickel

at ZOO'C

catalysts

proceeds

Catalysts

conversion
over

An increase

At 80'C and 5 MPa the same activity

properties

phases

acid strength.

conversions

activity

trimers.

dimerization

catalytically

At

(-25%).

for silica-alumina

a strong

structural

propene

coprecipitation

(-60%) and trimer

imposed

in ethene

of

urea has been investigated

to be the most

dimer

to the support

series

of

with aqueous

nickel

Chauvin
catalysts

solutions

sulphate

dimerizes

propene

al. (ref. 74) used a pore

et
by

impregnation

of nickel

nitrate,

of

silica,

sulphate

or

338
Calcination

chloride.
and

partially

in air at 5OO'C

removed

the

entirely

in the catalysts.

sulphate

and

nitrate
and

chloride

on alumina,

the

of sulphate

Bronsted

acidity,
anion

the

homogeneous

system,

of branched

chain

homogeneous

and

the

activity

inter-

and selectivity
and

impregnating

was

aluminium

After

then activated

chloride.

at 4.5 MPa,

The

dimerization

Zr0,/B033- has
sulphuric

been

were

of

evaporating

ethene

on a nickel
low valent

site
nickel

the

mass

in

formation

problematic.

and

of mechanisms

in the heterogeneous

over

Similar

dryness

The

catalyst

heat

transfer

influence

the

prepared

by

catalyst

of propene,

mainly

Less promising

80,81).

The

oxychloride

to dimers,

results
alkoxide

most

mixture

were

of nickel

in air

was obtained
obtained

NiO-Zr0,/P0,3
of

increased

and

these

NiO-

was

by treatment

treated

and the

for the enhancement

when

the

by coprecipitation

followed

not acid

the

and diethyl

(refs. 75-79).

active

upon heating

producing

calcining

were prepared

Catalysts

proposals

solution

chloride

NiO-Zr0,/S0,2-,

The catalysts

thus

and

aluminium

Dehydration

and OH site,

to

by an aluminium

to be responsible

ion.

favoured

however,

anhydrous

over

(refs.

catalyst.

samples.

of S=O were thought

with
as a

found

quite dramatically

oligomerized

by using

chloride-zirconium

ZrOJanion

that

The extrapolation

can often

HzSO,, H,PO, and H,BO,, respectively.

as were

to

of the support

is,

The

Lewis and

increasing

such as alumina with an aqueous

was replaced

studied

acid treated

from a nickel

systems

and aluminate

acts essentially

similar

is different

and LHSV = 2.5.

chloride

role

nickel

inactive.

of strong

sites

intra-particular

98% conversion

35-5O'C

the aluminium

systems

and

support

hexahydrate.

of

remained

of such catalysts.

butene

a porous

was

ions

containing
With

oxide

catalyst

that the nickel

oligomers.

of the nickel

of

in heterogeneous

Propene

catalyst

the acidity

and higher

ions

content.

of nickel

population

playing

heterogeneous

environment
presence

resistances

nitrate

to

anion

This

acidity.

and

nitrate

sulphate

ions induced the appearance

possibly
and that

the

the

of the Ni/Al,O, catalysts

increasing

They proposed

dimers

decomposed

whereas

led to a mixture

Lewis

strength

content.

catalyst,

electronic

with

or chloride

dimerizing

from

increased

of weak

addition

ions

The activities

calcination

appearance

increasing

chloride

completely

were

inactive

inductive

of electron
Bronsted

with

effect

deficiency

acidity

and a

were made in the case of NiO-TiO,/SO,*-

(ref. 82).

HOMOGENEOUS

NICKEL

Alkene
reviewed

(refs. 83-88).

literature
reaction
85,86)

CATALYSTS

oligomerization

relating

conditions,

has reviewed

using

Fel'dblyum

to the

homogeneous

and Obseschalova

dimerization

composition
the methods

catalysts

of

alkenes

of products
of preparation

had

been

extensively

(ref. 84) have reviewed

with

respect

and mechanisms.
and the control

the

to catalysts,

Bogdanovic

(refs.

of selectivity

in

339
nickel catalyzed
reviewed

olefin

alkene

telomerization
reviewed

oligomerization

and

using

alkyne

oligomerization,

organometallic

comprehensively

the

One of the major

is that

in general

can

heterogeneous
the

reactions

catalyst

important

system

class

is particularly

better

the

with

respect

to

reactions

corresponding

is usually
systems

controlling

the

have

by transition

the

for alkene dimerization

and

88)

catalyzed

than

based

(ref.

al.

propene

temperature

Nickel

catalysts

and

controlled

reaction

defined.

of homogeneous

et

of homogenous

easily

(ref. 87) have

al.

co-oligomerization

Pillai

of ethene

advantages

be more

because

suitable

compounds.

dimerization

metal complexes.
they

Keim et

reactions.

lower

and

constitute

an

because

mode

of

nickel

linking

of

olefins.
One of the most
oligomerization
(ref.

89)

olefins
which

and

important

uses of homogeneous

is in the Shell Higher

currently

producing

in

per annum. The oligomerization

is largely

immiscible

and 7-14 MPa a mixture

Schulz-Flory

distribution.

ligand

units
bond

starting

complexes,

oligomerization
membered
mechanism

FIGURE 1

nickel-ligand

: a n,a-coordinated
containing

the

catalysts,

P-O chelate
proposed

chelate

fragment

which

lead
must

tons

formed

consisting

active

square

(ref.
and

planar

90).

selective
and

by Keim

of

out in a polar

is converted

catalyst

during

must

linear
solvent

catalysis.

is formed

with

to highly

linear

typically

of two

The

nickel-

linear
possess

ethene
a

five-

obtained.

for ethene oligomerization

unicomponent

1 (ref. 92) shows the nickel-hydride

for the a-olefins

Nickel hydride mechanism

Used with permission]

million

C,-C,, a-olefins

ethene

for ethene

part, P-O, and a u-coordinated

ring (ref. 91). Figure

to account

one

(R,P)Ni-Ph

to
be

of

catalysts

(SHOP) developed

products

of mainly

In this process

using a non-Ziegler

carbon

excess

nickel

Process

is usually carried

with the a-alkene

At 80-12O'C

oligomers

Olefin

[From ref. 92.

340
The sulphonated nickel ylide organometallic complex I shown in Figure 2
is a powerful single-component catalyst for the oligomerization of ethene to
linear alkenes (ref. 93). Aluminium alkoxides (produced in reactions between
AlEt, or Al(iBu), and appropriate amounts of alcohols in toluene solution at
I, highly active catalysts for ethene

2O'C) produce, in combination with

oligomerization to mixtures containing predominantly linear 1-alkenes which have

even carbon atom numbers, from C, to C40+, and follow a Flory molecular weight
distribution.

Ph

FIGURE 2

Ph

Ph

Sulphonated nickel ylide organometallic complex I

Another important industrial application of nickel based homogeneous

oligomerization is the IFP OIMERSOL process for the dimeriration of light
alkenes such as propene and butenes (refs. 94-101).
under rigorously controlled conditions at

The process takes place

reduced pressures and

ambient

temperature in the presence of a nickel and aluminium alkyl complex which is

immediately destroyed in an NH,-Ha0 system on completion of the dimerization.
Although PdCl, and

RhCl, are more

selective than Ni

complexes for

the

dimerization of propene to linear hexenes, nickel is preferred because it is

cheaper and the activities are in general greater.
Afkene dimerization by Ni complexes in solution occurs by "degenerate
polymerization" which
insertion and

involves an

finally a

initiation reaction followed by monomer

transfer reaction (chain termination).

Typical

precursors of the active nickel species are the x-allylnickelphosphine-aluminium

halide system, and nickel(I1) complexes or salts associated with alkylaluminium
halides which have a reducing function associated with their alkyl groups and a
Lewis acid character which is due to the presence of halogen.
The environment of the nickel in the active species directly influences
the course of the dimerization reaction.

At each insertion step into Ni-H or

Ni-C there are two possibilities depending on whether or not insertion follows
Markownikov's rule.

Steric crowding, donor-acceptor strength of surrounding

ligands and electronic charge of the nickel will all influence the direction
followed. Figure 3 shows a scheme for the distribution of the products of

341

propene oligomerization. Insertion into the Ni-H bond is kinetically controlled

whereas the second step depends on the nature of the tigand.

CH,=CHCHLHdXGi,

TH,

Ni--C'HCH&HXHKH
Ni--C*
CH~CH=CHCH&H&H>
Ni-CH,CH,CH,
r4.sc,

CHa
CH3
Ni-CHICHCHICHICHs

-NW

CH,&H.CHKHI

M-C,

Ni-H+
CH,=CHCHa

CHJ
CH,=CHCH,CHCH.

Ni-CHCH,CHCHa

-NiH

CH,

N--C,

CHJCH-CHCHCH,

CHa
Ni-CHCH,
M-C,

FIGURE 3

CHI CHs
I
I
Ni-CHKH-CHCHa
M-C,

-N,"
-a--

,H:s

iHH:H

Simplified mechanism for oligomerizationof propene using homogeneous

nickel catalyst [From ref. 83. Used with permission]

In the dimerization of propene using NiCl*(PRs)f AlEt,Cl, for example, nhexane formation at -2O'C and 0.1 MPa varies from 21.6% to 1.8% when the
ligands used are P(tBu)a and P(iPr),, respectively (ref. 85). Similarly changing
the Lewis acid can also significantly change the amount of linear hexenes. The
selectivity of dimerization, however, is also strongly influenced by conversion.
The influence of ligands on the activity and selectivity of nickel based
catalysts has been extensively researched,

Since the majority of transition

metal catalysts give branched oligomers, an important area of investigation has

been the influence of ligands on linearity of the dimer.

Chelate ligands such

as phosphorous-oxygenand arsine-oxygen are associated with the oligomerization

of ethene to exclusively linear a-alkenes. Even in phosphine free systems very
high dimeritation activities are obtained with 58% selectivity to n-hexenes in
the case of propene dimerization at ISO'C (refs. 102,103). The use of olefinic
and diketonate ligands for the oligomerization of butenes results in the
formation of

linear dimers

(>80%). A

Schulz-Flory distribution of

oligomers was observed and activities of

butene

1200 mol products/m01 Nigh were

obtained (ref. 104). The oligomerization of ethene, propene and butene by the
catalytic system derived from Ni(sacsac)PR,Cl/Et,AlCl(sacsac = pentane-2,4dithionate anion) has been reported (refs. 105-109). All these catalysts showed
extremely high activities with enzyme-like TON values of 1000 s-l.

Cave11

342
(ref. 110) has also reported
lower

111)

alkenes,

produced

reported

been

over

reported

obtained

TONS

at 8O'C

to prepare

with

ethene

complexes

(refs.

In the case of ethene

ligand.

basic phosphine
an easier
(25-C,

desorption

2 MPa,

dimerization
ligands

was

also been

used

tri-(C,-C,,)
to

form

can be supported

Ni(I)

trialkylphos-

and ethene
supported

the ligands

dimerization
Ni"

required

oligomerization

to Ni' at

to build the

was observed

or over those containing

only

only one TAP

the electron

1-butene
linear

density

on the nickel

reaction

products.

was obtained

using

hexenes

At a conversion

of 23%

PEt, ligands.

In the

two

were observed

of

and allowed

only

in the presence

of H

(ref. 118).

The

correlation

for

121).

alkene

close

heterogeneous
hydrides

analogy

the

initiation

of

the
which

polymers.

formed)
catalysts

or

of

homogeneous

studied

between

are

occur

via

and

heterogeneous
et

al.

(ref.

NiCl,-RmAIC1,_,

on the fact

for

the

(by insertion)

catalyst

and

Fel'dblyum

based

reponsible

to

by

homogeneous

and NiO/SiO,-Also,

metal

postulated

catalyst
is

Ti (IV)
is

either
from
such

oligomerization

process
is

inhibited

used
by

complex

that

steps

thermal

In both

are proposed,
decomposition

to

and

coupled

catalysis.

reduction

modifiers
from

the
as

the

of

molar

Et,Al,Cls

ethene

on

metal

prevent

complexes

and
and

of

the

high

the
of

polymer

(ref.

of t-butene

the

to

to

Ti( III)
weight

formation

condition

shown

Ethene

catalyst

molecular

(at which

been

to I-butene,

122).

co-catalyst

have

At -25'C the product

to

formation
of

suppress

ratios

(ref.

agent

the

production

as

selectively

titanium

a modifying

such as P(OPh),

BFs-alcohol

catalysts.

based

thus

for

high Al/Ti
use

to dimerize

adding

and

responsible

Catalyst

can result

proposed

homogeneous

IFP Alphabutol
type

polymerization
stabilize

been

HNiCl or HNi(0)n_l.

In the

complex

mechanism

has

and propagation

was

the

heterogeneous

Ziegler

the

was

transition

termination

reduction

between

dimerization

NiCla/SiO,-Al,O,

of

cases similar
chain

recently

(ref. 116) it has been shown that the presence

of the primary

CzH4) 95%

(ref.
Ethene

products

catalyst

catalyst

the silica

Propene

catalysts

increased

of propene,

systems

ligands

the

are propene

The TAP reduced

nickel

have

loss in activity.

on silica

active entity.

over TAP free monovalent

has

of

of

(ref. 115).

and at the same time provided

alkene oligomerization

promoters

by reacting

of

if a homogeneous

any significant

supported

116-120).

room temperature

presence

et al.

EtAlCl.JC,H,Cl.

catalysts

and o-alkenes

the

can be gained

on a solid phase without

catalysts

in

and Cz-C,, a-alkenes

advantages

Bogdanovic

distribution

nickel

alumina

for the conversion

ligand

Schulz-Flory

and 6.5 MPa. Homogeneous

triethylaluminium

(TAP)

into oligomers.

n-CsHsNiBrP(C6H11)s

112-114).

process

alkylaluminium

phine

using

organophosphorus-sulphonate

(refs.

in a combined

Many

from methane,

similar

oligomerization

on the use of these catalysts

which

Ti(II1)

is

123).

Other

be

active

oligomerization

was

343
mainly

the trimer

the products

and tetramer

are mainly

The use of methanol

has been supported
and tetramers
been

used

effect

of adding

hydrogenation
involving
during
A

suitable

homogeneous

as

dimerization

former

breaking

promoted

Cobalt
catalyst

whereas

on

lubricant

catalyst

are

increased

tetramer

synthesized

High

pentafluoride

upon

Reaction

cyclopropane

pathways

intermediate
(ref. 127).

acetate

in conditions

and

over

the

WO, electrons

and

which

ReO, and WO,

latter

2,2'-

are

can

be

(ref.

not

129).

dimerization.

Bond-

are supplied

supplied

Thus double-bond

carbon

of alkenes

has

only

breakage

and the cobalt

was

essential
salt,

via

through

is difficult

obtained

in the

isobutene

at lOO'C,

TaCl,

and

lOO'C,

with

an

to dimer

3.5 MPa

contacting

(11.8%)
10 MPa

and
and

at conversion

in graphite

Cu

LHSV

this

metal

trimer

with

(1.9%)

supported

100%

levels

selectively

1.

at 9O'C

= 22 over

vapour

catalyst

: 100 parts
In

hexenes

(51%)

and

a catalyst

silica

(ref.

on a-alumina

selectivity

of 47% (ref. 133).

dimerized

and

promoter

of linear

(37%),

using

conversion.

alkali

and WHSV

Carbon

synthesis

of the

obtained

60% of the dimer consisting

of

comprising

was obtained

activation

suitable

when

(20 parts Co
were

(ref. 130).

features

dimerization

be

exhibited

contacting

concentration

in ethene

to

: t-butene increasing with decreasing

four-fold,

intercalated

shown

to linear oligomers

nitrate

at

been

and no activity

of the

dimerization,

propene

methyl-1-pentene

which

126).

palladium

out

Other

subliming

A catalyst

oligomerized

reactions

conversions

were

by

carried

as a support.

the activity

(12%)

been

with

conversions

propene

131).

The

product

have been proposed

on

the use

solution,

Maximum

of

reaction
based

ingredient

12 MPa, the ratio I-butene

case

(ref.

a protonated

to be active

activated

catalyst

or kieselguhr

carbon).

132).

a heavier

have

BF,.

is favoured.

supported

with an ammonia

(ref.

is to produce

from the Fermi level.

for oligomerization

of this

to di-, tri
oxides

using

to occur readily with ReO, where electrons

band

an essential

alumina

BF,

METALS OTHER THAN NICKEL

has

metathesis

was thought

and dimerization

124).

(ref. 128).

dimerization

activation

(ref.

difference.

oligomerization

of a-olefins

through

reported

range

little

a mixture

catalyst

been

USING TRANSITION

conduction

thermal

has

anhydrous

Propene

the

rearrangement

ligands

made

such as nickel-copper-chromium

of

at -35'C

In the case of propene

to decamer

and used for isobutene

oligomerization

is

DIMERIZATION

was

in the tetramer

acid as co-catalyst

Promoters

promoters

(78% combined).

the course of the oligomerization

necessarily

the

on alumina

skeletal

bipyridyl

The

oligomers

or acetic

(ref. 125).

in the

fractions

f-butene

to 4-

Antimony
at 2OO'C

and 2.6 MPa (ref. 134).

The dimerization
(ref.

135).

Silicates

of propene
of

alkali

using alkali metals

and

alkaline

earth

has been reviewed

metals,

by Pines

a-aluminas

and

344

graphite are satisfactory supports.

porous.

The support should preferably be non-

K/KzCC$ had a high propene dimeriration rate (1509 hexene/g atom K+h)

at 150C and 10 MPa.

79% of the products were 4-methyl-1-pentene. When reacted

homogeneously in benzene solvent, an optimum conversion of 58% at 214-C yielded

16% propane and 48% branched C, olefins.

The dimerization proceeds through an

initial formation of an organoalkali compound followed by metalation of the

propene.

Isobutene and Z-butene undergo dimerization with difficulty in the

presence of alkali metal catalysts.

This paper has reviewed the literature on the oligomeriration of alkenes.

Heterogeneous acid catalysts, exemplified prominently by 2519-5,are particularly
suitable for the production of liquid fuels ranging from gasoline to diesel.
Homogeneous catalysts are mostly based on nickel and are used for converting low
molecular weight alkenes into either dimers or high molecular weight linear
oligomers.

Transition metals such as nickel can also be incorporated into

heterogeneous acid catalysts to yield a bi-functional type catalyst.

this

literature is

dominated by

reports on

the

Although

synthesis, activity and

selectivity of homogeneous catalysts, these have not been very widely used in
the synthetic fuels industry apart from the production of dimers of C,,
alkenes.

Historically solid phosphoric acid has been used to oligomerize

alkenes into synthetic gasoline but recent developments using zeolites, as

described in this paper, may see the use of this class of catalyst grow
extensively in the future.

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