Applied Catalysis A, General 543 (2017) 82–97

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Applied Catalysis A, General

journal homepage: www.elsevier.com/locate/apcata

Feature Article

Applications of light olefin oligomerization to the production of fuels and MARK

chemicals
Christopher P. Nicholas
Exploratory Catalysis and Materials Research, Honeywell UOP, 25 East Algonquin Road, Des Plaines, IL 60017, USA

A R T I C L E I N F O A B S T R A C T

Keywords: The oligomerization of the light olefins ethene, propene, and butenes into fuels and chemicals has been in-
Catalysis vestigated and commercially practiced for many years. While the area appears on the surface to be mature, many
Zeolite advances have been made in recent years. In this feature article, I discuss the mechanisms of reaction and
Nickel showcase catalysts and processes useful for oligomerization from both the open and patent literature.
Resin
Commercially practiced processes are spotlighted. Among the catalysts utilized in the art are acidic catalysts
Solid phosphoric acid
such as solid phosphoric acid and zeolites, as well as metal based catalysts including aluminum alkyls, and nickel
Metallacycle
Fuels and zirconium based complexes and solids. A short section on catalysts and processes which utilize a metalla-
Chemicals cycle mechanism in order to achieve high selectivity to 1-hexene or 1-octene is followed by a discussion of multi-
functional materials possessing both acid and metal active sites. Finally, processes where oligomerization is a key
step in a multi-step or multi-reaction process are discussed.

1. Introduction is divided according to the mechanism utilized by the catalysts, with

The oligomerization of the light olefins ethene, propene, and bu-
tenes into fuels and chemicals has been investigated and commercially
practiced for many years [1]. Initially, non-catalytic thermal methods
had been utilized to convert light olefins into more useful compounds
[2–4], but Ipatieff’s discovery of solid phosphoric acid catalyzed oli-
gomerization 80 years ago sparked the first widespread use of oligo-
merization as a method of synthesizing transportation fuels [5,6]. Mobil
then advanced acidic oligomerization technology with commercial
application of MFI zeolite in the conversion of light olefins derived from
methanol to fuels in their New Zealand refinery from 1985 to 1997. A
key step in the overall process is the oligomerization of light olefins to
gasoline and distillate [7]. In the meantime, Ziegler had discovered
metal catalyzed oligo/polymerization [8], several of which catalyst
types have since been commercialized. While thermal methods have
been recently investigated again, and radical mediated oligomerization
is also feasible, catalytic methods dominate the market due to the
control afforded over the product [9,10].
In this feature article, I discuss recent developments in catalytic
olefin oligomerization of C2eC5 olefins, with highlights both from the
patent and open literature that have occurred, largely since O’Connor
and Kojima’s review [11]. To help focus the text, alcohol and other
oxygenated molecules are not covered as feedstocks here unless a
specific step to produce olefins has been reported, although biomass
conversion via oligomerization routes has been successful [12]. The text
acid-catalyzed carbenium chemistry and metal catalyzed 1,2-insertion
the two most frequently utilized mechanistic routes for oligomerization.
Both types of catalysts are used in currently commercially practiced
processes. In these reactions, the relative rates of oligomerization and
side reactions such as isomerization (both double bond and skeletal),
cracking (mono- and bi-molecular), aromatization, hydride transfer,
and coking are a strong function of structure and reaction conditions
(e.g. temperature, pressure, contact time) [13,14]. In general, cracking
reactions and hydride transfer reactions often leading to aromatics and
coke precursors are favored at higher temperatures (> 300 °C) [15],
with oligomerization favored at lower temperature (< 200 °C) [16].
Thus, the selectivity to specific products is dependent both on catalyst
and process conditions.
Understanding the impact of mechanism on oligomer molecular
weight distribution is also important. Two are frequently observed,
both of which describe asymmetric oligomer distributions. Because zero
insertions is the monomer, negative insertions by definition cannot
occur, but production of any length chain is feasible, an asymmetric
distribution of oligomers is mathematically necessary.
A long known mathematical function, the Poisson distribution [17],
is the less frequently observed and can be utilized to describe dis-
tributions of oligomers where production of each oligomer number is
independent of others [18]. Acid catalysts need to build a high con-
centration of dimers before trimers are produced, therefore, acid cata-
lysts should never give a Poisson distribution of oligomers since this key

E-mail address: Christopher.Nicholas@honeywell.com.

http://dx.doi.org/10.1016/j.apcata.2017.06.011
Received 17 March 2017; Received in revised form 5 June 2017; Accepted 7 June 2017
Available online 09 June 2017
0926-860X/ © 2017 Elsevier B.V. All rights reserved.
C.P. Nicholas
condition is not met. Metal based catalysts sometimes give Poisson
distributions, but chain termination needs to be independent of
monomer insertion as well as chain length independent, and oligomer
reinsertion cannot occur.
The Schultz-Flory distribution can be used to describe oligomer
distributions where chain termination is kinetically competitive with
the rate of propagation and/or reinsertion of oligomers occurs [19,20].
Cracking or other side reactions should not be present at kinetically
relevant rates. Most metal catalysts will therefore give Schultz-Flory
distributions of oligomers; these tend to be broader than Poisson dis-
tributions [21].
Following a discussion of catalysts using acid and insertion me-
chanisms, I then explore the typically homogeneous catalysts which
utilize a metallacycle mechanism to oligomerize ethylene and other
light olefins into dimers and trimers. These catalysts are the base of a
growing industry to produce C4eC8 olefins as comonomers for poly-
ethylene and polypropylene production. After discussing bifunctional
catalysts which utilize both metal and acid sites/mechanisms, I finish
by looking at several combination processes where oligomerization is
one of the key steps.
2. Acid catalyzed oligomerization
While olefin oligomerization is a deactivation or undesired reaction
mechanism in many acid catalyzed transformations of olefins [22], it is
also a useful method of carbon–carbon bond formation, provided that
proper catalyst and conditions are utilized. For over 80 years, C2eC5
light olefins have been oligomerized over acidic catalysts to fuels,
principally gasoline, but recently to distillates as well. Market sizes are
difficult to estimate as the fuels produced via oligomerization are ty-
pically not accounted separately from other refinery sources, but an
installed base of approximately 60 oligomerization units primarily
converting propene, butenes, or combinations thereof with nameplate
capacity of about 67.5 M barrels/year of feed remain. Just under 650
oil refineries exist in the world, so 9% of refineries currently practice
oligomerization [23].
In addition to fuels, this total capacity includes the primary pro-
duction of olefin oligomers as precursors to petrochemicals including
branched alkylbenzenes (BAB), alkylated phenols, and oxo alcohols.
Marketshare of BAB for sulfonation and use as a detergent has been
significantly declining in favor of the more readily biodegradable linear
alkylbenzenes (LAB, Section 3) [24], but still sees use as oilfield che-
micals. The largest alkylated phenol use is in nonylphenolethoxylate
non-ionic surfactants, where over 300 million pounds are produced
yearly, though market share will decline rapidly in upcoming years
[25,26].
Oxo alcohols synthesized from mixed octenes and nonenes see end
uses in plasticizers for polyvinylchloride (PVC) including diisono-
nylphthalate (DINP), the hydrogenated non-phthalate version cyclo-
hexane dicarboxylic acid diisononyl diester (DINCH®), diisode-
cylphthalate (DIDP), trimellitates, and adipates. The use of DINP and
DINCH® in particular have been increasing significantly as di-2-ethyl-
hexylphthalate (DEHP) has declined due to environmental concerns. Of
the approximately 6 million ton/yr plasticizer market, these molecules
had about 33% market share in 2014, with the total share expected to
grow in the next several years [27]. Other significant uses for oxo al-
cohols are in alkylethoxylate non-ionic surfactants whose market share
is also increasing [28].
Multiple acidic solids [29] have been utilized as oligomerization
catalysts, ranging from the classical silica-supported phosphoric acid, to
acidic ion-exchange resins, amorphous silica-aluminas, zeolites and
even acidic clays and sulfated metal oxides [30]. The primary me-
chanism utilized over these materials is a classic carbenium route [31],
shown in Fig. 1.
The Brønsted acid site attacks the olefin in reaction 1 leading to the
formation of an ion-pair. The carbenium ion formed can react with
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Applied Catalysis A, General 543 (2017) 82–97
Fig. 1. Carbenium ion mechanism utilized in acid catalyzed oligomerization reactions.
The first olefin inserted is black, the second blue, and the third red. Numeration is de-
scribed in the text. (For interpretation of the references to colour in this figure legend, the
reader is referred to the web version of this article.)
another olefin in reaction 2 to give a longer carbon chain. The inser-
tion/chain growth can continue (reaction 3) or terminate (reaction 4) to
yield an olefin and the starting acid site. With substitution on the olefin,
each olefin addition (dimer, trimer, etc.) yields a branch in the hy-
drocarbon chain. Isomerization is also quite prevalent in many systems
with H-shift (reaction 5) and alkyl shifts (reaction 6) frequently oc-
curring to yield more thermodynamically stable carbenium ions. Thus,
true oligomerization products are often not the only products formed.
Reaction 1 can be responsible for double bond migration and E to Z
transitions. Once the planar carbenium ion is formed, if reversed, the
position of the olefin and relative E or Z configuration can change from
the initial olefin. The particular acidic solid utilized and confinement
effects drive differentials in the relative rates of the multiple reactions
as Iglesia and coworkers have shown [32].
2.1. Solid phosphoric acid (SPA)
Phosphoric acid, as a high concentration aqueous solution, had been
shown to be catalytically active for the oligomerization of olefins
[33,34], with significantly higher yields than thermal polymerization
and with activity dependent on the concentration of H3PO4 [35,36]. It
wasn’t until the development of solid phosphoric acid (SPA) that in-
dustrial processes for olefin oligomerization were commercialized
[37,38]. 80 years after Ipatieff’s discovery [5], SPA continues to be
utilized commercially due to its high selectivity to gasoline and cost
effectiveness.
In addition to UOP’s Catalytic Condensation™ process [39], of which
more than 250 units have been licensed since 1935 (also called Cat-
Poly) [40], and Standard Oil’s development of a similar process [41],
Sasol have been practicing a SPA based oligomerization process [42]
and have published much research in the area. SPA is formed by
combining H3PO4 with silica sources such as the natural products kie-
selguhr or diatomite [43], synthetic silicas [44,45], or quartz followed
by extrusion [46]. High silica content solids are traditionally utilized,
but even low silica content kieselguhr with CaO and MgO contents
above 3 wt% (combined) are acceptable as long as the bulk density is
less than about 0.3 g/mL [47]. During the reaction between H3PO4 and
the SiO2 support, a number of silicon phosphates and hydrogen phos-
phates including orthophosphate Si5O(PO4)6, pyrophosphate SiP2O7,
hydrogen phosphate Si(HPO4)2·H2O, and tripolyphosphate SiHP3O10
are formed [48]. The orthophosphate is the preferred phase for activity
[49], the pyrophosphate for strength [46,50] and the hydrogenpho-
sphate a non-preferred phase. As for many of the other catalyst systems
C.P. Nicholas
Fig. 2. The phosphate ester mechanism exhibited by SPA. Reprinted with permission
from Ind. Eng. Chem. Res. 45 (2006) 578–84. Copyright 2006 American Chemical
Society.
utilized for olefin oligomerization, it may be beneficial to have large
macropores [51].
The acidity (and activity) of SPA has been shown to be due to
phosphoric acid oligomers supported on the silicon phosphate phases.
Here, the mechanism involves not a true acid derived carbocation, but
instead a phosphate alkylester with significant interaction between the
cationic protonated olefin and anionic phosphate, as shown in Fig. 2
[48,52]. This mechanism effectively controls the product selectivity to
gasoline, but selectivity can be adjusted towards distillate by decreasing
catalyst hydration levels [53]. High concentrations of H3PO4, ranging
between 110 and 120%, were shown to be optimal, similar to that
observed in the liquid H3PO4 system [35], with the pyrophosphate
phase concentration increasing with H3PO4 concentration [46] and
calcination temperature [46,49]. Due to a lack of spatial constraint,
branching is quite significant in distillate products, reflected in cetane
numbers of hydrogenated distillate near 30 [54]. Additionally, as
temperature is increased to increase selectivity to distillate, hydrogen
transfer reactions yielding paraffins and aromatics occur.
A new version of SPA, which contains BPO4 in addition to the above
silicon phosphate phases, is being marketed in China as T-99 and ap-
pears to be of lower activity than traditional SPA, possibly due to di-
lution of the active phase [50].
Isobutene is typically the most reactive olefin over SPA, with n-
butenes more reactive than propene [41,55]. When pentenes are in-
cluded, methylbutenes are more reactive than n-butenes, and n-pen-
tenes are the least reactive species [56]. Octenes follow the same re-
activity pattern, with 2,2,4-trimethylpentenes significantly more
reactive than linear octenes, in particular 1-octene, due to the phos-
phate ester mechanism [52]. Olefin isomerization is typically quite
rapid and favors Z-olefins as products [57].
Several recent processes using SPA have been developed. UOP has
utilized the high reactivity of isobutene in the InAlk™ process where the
isobutene in butene containing feeds is dimerized to 2,2,4-tri-
methylpentenes, separated from the unreacted linear butenes and hy-
drogenated to isooctane [58]. A portion of the hydrogenated isooctane
product is recycled back to the reactor inlet to significantly improve
catalyst life [59]. Honeywell UOP has also been working recently on
utilizing SPA, amongst other catalysts, for the oligomerization of flui-
dized catalytic cracking (FCC) derived olefins as part of integrated
processes and apparatuses [60,61] in the Catolene™ family to produce
gasoline and/or high propylene yields [62]. Exxon has worked on
several catalysts, among them SPA, for the oligomerization of propene
to nonene/dodecenes (trimer/tetramer) as the intermediates to produce
alcohols and aldehydes [63,64]. SPA produces a particular branch
pattern and molecular weight (MW) distribution that is desired in the
product utilized as carbonylation feed [64,65].
Though branching, MW, and other properties are dependent on feed
and process conditions, SPA gives a product with significant methyne
(CH) and methylene group (CH2) content also corresponding to a
84
Applied Catalysis A, General 543 (2017) 82–97
Fig. 3. Use of multi-dimensional NMR to show SPA product speciation differences from
MTW zeolite based catalysts. Gradient enhanced inverse-detected HSQC NMR spectrum;
Red is MTW, Black is SPA; Regular 1H and 13C NMR spectra are plotted on top of hor-
izontal and vertical axes, respectively. Adapted with permission from Ind. Eng. Chem.
Res. 55 (2016) 9140–6. Copyright 2016 American Chemical Society. (For interpretation
of the references to colour in this figure legend, the reader is referred to the web version
of this article.)
relatively high quantity of Type III isoolefinic alkenes [66]. Due to the
number of products formed during acid catalyzed oligomerization
processes and the difficulty of separation, significant efforts have oc-
curred to better understand the catalyst-oligomeric product structure-
property relationship. Characterization of the hydrocarbons formed has
utilized advanced GC–MS [67], GCxGC [68], and NMR [66] techniques
to determine product speciation (Fig. 3), where up to 48 compounds in
the C8 region have been molecularly identified [69], including cyclic
alkanes [68].
In addition to water tolerance and subsequent corrosion concerns
from H3PO4, one of the difficulties with SPA, and the typical reason
alternative catalysts have been investigated, is the limited lifetime and
disposal of spent catalyst [65]. Typically, spent SPA is considered ha-
zardous waste, but recent efforts have shown that it can be a phos-
phorus source for fertilizer [70].
2.2. Acid resins
An acidic material frequently utilized as an alternative to SPA cat-
alysts are the polymeric resins usually sold for ion-exchange such as the
Amberlyst line of products [71]. These typically styrene-divinylbenzene
copolymers have sulfonate groups serving as the anion to the H+ ca-
tion. Different grades have different cross-linking agents in place of the
divinylbenzene, amounts of cross-linking, or sulfonate group content.
Another class of these resins are the perfluorinated polymeric resins
also containing sulfonate groups often sold under the Nafion product
line [72]. The chemical structures of both types of polymeric material
are illustrated in Fig. 4. Discussion here focuses on recent developments
in this active area as Antunes, et al. recently reviewed the use of these
materials in oligomerization for fuels production [73].
The highly acidic catalysts, with proper control of polar compounds
such as water [74,75], have been most successfully utilized at low
temperature (0–100 °C) to selectively oligomerize highly reactive ole-
fins such as isobutene to the dimeric 2,4,4-trimethylpentene product
which is then hydrogenated to isooctane as in the Neste NExOctane™
C.P. Nicholas Applied Catalysis A, General 543 (2017) 82–97

Fig. 4. The chemical structures of A) sulfonated styrene – divinyl benzene copolymers

and B) tetrafluoroethylene – sulfonated perfluorovinylether polymers. Both representa-
tions are somewhat simplified, but give a good idea of the complexity and number of
potential acidic polymers.

and Honeywell UOP InAlk™ processes [1,76]. Recently, Taylor and

coworkers have been developing processes to dehydrate isobutanol
obtained from biological fermentation processes to isobutene [77] and
then oligomerize the isobutene to fuels [78], often targeting the jet
range [79]. The resin catalysts used provide good selectivity to primary
oligomerization products, with GC traces showing only a small number
of compounds produced, unlike SPA and most zeolitic catalysts (Section
2.4) which provide a plurality of products from concomitant oligo-
merization, backcracking and isomerization.

2.3. Amorphous silica-alumina (ASA)

Amorphous silica-aluminas have been used as acidic solids for oli-

gomerization for many years [80], in part because the class of materials
has been around for a significant time, but largely because the materials
are stable to higher temperatures than acid resins or SPA, and hence
regenerable by carbon burn [81]. The reactivity of silica-aluminas has
been known to be dependent on the strength of the Brønsted acidity of
the site, but these sites also coke relatively rapidly. Hence, it is the
moderately strong acid sites that are responsible for the oligomerization
reaction after the initial time on-stream [82]. Operating in the liquid
phase at temperatures between about 150 °C and 250 °C, long run
lengths of multiple months prior to regeneration can be accomplished.
Oxygenates in the feed cause a higher coking rate as carbonyls are
readily converted to coke precursors [83]. Additionally, while run
lengths are shorter, ASA based catalysts are capable of converting feed
in the presence of significant quantities of poisons such as CO, thio-
phene, NH3 and H2S [84,85]. Silica-aluminas are cheap to manufacture
and can have single pass distillate selectivity approaching 70% from
light olefins, but tend to have high hydrogen transfer rates and hence
produce low cetane value (20–30), relatively aromatic distillate
[81,83]. Octane values are typically relatively high, with 92–94 RON
quite commonly reported [81], and the olefins produced by these
processes have extremely high blending octane values [86,87].
The relative prevalence of tetrahedral and octahedral Al sites is
related to aluminum content in these materials [88], with higher Al
contents approaching γ-Al2O3 at 25% tetrahedral sites. Low Al content
materials can approach 100% tetrahedral coordination [85,89]. Alu-
minum content is frustratingly inconsistent in the effect on olefin
conversion level, but does tend to influence selectivity patterns, with
high silica content materials showing less cracking selectivity [86,90].
In addition to traditionally precipitated silica-aluminas, mesoporosity
has been introduced by using materials such as MTS, SBA-15, and
MCM-41 [91,92]. Researchers have also utilized amorphous materials
prepared by methods that would traditionally yield zeolite products;
these proto-zeolitic solids are also useful for oligomerization [93].
Recently, Chizallet, Raybaud, and coworkers have studied many
aspects of these materials with a computational approach in an effort to
unravel the features that contribute to conversion and selectivity in
ASAs. They developed a surface model for ASAs highlighting the di-
versity of potential hydroxyls and established the existence of silicic
and aluminic pseudo-bridging silanols (PBS-Si and PBS-Al, respectively,
Fig. 5) [94]. The acidity of ASAs is dominated by the stability of the
Fig. 5. Surface models of hydroxyls on amorphous silica-aluminas calculated by Chizallet,
Raybaud and coworkers. Reprinted from J. Catal. 325 (2015) 35–47, with permission
from Elsevier.
conjugate base after deprotonation, hence even PBS can transfer pro-
tons to probe molecules such as lutidine and presumably catalyze oli-
gomerization [95,96]. However, it is impossible to simply utilize luti-
dine (or low temperature CO) as a probe molecule to easily characterize
ASA materials as the interaction of the olefin feed or probe molecules
results from multiple interactions/contributions [96,97]. They also
confirmed the long observed effect of water on ASA materials, showing
that water helps serve as a proton reservoir and obscures acid site
strength.
Mixed metal oxides, of which silica-alumina is the most studied
example, are well known as acidic solids [29]. Both oligomerization
and cracking occur over boria-alumina, with true oligomerization fa-
vored in the liquid phase at 150 °C [98].
2.4. Zeolitic materials
A special class of silica-aluminas are the crystalline, microporous
zeolites [99]. They have been one of the most investigated class of
materials for the oligomerization of olefins, partially due to the prior
commercial application of MFI zeolitic materials in the Mobil Olefins to
Gasoline and Distillate (MOGD) and PetroSA Conversion of Olefins to
Distillate (COD) processes [7,100], but also because of the control af-
forded the scientist in picking the pore size, connectivity and thus the
shape selectivity exhibited [101,102]. Over 230 individual structure
types are now known, with each type afforded a 3 letter designation by
the International Zeolite Association (IZA) Structure Commission [103].
Zeolites are given proper names when synthesized under different
conditions, for example, UZM-9 [104] or ZK-4 [105], but are classified
by structure type, which for these two materials is LTA. The structure
types are classified by pore size and connectivity, with 8-membered
ring (8MR), 10-membered ring (10MR), and 12-membered ring (12MR)

85
C.P. Nicholas
delimited pore channels all frequently encountered with typical size
openings of 4.0 Å, 5.5 Å and 7 Å, respectively.
In Fig. 6, several characteristics of olefin oligomers produced over
zeolite catalysts [69] are plotted against the geometric surface area of
the zeolite pore opening. MTT, MFI and MTW geometric surface areas
were calculated using the formula for surface area of an ellipse
(π*(0.5*A)*(0.5*B)) where A and B are the pore openings given in the
IZA database [103]. MTT, MFI and MTW had pore openings of 18, 23,
and 26 Å2 respectively, moving from highly constrained to less con-
strained pore openings. Solid phosphoric acid was assigned a value of
50 as an unconstrained solid for comparison. High constraints from
pore walls (smaller pore openings) lead to more linear products.
Branching in the C8 fraction, whether as average branch number (red
open circles) or the trimethylpentene percentage in the C8 fraction
(blue triangles), increases significantly as pore constraint decreases. At
the same time, the linear olefin percentage in the C8 fraction decreases
exponentially (gray open boxes). The cetane number of the distillate
boiling point range product produced (purple diamonds), a bulk
property which is dependent on branching, with linear molecules pre-
ferred for high cetane number, decreases as pore constraint decreases.
Effects on branching thus clearly occur throughout the molecular
weight range, not just in the more readily characterized C8 region. Ef-
fects of pore constraint are also visible via the substitution around the
double bond, with the percentage of C8 olefins having 3 substituents
(out of 4 possible) on the double bond decreasing as pore constraint
decreases (yellow circles) [69].
2.4.1. MFI
Since the progress shown by Mobil in commercializing the MOGD
technology, the highest number of studies have been carried out with
catalysts based on the 3-dimensional, 10 membered ring MFI zeolite
[106]. In addition to traditional methanol sources, coal has also been
utilized as the source of syngas, allowing complete coal to gasoline
processes [107]. PetroSA has also commercialized and is practicing a
MFI based oligomerization process they call Conversion of Olefins to
Distillate (COD) [100,108]. As discussed above, MFI based catalysts
produce low degrees of branching, primarily methyl in character,
making it a good catalyst with which to produce distillate range fuels
[109].
Feed and process conditions both impact fuels properties.
Temperature significantly affects the amount and type of olefin ad-
sorbed on the catalyst, hence ethene and propene show decreasing
conversion as temperature increases, while butenes have increased
conversion at higher temperatures [110]. Space velocity can be utilized
86
Applied Catalysis A, General 543 (2017) 82–97
Fig. 6. Product oligomer characteristics as a function of
geometric pore surface area showing how pore constraint
changes several important product property markers. Data is
from Nicholas, et al. for MTT, MFI, MTW, SPA catalysts [69].
Arrows in the plot indicate the axis on which the labeled data
series are plotted.
to alter the amount of consecutive reactions observed [111]. Isomer
distributions are not necessarily equilibrated even when conversion is
complete as de Klerk showed in studies using propene, 1-hexene, and
mixed Fischer-Tropsch C5eC9 cuts as feed [112]. Reported research
octane number (RON) produced from these feeds is low, typically below
80, with good cetane values in the 40–50 range. Eni oligomerized
cracked naphthas containing mixed C5 and C6 olefins to distillate fuels
with cetane values around 55 [111]. At Honeywell UOP, we showed
that mixed butene feeds including isobutene achieved higher RON va-
lues of 95, but with poorer cetane of 36 [113].
Most of these studies were performed with relatively high percen-
tages of olefin in the feed, including the COD and MOGD processes, but
de Klerk and coworkers have recently utilized MFI to oligomerize, in
the presence of poisons such as CO, dilute (as low as ∼7%) C2eC4
containing Fischer-Tropsch (FT) tail gas feeds to fuels. Interestingly, no
evidence was found for reaction of CO with the olefins, nor for an effect
on olefin conversion [114].
Researchers from Eni have also recently shown that deactivation for
any particular MFI is dependent only on the amount of olefin processed
although different MFI catalysts have different deactivation rates
(Fig. 7) [111]. One reason is that crystal size of the MFI zeolite utilized
has been repeatedly shown to impact performance, with smaller crys-
tals yielding longer lifetimes and lower coking tendencies [115,116].
Recently, mesoporosity has been shown to significantly impact lifetime,
one of the main drawbacks to utilizing a three-dimensional material
versus the one-dimensional materials described later [106,117]. Thus,
what is important is shortening the diffusion path length, whether by
making small crystals or introducing mesoporosity, so that oligomeric
products do not become coke.
Acid site density is related to the SiO2/Al2O3 ratio and has been an
area of interest for some time [118,119]. Regardless of whether alu-
minum gradients exist in the MFI zeolite, high aluminum content, and
hence high acid site density, leads to significant coking and reduced
lifetime [120,121]. The proximity of acid sites is correlated with aro-
matic molecule formation [121]. By looking at the distribution of di-
methylhexenes within the C8 fraction, it becomes clear that significant
fractions of catalysis actually occur on the outside surfaces of the
crystals for high acid site density materials. This effect is likely due to
significant coking of internal channels [120]. An approach taken to
increase shape selectivity provided by MFI zeolite has been to deacti-
vate the surface acid sites by titration with an amine. While this ap-
proach hurts overall distillate yields compared to the unmodified MFI,
the resulting distillate product can be nearly linear [122].
Care must be taken in these studies as the zeolite crystallite size can
C.P. Nicholas
Fig. 7. Deactivation of MFI catalyst (lower conversion) is only dependent on amount of
olefin fed over the catalyst and is independent of space velocity. Reprinted from Bellussi,
et.al., Micro. Meso. Mater. 164 (2012) 127–34, with permission from Elsevier.
increase significantly as the acid site density decreases unless synthetic
precautions are taken [119]. With large crystal size, even low acid site
density MFI zeolites can exhibit significant fractions of external cata-
lysis due to site/pore blocking [118]. For MFI then, each feed olefin has
a different optimal combination of diffusion path length and acid site
density for optimal catalysis as Corma and coworkers showed in studies
using propene and pentene as feeds [117].
2.4.2. Other 3-dimensional zeotypes
Beta zeolite, an inter-grown mixture of two 3-dimensional 12-
membered ring zeotypes [123], has also been frequently utilized for
oligomerization. Recently, Lobo observed, as is typical with acid cata-
lysts, that olefin positional isomerization is the fastest reaction occur-
ring. They also studied diffusional restrictions, concluding that oli-
gomer transport out of the crystals controlled the rate of
oligomerization, which may also explain the inability to form only di-
mers using H-beta under any condition [124]. Chang, Jhung, and
coworkers utilized this property to trimerize isobutene with selectivities
up to 70%, showing that beta gave higher selectivities to trimer than
other zeotypes including FAU, another three-dimensional 12MR [125].
Conversion stability could be increased in the FAU catalysts by deal-
umination via steaming, but trimer selectivity decreased concomitantly
[126]. Beta has also been used to catalyze 1-pentene oligomerization,
showing, even at 25% conversion, 40% selectivity to trimer (C15) pro-
ducts [127].
2.4.3. 2-dimensional zeotypes
Celik and coworkers have also studied the oligomerization of pen-
tenes using, amongst other zeotypes, the FER structure, a 10 × 8MR
two-dimensional zeotype, as catalyst [128]. FER showed very different
reactivity patterns, with higher selectivity to decene of 74%, than the 3-
and 1-dimensional zeotypes also tested at 200 °C. This reaction pattern
was ascribed to a lack of bimolecular cracking reactions, behavior also
observed by Huber and coworkers in 1-butene oligomerization [129].
Trimers of isobutene were obtained selectively over FER catalysts at
low temperatures of about 70 °C, with trimer selectivity increasing to
about 70% with increasing isobutene conversion at these temperatures
due to a lack of cracking [130]. GCxGC techniques showed branching in
the octene dimers produced increases with increasing butene conver-
sion, with product molecular weight following a Schultz-Flory dis-
tribution [129].
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Control of the oligomer product branching pattern has been one of
the driving factors behind use of the MFS (ZSM-57) zeotype, another
10 × 8MR structure, in oligomerization [131]. MFS exhibits a higher
dimer selectivity than other zeotypes during 2-butene oligomerization,
including beta and FER, and a lack of cracking/reoligomerization re-
actions until about 473 K [132]. The selectivity to dimers can be further
improved to above 90% during butene oligomerization when used in a
catalytic distillation reactor, although selectivity falls at high conver-
sion in autoclave testing [133–135].
The MWW zeotype, containing both 10-membered and 12-mem-
bered rings [136], delivers high conversion during olefin oligomeriza-
tion, often in the form of MCM-22, where influence of silanol groups at
channel mouths in interactions with butenes has been observed
[132,137,138]. Exxon developed, and commercially tested, the
EMOGAS process to replace SPA in CatPoly units [139].
2.4.4. 1-dimensional zeotypes
We have recently investigated, amongst other catalysts, the use of
one-dimensional zeolites such as MTW and MTT for the oligomerization
of C4 and C5 olefins to gasoline and distillate [113,140], as these 1-
dimensional materials have longer lifetimes in oligomerization than
many multi-dimensional materials [106,141]. MTW, a large pore zeo-
lite containing a relatively small 12MR, shows good selectivity to ga-
soline, particularly once treated with phosphates [142]. Selectivity to
distillate range products is 15% prior to phosphorus treatment. As the
phosphorus content of the 80/20 MTW/Al2O3 catalyst increased, se-
lectivity to gasoline improved markedly to about 3 wt%, virtually
identical to that of SPA, as shown in Fig. 8. At the same time, acidity
changed significantly as Si-O-Al-O-P moieties form, and activity de-
clined, even as the binding matrix was converted from Al2O3 into
crystalline or amorphous AlPO4 depending on the phosphate precursor
[140,142].
MTT, a medium pore zeolite containing a relatively small 10MR, can
show excellent selectivity to distillate range products from butene
containing feeds, with over 70% yield of C9+ per pass [143]. Jet range
material, the C9eC20 portion of the distillate boiling point range, can
also be produced selectively by processes where heavy olefins are re-
cycled back to the reactor [144]. MTT is quite shape selective, produ-
cing only 23% selectivity to trimethylpentenes within the C8 fraction
versus 44% for MFI, 59% for MTW, and 75% for SPA at identical
conditions. Also, as the pore size decreases, the share of multiply
branched olefins produced decreases and the cetane number increases
(Fig. 6) [69].
Another frequently utilized 10-membered ring zeotype is TON
(ZSM-22), a material structurally related to MTT [145,146]. Control to
mono-methyl branching with high yields of dimer and trimer products
Fig. 8. Effect of phosphorus on oligomerization of C3/C4 feed at 65% conversion showing
the effect of phosphate treatment on 80/20 MTW/Al2O3 zeolite based catalysts in com-
parison to reference solid phosphoric acid (SPA). Reprinted from Nicholas, et.al., Appl.
Catal. A (2017), with permission from Elsevier.
C.P. Nicholas
and low tetramer formation are hallmarks of ZSM-22 [147]. Exxon
researchers have shown that small levels of water in the feed improve
lifetimes of these catalysts [148,149], while still maintaining the
branch structure desired in the nonene/dodecene product, used as a
feed for hydroformylation, although some oxygenates are detrimental
to lifetime [150]. The introduction of mesoporosity by first desilicating
with NaOH, then dealuminating with oxalic acid appears to increase
lifetime for TON materials and can result in increased distillate se-
lectivity [151]. Exxon researchers have also sometimes utilized TON in
combination with MFS or MFI to deliver the desired branching structure
[152,153]. Process conditions including relative amounts of the cata-
lysts, temperature, and WHSV control selectivity to mono-, di-, and tri-
branched products. Another method utilized to control branching
during oligomerization with TON or MTT is selectivation of external
acid sites with a bulky amine, ensuring only internal, shape selective
acid sites are available for reaction [154].
When control of branch structure has not been a significant concern,
the large, 12-membered ring MOR material has been utilized
[155,156]. High SiO2/Al2O3 materials showed good selectivity to dimer
product and preferential oligomerization of isoalkenes during pentene
and light cracked naphtha conversion [127].
2.5. Other non-zeolitic acidic solids
In addition to the silica and alumina based materials described
above, other acidic solids including clays, sulfated metal oxides (SMO),
and polyoxometalates (heteropolyacids) can catalyze oligomerization.
Classically, clays, whether pillared or acid treated, have been used for
oligomerization, although most show a mixture of oligomerization,
cracking and cyclization reactions [157–159]. Due to their lower
acidity, they are usually regarded as having lower activity than zeolites
and silica-alumina, but can survive higher quantities of poisons in the
feedstream [160].
Due to their high acidity, sulfated and tungstated metal oxides show
high activity, with good selectivity to true oligomerization products as
long as the temperature of reaction is kept low enough to avoid
cracking. Typically, high selectivity to trimerization of isobutene with
some tetramer production is observed over sulfated titania and tung-
stated zirconia [161,162]. The method of preparation of materials,
particularly how the anion modification/sulfation is carried out, has a
large impact on catalytic properties, perhaps due to the varying ratio of
Lewis to Bronsted acid sites, with higher Lewis site density giving
higher stability [163]. Leading data, for both the SMO and boria-alu-
mina mixed metal oxide systems, suggest that Lewis acid sites may be
capable of acting as the catalytically active site [98,164].
Polyoxometalates, also referred to as heteropolyacids, have his-
torically found utility in olefin oligomerization but had not seen much
development recently until Iglesia and coworkers studied them to ex-
pand their study of deprotonation energy as a descriptor of oligomer-
ization rate [32,165]. A wide range of elements have been studied as
the central atom in the Keggin structure with Si and P the two most
frequently studied. With the lowest deprotonation energy, and thus
weakest conjugate base, the P substituted Keggin has consistently been
shown to be the most active heteropolyacid, whether tested as
H3PW12O40 or as the Al salt thereof [32,166]. Oligomerization of pro-
pene over various salts of phosphotungstic acid gave liquid distribu-
tions centered around trimers, with cetane numbers in the range of
35–40 for Al salts [166]. The preferential oligomerization of isobutene
in the presence of linear butenes over silica-supported tungstosilicic
acid also yielded a mixture of oligomers (dimers, trimers, tetramers,
etc.) at 60 °C [167]. The largest difficulty with polyoxometalates has
consistently been the production of heavy oligomers and coke pre-
cursors.
2.5.1. Ionic liquids
In addition to the solid catalysts utilized above, liquid systems are
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Applied Catalysis A, General 543 (2017) 82–97
also known as catalysts. In a recently reported FeCl3 containing tetra-
alkyl ammonium ionic liquid system, isobutene appears to be oligo-
merized to dimers and trimers via Brønsted sites. As for most acids,
cracking reactions were favored at higher temperatures, in this
case > 60 °C [168].
Previously, alkylsulfonate imidazolium triflate ionic liquids had
shown utility for oligomerization of olefins at 90 °C in batch reactions.
Isoolefins such as isobutene were more reactive than 1-butene, and
significantly more reactive than long chain mono-olefins. Selectivities
to dimers/trimers of up to ∼90% were achieved at conversions greater
than 60% [169].
1-Butyl-3-methylimidazolium tetrachloroaluminate ionic liquids
were also shown to oligomerize C2eC8 olefins to dimers and trimers
[170]. Yields up to 67% were achieved and decreased monotonically as
the olefin chain length increased. Longer chain lengths were preferred
on the imidazolium for activity, presumably for greater lipophilicity
[169], so the decrease in oligomer yield as the olefin chain length in-
creases observed here could be due to a mismatch in product/ionic li-
quid properties.
3. Metal catalyzed oligomerization
Due to the industrial importance of the production of linear alpha
olefins (LAO), a reaction often carried out using homogeneous catalysts,
chemists have “traversed the periodic table searching for new transition
metal and lanthanide-based olefin polymerization systems” and a sig-
nificantly greater number of systems than can be discussed here have
been explored [171]. The market for LAOs is currently over 5 million
metric tons with about 40% of the LAO market used for lubricants,
detergents (sulfonated linear alkylbenzenes), oilfield chemicals and
other fine chemical products, while the other 60% is utilized as co-
monomer during polymerization of ethene and propene [172].
Metal based catalysts typically utilize a Cossee-Arlman 1,2-insertion
mechanism [173], shown in Fig. 9A, to catalyze olefin oligomerization.
Following coordination, the olefin inserts into the metal-hydride or
metal-alkyl bond with the least substituted carbon bonded to the metal.
This is then typically followed by β-hydride elimination to yield a vi-
nylidene substituted product. Significant steric interactions with the
alkyl chain on the incoming olefin inhibit coordination of the olefin
prior to insertion, so many catalysts only oligomerize ethylene or 1-
olefins. For this reason, metals typically have significantly higher re-
activity towards ethene than substituted olefins, so much work has
focused on oligomerization of ethene, with some studies also using
propene [174]. Work resulting in polymerization of the olefin feed is
not discussed here. Mis-insertion of olefin to give 1,2-insertion followed
by 2,1-insertion as illustrated in Fig. 9B is rare, but possible as is the
opposite case of 2,1-insertion followed by 1,2-insertion (Fig. 9C). These
two instances yield linear internal olefins and methylbranched vinyli-
denes respectively. This author has not seen a non-polymerization
catalyst system performing regioregular 2,1-insertion as illustrated in
Fig. 9D to yield methylbranched internal olefins, but this reactivity
pattern should be possible. Regioregular insertions are normally the
products, and while chirality is not reported in any of the products
reviewed here, it is worth noting that insertion of substituted olefins
creates a prochiral metal-alkyl chain. In addition to β-hydride elim-
ination, chain transfer to monomer, hydrogen, or aluminum alkyls can
be observed as growth termination modes [175].
3.1. Aluminum
Ziegler’s discovery of the Aufbau reaction 65 years ago was the first
indication that metals could catalyze the formation of CeC bonds from
olefins [8]. The insertion of ethene into an aluminum alkyl gives a
pseudo-Poisson distribution of even numbered carbon olefins and is
used as the primary method of producing linear alpha olefins (LAO)
[176,177]. Both the Gulfene [178,179] (now Chevron Phillips
C.P. Nicholas
AlphaPlus®) and Ethyl [180] (now Ineos) processes utilize solution
based processes with trialkylaluminum as the key propagating species.
In addition to these well-developed solution phase processes, hetero-
geneous catalysts with surface Al-H moieties are also catalytically ac-
tive for ethene insertion and chain growth as we showed recently
[181,182].
3.2. Nickel
While a number of metals have been utilized for olefin oligomer-
ization, the most frequently utilized catalysts contain Ni, including the
homogenous catalysts utilized in the well-known Shell High Olefins
Process (SHOP) [183,184]. The general structure of the SHOP catalyst
is shown in Fig. 10 [185]. Because of the ability to fine tune the
structure-property relationships using small modifications of the li-
gands in the SHOP type Ni complexes, a number of complexes have
been investigated and recently reviewed [186,187].
Coverage here focuses on newer discoveries in this active field and
is briefer than historically justified given that the utility of nickel in
oligomerization has been known since early investigations of the
Aufbau reaction, with both homogeneous and heterogeneous catalysts
recently investigated [188]. The biggest difficulty in preparing het-
erogeneous Ni catalysts for oligomerization has been preparing mate-
rials with isolated Ni sites, which have been shown to yield active sites
Fig. 10. Conceptual pictogram of Ni based SHOP-type catalysts during oligomerization.
Reprinted with permission from Ref. [185].
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Fig. 9. 1,2- and 2,1-insertion mechanisms of an
olefin into a metal-hydride or metal-alkyl bond
leading to longer chain olefins after beta-hydride
elimination to regenerate the hydride. As illustrated
by the red box in part A, almost all systems utilize
regioregular 1,2-insertions. (For interpretation of the
references to colour in this figure legend, the reader
is referred to the web version of this article.)
for oligomerization. Davis and coworkers recently synthesized Zn-
containing silicates CIT-6 (BEA* zeolite topology) and MCM-41 and
showed that exchange of Ni2+ into these materials led to higher se-
lectivity to direct propene oligomerization than materials made by
exchanging Ni2+ into Al containing materials due to a significant re-
duction of acid catalyzed side reactions [189]. As also observed by Bell
and coworkers in comparisons of Ni2+ exchanged FAU and MCM-41
materials [190], the mesoporous silicates gave more stable conversion
profiles [191]. Bell also showed that Ni2+ migrates to the largest space
in the FAU zeolite to yield higher stability. It appears that residual acid
sites in these materials catalyze isomerization of product olefins in the
zinc materials and cracking/isomerization in Al materials. This beha-
vior can be utilized, as discussed below in the bi-functional oligomer-
ization section, but is often a detriment here.
Another method of controlling residual acid sites in supported
nickel catalysts is to over-exchange the sites such that some nickel is
wasted as NiO on the support surface [192] as we showed recently in
conversion of dilute ethylene to liquids using silica-alumina supports
[193,194]. Fluorotetrasilicate micas have also been shown to be useful
supports for ethylene oligomerization, with intercalation of fluoro-
containing α-diimine ligands into Ni-exchanged micas yielding Schultz-
Flory distributions of even carbon number oligomers with alpha values
of between 0.55 and 0.65 for highly active catalysts [195].
Dinca and coworkers avoided the use of acidic supports, exchanging
Ni2+ onto the Zn2+ cation site in a tris-pyrazolylborate based metal-
organic framework (MOF) framework in order to achieve 95% se-
lectivity to butene with just under 5% selectivity to hexenes at 25 °C,
30 bar ethylene after activation of the catalyst with methylalumoxane
(MAO) [196]. MAO yields Ni-CH3 species, and the catalyst has been
shown to produce butene by the expected Cossee-Arlman 1,2-insertion
pathway [197]. Pyrazolyl based ligands on Ni also show high selectivity
to butene in analogous homogeneous systems [198]. Selectivity to bu-
tene is higher at higher ethylene pressures, suggesting that chain
transfer to monomer rather than β-hydride elimination drives the se-
lectivity pattern for these catalysts.
Ni-diimine catalysts synthesized by post-synthetic modification of
Fe-MIL-101 showed turnover frequencies (TOFs) of ethene up to
∼10.5 × 103 mol (mol Ni h)−1 with selectivity to 1-butene > 90%
[199]. The hydroxyl groups of the Zr6 nodes in the MOF NU-1000 have
also served as a scaffold on which to site-isolate Ni. After activation
with diethylaluminum chloride, the catalyst produced largely butene
C.P. Nicholas
Fig. 11. Chain transfer to monomer in zirconium catalyzed oligomerization reactions.
Reprinted with permission from J. Am. Chem. Soc. 118 (1996) 11670–1. Copyright 1996
American Chemical Society.
and octene at low ethene conversion at 45 °C, 2 bar [200].
3.3. Group IV: titanium, zirconium and hafnium
The next most commonly utilized metal has been zirconium, well-
known in olefin polymerization catalysis [201]. To produce oligomers
rather than polymers, chain transfer agents such as trialkylaluminums
or inhibitors such as thiophene or arylethers are utilized to control the
molecular weight of the product. Multiple commercialized LAO pro-
cesses including those from Idemitsu [202,203], the Alpha-Sablin pro-
cess from Sabic/Linde [204], and Alphaselect process from IFP-Axens
[205] utilize this general concept. They run at moderate pressures of
20–40 bar and relatively low temperatures of about 25–100 °C. Zr based
catalysts typically provide Schultz-Flory distributions of product,
though via the use of high concentrations of chain transfer agents
pseudo-Poisson distributions are possible. Work on the mechanism of
reaction shows that instead of β-hydride elimination, chain-transfer to
monomer can drive these narrow carbon number distributions of olefin
oligomers (Fig. 11) [206].
Hessen and coworkers also showed that the insertion of ethene into
the Hf complex is 40 times slower than the same Zr complex, leading to
low overall productivity [206]. Slow insertion of propene into Hf-CH3
versus Zr-CH3 was observed by Teuben and coworkers in a [Cp*2M
(CH3)2(tetrahydrothiophene)]+ [BPh4]− catalyst system [207]. The Zr
catalyst produced a range of oligomers from C6 to C24, but Hf selectively
produced only one isomer of C6 and C9.
In addition to the homogeneous systems described above, hetero-
genous zirconium catalysts have been utilized for oligomerization re-
actions. Zr-H systems prepared by reacting organometallic precursors
with hydroxyls of a silica-alumina support followed by H2 treatment to
hydrogenolyze remaining Zr-C bonds dimerize 2-butene quite effec-
tively to mono- or di-branched octenes [208].
Prior to the development of the Zr/Hf based catalysts, titanium was
a key metal for oligomerization. Ziegler reported one of the first catalyst
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Applied Catalysis A, General 543 (2017) 82–97
systems for dimerization of ethene to 1-butene using Ti(OBu)4 and
trialkyl aluminum [209]. Shortly thereafter, Toyo Soda developed the
Toso dimerization process using phenoxytitanium complexes to achieve
up to ∼85% selectivity to butenes [210]. Titanium alkoxides are the
catalytic precursors still utilized in combination with aluminum alkyls
to generate linear butenes on large scale today, including in the Al-
phaButol® process [205].
Classical thought for these catalysts on the origin of high selectivity
to 1-butene followed a metallacycle mechanism (see Section 4). Recent
work utilizing thorough labeling studies, DFT calculations, and altera-
tions of the aluminum alkyl chain transfer agent have been used to
confirm the reaction mechanism as actually that of Cossee-Arlman (1,2-
insertion) with a high ratio of chain transfer to polymerization
[211,212].
Bercaw, Labinger and coworkers have recently utilized phenox-
yimine (FI) based ligands forming a tridentate ONO coordination en-
vironment on (FI)Ti(CH3)3 activated with B(C6F5)3 to yield primarily 1-
hexene and C10 olefins at 25 °C, 1 atm C2H4 [213]. Catalyst decom-
position is relatively rapid, but supporting the catalyst on MAO coated
silica significantly increases lifetime while retaining selectivity to 1-
hexene and branched C10 olefins [214]. C10 olefins are generated from
cotrimerization of a 1-hexene with 2 ethenes, so this ligand set may
actually oligomerize olefins through a metallacycle mechanism rather
than the typical 1,2-insertion mechanism. Related ligands with an N-
heterocyclic carbene in place of the imine such that an OCO co-
ordination environment is achieved have been used for Zr and Hf
complexes for trimerization of 1-hexene [215,216]. Upon activation of
the benzyl derivative (OCO)MBz2 with HN(CH3)2Ph+B(C6F5)4−, the Zr
complex is 77% selective to C18 compounds at room temperature in
liquid hexene. As observed previously, the Hf derivative is considerably
slower [215].
3.4. Group V: vanadium and tantalum
Moving over a group, homogeneous vanadium complexes chelated
with nitrogen based ligands [217] have shown high (> 90%) selectivity
to 1-butene or 1-hexene during ethene oligomerization [218,219]. Both
vanadium (V) and (III) complexes (Fig. 12) have been reported for
oligomerization of ethylene to Schultz-Flory distributions of olefins.
The size of imido substituents in vanadium (V) complexes plays a sig-
nificant role in controlling the oligomerization, with smaller sub-
stituents giving rise to polyethylene instead of oligomers [220].
In one of the few studies where both ethene and a larger olefin were
tested, V(III) complexes were shown to have significantly lower re-
activity with propylene than with ethylene [218]. Highest productivity
was observed with X = Cl while still achieving high 1-hexene purity
[219]. The steric bulk of the ligands also affects 1,2- versus 2,1-inser-
tion of the second propylene showing again that steric interactions,
both of the ligands and of the incoming olefin, play a significant role in
selectivity to oligomers in these group IV and group V catalysts. All the
Fig. 12. Vanadium complexes utilized in ethylene
oligomerization. A) vanadium (V) complexes, B)
vanadium (III) complexes [217–220].
C.P. Nicholas
Fig. 13. Control of ethylene oligomerization in homogeneous catalysts by metallacycle
formation. Reprinted with permission from Chem. Rev. 111 (2011) 2321–41. Copyright
2011 American Chemical Society.
vanadium complexes are first activated with MAO, a reaction that has a
complicated, time-resolved impact on oligomerization activity and
performance [221]. V-alkyl and/or -hydride species appear to be
formed during this activation step which are responsible for the cata-
lytic activity [222]. Supporting these complexes on supports results in
significantly increasing product molecular weight as we have observed
previously [223,224].
Tantalum has also been utilized, with Ta-H systems prepared as
above for Zr-H showing a mixture of dimerization and metathesis be-
havior at 150 °C [208]. Metathesis is favored at higher temperature,
with oligomerization favored at lower temperatures as we recently
showed [225]. Grafting Ta(CH3)3Cl2 onto partially dehydroxylated si-
lica gave a species that, upon exposure to ethene, reduces to a TaIII
intermediate with two chloride ligands and one siloxy bridge to the
surface [226]. This species is trigonal bipyramidal and selective to 1-
hexene during ethene oligomerization. Thermal treatment of the silica
supported Ta-H catalyst above leads to a silica-supported TaIII species
which polymerizes ethene, a behavior Basset and coworkers showed
was due to a square pyramidal coordination environment [227].
3.5. Cobalt- and iron-based catalysts
In an attempt to produce linear oligomers from 1-olefins, Hermans,
Huber and coworkers utilized cobalt oxides supported on carbon sup-
ports to dimerize 1-butene to linear octenes, achieving up to ∼80%
selectivity to linear octenes [228]. Selectivity to linear products is de-
pendent on conversion, with higher conversion leading to more bran-
ched products. Linear octenes could be formed from 1-butene by 1,2-
insertion followed by 2,1-insertion as shown previously in Fig. 9B, or by
collapse of a 1,4-disubstituted metallacycle (Section 4). Hermans,
Huber and coworkers proposed cobaltocyclopentanes as the catalytic
intermediate and noted the mixed oxidation state oxide Co3O4 was the
more active precatalyst [228]. Previously, in a series of papers, Schultz,
et.al., had utilized similar catalysts to dimerize propene, butene, hexene
and ethene, invoking a Co-H species as the key intermediate [229–231].
While the reaction mechanism and catalytically active species remains
under debate, it is clear that these cobalt oxide on carbon catalysts
provide higher selectivity to linear products than most other oligo-
merization catalysts.
While better known as highly active olefin polymerization catalysts,
a number of iron complexes, often in combination with chain transfer
agents, have shown utility for oligomerization [171]. A number of bi-
siminopyridine (PDI) ligands, forming either Fe or Co complexes, have
excellent dimerization selectivities for 1-butene feed at low tempera-
ture. The mechanism reported here is Cossee-Arlman, with a 1,2-in-
sertion into the metal hydride then often followed by a 2,1-insertion to
obtain a linear dimer followed by β-H elimination [171]. A number of
variations of this ligand have been synthesized, with 1,10-
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phenanthroline ligands showing some interesting selectivity patterns
towards oligomers during ethene oligomerization [232]. Recently,
Cariou, et.al., at BP showed iron-bipyridyl complexes in combination
with ZnEt2 and the aforementioned Fe-PDI type catalyst are capable of
regenerating the ZnEt2 chain transfer agent and provide for a single-pot
ethene oligomerization system. Higher quantities of ZnEt2 lead to
higher selectivity to oligomerization, but at a cost of product α-olefin
purity [233].
4. Metallacycles for ethylene dimerization, trimerization and
tetramerization
The selective conversion of ethene to butene, hexene and octenes
has been extensively investigated since the advent of the nickel cata-
lyzed SHOP technology [234,235]. These processes are often catalyzed
by homogeneous, well-defined molecular catalysts with intricate
structure property relationships, some of which were discussed pre-
viously in the metal catalyzed oligomerization Section 3.
It is often difficult to determine whether a particular catalyst system
utilizes a metallacycle mechanism as drawn in Fig. 13, a combination of
metallacycle and 1,2-insertion (Cossee-Arlman) mechanisms (i.e. the
relative rates are competitive) or simply the 1,2-insertion mechanism as
discussed above in Section 3 for metal catalyzed oligomerization. Im-
plicit in the metallacycle mechanism is a two electron oxidation and
reduction of the metal center upon formation and elimination, respec-
tively, of the metallacycle. Using detailed labeling experiments, often
coupled with theory, it is possible to determine that most catalyst sys-
tems based on zirconium, titanium, iron, nickel, and vanadium utilize
the 1,2-insertion mechanism, but eliminate primarily to a single pro-
duct for one reason or another [212,236,237]. Chromium based cata-
lysts appear to be a significant exception as noted by McGuinness [238].
A large number of ligands have been utilized with chromium based
catalysts to control activity and selectivity to 1-olefins, in particular 1-
hexene [239]. Building off of discoveries made at Union Carbide [240],
CP Chem commercialized the Phillips Trimerization System which
utilizes a Cr based catalyst with a pyrrolide ligand(s) and aluminum
alkyl activation/chain transfer agents [241,242]. While significant de-
bate still occurs as to whether the catalyst proceeds via a Cr(II)/Cr(IV)
or Cr(I)/Cr(III) catalytic cycle [243,244], 2nd order dependence of
ethene pressure and theoretical work show that a metallacycle me-
chanism is at work [245]. Branched C10 olefins appear to be an inherent
side product due to co-trimerization of 1-hexene with ethene [246]. In
addition to studies of the mechanism, significant work on synthesis and
repeatability of the catalyst preparation have also occurred [247]. Ac-
tivities up to about 106 g hexene mol−1 Cr h−1 have been achieved. A
complex generated using tetramethylpyrrole showed 95% selectivity to
1-hexene with an activity of 7 × 105 g mol−1 Cr h−1 in methylcyclo-
hexane solvent [248]. An important point from all these studies is that
hemi-labile halide and/or ether ligands are an important component to
achieve selectivity to 1-hexene.
Tridentate ligands containing a nitrogen and two additional soft
donors have also been well studied. PNP ligands coordinating through 2
sterically unhindered phosphines and an amine were some of the first
utilized [249]. Recent theoretical work shows that substitution on the
o-carbon of the arylphosphine increases selectivity to hexene by en-
suring single ethene insertion into the chromacyclopentane [250]. In
this system as well, hemilabile methoxy and chloride ligands are quite
important to the trimerization selectivity [251,252]. Researchers at
Sasol have recently calculated a cone angle based parameter for the
steric bulk around the N center of a family of PNP ligands and shown
that intermediate steric bulk at the N leads to higher selectivity to
tetramerization to 1-octene [253]. Thus, a complex synthesized with a
ligand having an isopropyl substituted N gave 70% selectivity to 1-
octene, while n-propyl, t-butyl, or cyclohexyl (Fig. 14) only allowed
selectivity of about 60% [253,254]. At 45 °C, the isopropyl substituted
ligand was also extremely active, converting up to 5.9 × 106 g ethene
C.P. Nicholas Applied Catalysis A, General 543 (2017) 82–97

Fig. 15. 1-hexene trimerization intermediates. The three chromacyclopentanes possible

into which the third insertion can take place. Reprinted with permission from ACS Catal.
6 (2016) 3008-16. Copyright 2016 American Chemical Society.

coupled with production of polymer, both of which were concomitant

with CrII formation by reduction of CrIII.
Fig. 14. Molecular structure of [Cr(PNP)Cl2(μ-Cl)]2. Reprinted with permission from J.
Am. Chem. Soc. 126 (2004) 14712-3. Copyright 2004 American Chemical Society.
5. Multifunctional metal and acid catalyzed
−1 −1
g Cr h .
While many metal catalysts, whether utilizing metallacycle or
SNS ligands coordinating through 2 thioethers and an amine also
Cossee-Arlman mechanisms, have been used, catalysts containing both
showed upwards of 97% selectivity to hexene (99.6+% 1-hexene in the
metal and acid sites have been used extensively, particularly for the
C6 fraction) with TOFs at 85–90 °C approaching 300,000 [255]. Pyr-
oligomerization of ethylene, which is difficult to oligomerize with only
rolidine containing NNN ligands exhibit selectivity dependence on the
acidic sites [265]. Most multi-functional catalysts studied use Ni as the
amount of MAO utilized in activation at 80°, 20 bar ethene, with
metal site with a variety of solid acids [188]. IFP’s development of the
500–1000 equivalents Al/Cr leading to > 90% selectivity to mixtures of
Dimersol and Difasol processes provided one of the first multi-func-
C4eC8 olefins [256]. Dearomatized PNP variants on pyridine based
tional homogeneous systems comprising both dimerization and iso-
pincer complexes showed moderate activity and also gave > 90% se-
merization [1,205]. The cationic nickel complexes utilized as the
lectivity to mixtures of C4eC8 olefins. The aromatic PNP or PNC (N-
AlCl4− salt catalyze dimerization of propene or butene feeds to iso-
heterocyclic carbene) variants instead yielded polymer [257].
hexenes or octenes, respectively [266,267]. The octenes are feed for
A family of ligands containing N-heterocyclic carbenes with P do-
isonanol production [268]. Difasol incorporated tetrachloroaluminate
nors have also shown utility in oligomerization of ethene. Square-pyr-
ionic liquids into the process to ease the separation and recycle of the
amidal CrIII complexes with 3 benzyl ligands produced a full range of
nickel catalyst [269,270]. In total, Axens has licensed 35 of these units
oligomers with activities up to 8.8 × 104 g C2H4 g Cr−1 h−1 at 30 °C,
worldwide [271,272]. On the heterogeneous side, Nicolaides and
10 bar ethene after activation with MAO. Use of EtAlCl2 as the acti-
coworkers carried out the classic work using nickel loaded onto
vating agent turned the complexes into polymerization catalysts while
amorphous silica-aluminas to produce fuels [273,274].
square planar CrII complexes were poorly active [258]. Similarly, mixed
UOP has recently also utilized Ni/ASAs in efforts to oligomerize
valence complexes using phosphino-amino ligands show a dependence
dilute (∼25%) ethylene feeds to mixtures of distillate and gasoline
of activating agent on selectivity, with triethylaluminum added to tri-
[275,276]. Even in the presence of significant quantities of impurities
methylaluminum depleted MAO showing excellent selectivity to 1-
including H2, CO, NH3 and H2S, these Ni/ASA based catalysts continue
hexene while other activating agent combinations yield mixtures of
to convert feed [277]. The multi-functional catalysts have significantly
olefins/polymer [259]. Diphosphine (PP) based ligands have also
higher conversion and selectivity to distillate versus the single function
shown utility. A series of silicon bridged phosphines gave up to
ASA base catalysts [84]. Hulea and coworkers have utilized Ni on
4 × 106 g C2H4 (molCr h)−1 with 78% selectivity to 1-octene at 45 °C,
mesoporous silica-aluminas to oligomerize ethene to a full range of
4 MPa C2H4. Activity and selectivity were always to a mixture of C6 and
oligomers with productivities up to 130 g oligomer/g catalyst [278].
C8 with varying percentages depending on temperature, solvent and
Activation temperature/condition of the materials is important as it
pressure [260].
appears Ni+ or dehydrated Ni2+ are the nickel-based active sites [279].
Theopold and coworkers have shown that 2,4-dimethyl-diketimi-
Catalysts comprising Ni on zeolites including MFI have been studied
nate (nacnac) based ligands on chromium produce useful ethene tri-
for a number of years [188,280]. Recently, Ni on MWW materials in-
merization catalysts. CrI dimers with μ-η2:η2 bound N2 gives essentially
cluding MCM-22 and MCM-36 have been used. The more mesoporous
100% selectivity to 1-hexene at 30 °C, 1 atm H2 without need for acti-
Ni-MCM-36 materials exhibit 2–5 times higher activity than the mi-
vation [261]. Triazacyclohexane ligands have been explored by Köhn
croporous Ni-MCM-22 materials [281]. Exchanging additional Ni onto
and shown selective (> 80%, often greater than 90%) trimerization of
the MCM-36 up to 0.28 Ni2+/H+ gave higher average activity in ethene
propene, 1-pentene, -hexene, -octene, or styrene [262,263]. Due to the
oligomerization [282]. The same increase in activity with increasing
substituents on the alkene, mixtures of trimeric compounds are formed,
nickel loading was seen in the Ni-beta system up to the point at which
the ratios of which can be explained by looking at the steric hindrance
NiO was visible by XRD. The Ni-beta catalyst gives non-Schultz-Flory
of insertion of the third olefin into the chromacyclopentane (Fig. 15).
distributions of oligomers with significant branching as one would ex-
1,2-insertions into the 1,3-disubstituted chromacyclopentane appear to
pect for a bifunctional metal-acid catalyst [283].
be favored [262].
The highly acidic sulfated and tungstated metal oxides have also
In addition to the homogeneous catalysts shown above, solids have
been combined with nickel to form bifunctional oligomerization cata-
also been utilized for selective oligomerization of ethene. Cr-MIL-100
lysts. Zong and coworkers supported NiSO4 on γ-Al2O3 containing
was synthesized and evacuated at different temperatures in order to
Fe3O4 to form a Ni-sulfated alumina catalyst for oligomerization of FCC
remove free and bound water molecules or F−/OH− anions co-
cracked gasoline (C5/C6 olefins). Diesel yield was dependent on Ni
ordinated to the Cr centers. After evacuation at 150 °C and activation
loading, with 7 wt% giving the optimum 45% yield [284]. Nickel on
with Et2AlCl, Cr-MIL-100 showed 69% selectivity to C8, 26% to C6 and
tungstated alumina catalyzed isobutene dimerization, showing up to
4% to C10 olefins at 5 × 105 g C2H4/(mol Cr h)−1 activity [264].
80% selectivity to octenes with sol-gel produced catalysts. Reaction at
Higher evacuation temperatures gave higher oligomerization activities
150 °C was optimal for dimer selectivity while the method of catalyst

92
C.P. Nicholas
preparation significantly affected catalyst stability [285]. Impregnated
catalysts showed decreased selectivity to dimer with increasing tem-
perature (50–150 °C) as had been previously observed for sulfated ti-
tania supported catalysts [286].
6. Oligomerization using combination processes
In addition to catalysts containing two functions, combination
processes where either two different oligomerization catalysts or two
reactions, at least one of which is oligomerization, have also been de-
veloped to make use of the reactivity patterns of oligomerization.
6.1. Oligomerization/Alkylation
While the initial use of solid phosphoric acid was for oligomeriza-
tion, a quickly developed second use was for alkylation of benzene with
light alkenes [287]. Recently, these two uses have been combined in
processes where oligomerization of olefins and removal of benzene
from gasoline by alkylation are both goals. In the process, benzene is
converted to mixtures of ethylbenzene, cumene, and multiply alkylated
benzenes in a mixture with oligomers [288,289]. Sasol utilized sig-
nificant excesses of olefin to achieve up to 80% benzene reduction with
SPA catalyst. About 70/30 gasoline/distillate ratios were observed with
propene converted at higher rates than butenes [289].
At UOP, we have utilized UZM-8 zeolitic materials as the catalyst for
this process, showing equivalent reaction rates of the olefin with ben-
zene and toluene and slower reaction rates with higher alkylated arenes
including xylenes and mesitylene [290,291]. Using dilute (∼25vol%)
ethylene as the olefin feed, over 20% reduction of benzene was possible
in a full reformate (BTX, A9) feed even in the presence of H2, H2S, CO
and CO2 [292].
Following on the success of MWW based alkylation processes [293],
multiple researchers have studied MWW materials including MCM-22
for combination oligomerization/alkylation processes for benzene re-
duction. Laredo and coworkers have shown that MCM-22 is sig-
nificantly more stable and active than beta zeolite catalysts for con-
version of benzene in refinery derived aromatic feeds [294]. As seen
previously, high olefin to benzene ratios are necessary for efficient re-
duction of benzene and they also observed that higher benzene contents
in the aromatic feedstock are beneficial to C6H6 reduction [295,296].
EMRE, Mobil and Badger workers converted C2eC4 olefins, preferring
C3eC4 mixtures, over MCM-22 or MCM-49 in the presence of various
benzene containing refinery streams to provide an alternative benzene
reduction strategy to meet MSATII regulations [297–299]. The
BENZOUT™ process was scaled up and tested in a refinery [300–302].
Distillate range fuels, whether jet fuel or for transportation, have
been the target in a number of combination processes. Sasol researchers
used SPA to catalyze oligomerization and alkylation of propene and
benzene or toluene to make jet fuels containing some aromatic mole-
cules. Oligomerization rates are faster at higher propene/arene ratios
and alkylation rate faster at low propene/arene ratio [303].
6.2. Oligomerization/Oligomerization
Harvey and coworkers have recently utilized combinations of oli-
gomerization processes to synthesize distillate range materials
[304–306]. Fig. 16 shows an envisioned process where ethylene is
converted to hexene via one of the metallacycle derived trimerization
catalysts. They then utilize Cp*2ZrCl2/MAO to convert 1-hexene to C12
and C18 branched molecules via 1,2-insertion pathways [304]. Pre-
viously, they had showed 1-butene conversion to 2-ethylhexene via 1,2-
insertion over Group IV catalysts followed by acid catalysis to convert
the C8 molecules to jet fuels [305,306].
Hwang and Chae have also shown the conversion of ethene to jet
fuels with a combination of processes. They used Ni supported on Al-
containing SBA-15 at 200 °C/10 bar to transform ethene to liquids rich
93
Applied Catalysis A, General 543 (2017) 82–97
Fig. 16. Use of multiple oligomerization techniques to synthesize fuels. Harvey, et.al.,
utilize first a metallacycle mechanism, then a 1,2-insertion mechanism to synthesize
distillates. Reproduced from Ref. [304] with permission of The Royal Society of Chem-
istry.
in the C8 fraction at a WHSV of 0.38, followed by oligomerization of the
obtained liquids over Amberlyst-35 to achieve overall yields of ∼42%
jet fuel [307].
6.3. Alternative CeC bond formation/Oligomerization
Willauer and coworkers took a different tack, hydrogenating CO2 to
C2H4 containing feeds over modified Fischer-Tropsch catalysts and then
studying the oligomerization of C2H4 over Ni/ASA bifunctional cata-
lysts, achieving 56% yields of jet fuel range materials at 0.15WHSV
[308]. The use of methanol to olefins to produce light olefins for oli-
gomerization processes has been commercially practiced, as noted
earlier, but deserves mention here [7,106]. Finally, dimethylether was
converted to jet fuels in a hypothetical process by NREL researchers.
Triptene (2,3,3-trimethyl-1-butene) and other C6eC8 branched olefins
whose carbon skeletons are available from acid catalyzed homologation
of DME [309] were oligomerized to C10eC20 distillate range oligomers
with up to 52% yields at 80 °C over Amberlyst-35 with some concurrent
isomerization and cracking [310].
7. Conclusion and future outlook
After 80 years of work following Ipatieff’s initial discoveries, the
oligomerization of light olefins is still an active research area of com-
mercial importance. Acidic catalysts such as solid phosphoric acid and
zeolites are utilized in multiple commercial processes and continue to
be under investigation as new material types and processes are dis-
covered/developed. Significant work has been performed using the
most common zeotypes and from that, general rules about stability and
product shape selectivity have been developed on the basis of pore size
and connectivity.
Work is still needed as new zeotypes are discovered, partly to ensure
that the rules continue to hold even for new zeotypes, but also to ex-
plore zeolites containing multiple size channels in a single material.
Will oligomerization in a material containing both a 10MR and a 12MR
channel produce product like that from a 10MR or that from a 12MR?
What about oligomerization in a material containing multiple size rings
in a single channel? How linear will the product be from a uni-di-
mensional 8MR zeolite? These are the types of questions that remain to
be answered, frequently addressing shape selectivity, but which will
often require material discovery before the question can be addressed.
An area that has held back the development of novel acid catalysts is
the ability to characterize the product produced by the new catalyst.
While GC techniques, including GCxGC, have developed significantly
since the advent of the field, additional molecular based characteriza-
tion of the products produced is necessary. Today, it is possible to
characterize, in significant detail, the molecules produced by oligo-
merization in a single carbon number range such as the C8 region.
However, this same detail is often not available for the C9 or C10 regions
of the same product and therefore assumptions are made that dis-
tribution of the C9 and C10 fraction is similar to that of the C8. For a
given catalyst, this may be true, or may start to break down as Exxon
C.P. Nicholas
researchers have shown for MFI based catalysts. Additional efforts, both
to ease the time spent to characterize a particular region of the product,
and to be able to establish the identities of molecules within that region
are needed.
Metal based catalysts have become of significant importance over
the last 10 years, particularly with the development of homogeneous
catalysts capable of selective dimerization or trimerization which
achieve high selectivities to 1-butene, 1-hexene, or 1-octene. The next
frontier of development here will be to develop selective oligomeriza-
tion to longer chain oligomers such as C12, C14, or C16, currently
available only by fractionating the total product from a full range LAO
process. Another area where needed development will occur is in the
production of linear oligomers from substituted olefins, such as the
reasonable selectivity to linear octenes from 1-butene reported in
Section 3.5. Head to tail coupling has been a long sought goal, so
continued development of understanding of the reaction mechanism
and structure-property relationship will help. Additionally, the advent
of heterogeneous catalysts capable of the same tight structure-property
relationships developed in the homogeneous cases would make devel-
opment of selective oligomerization processes even more commercia-
lizable.
In addition to oligomerization only processes, researchers have de-
veloped multiple processes where oligomerization is one of the steps or
key reactions in a process. Impediments here are largely due to the
necessity to match oligomerization conditions with the conditions uti-
lized for another reaction, so advancement of oligomerization catalysts
capable of operating under different temperature or pressure regimes,
or the development of suitably scalable dual batch processes will cer-
tainly help progress in this area.
Overall, oligomerization has been a commercially useful reaction to
upgrade low valued light olefins to higher valued products for over 80
years and will continue to be with the further development of the new
and soon to be discovered advancements detailed within.
Acknowledgment
CPN acknowledges Honeywell UOP for permission to publish.
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Christopher P. Nicholas is Principal Scientist at
Honeywell UOP. He joined Honeywell UOP in 2006 and has
worked throughout the Research departments at UOP, pri-
marily focused on inventing and catalytically testing new
materials and processes. Particular foci have included het-
erogeneous catalytic processes such as olefin oligomeriza-
tion and alkylation, synthesis of inorganic materials (in
particular metal oxides and zeolites), process engineering,
molecular adsorption, and olefin metathesis. Chris is an
inventor or co-inventor on more than 75 US and foreign
patents and coauthor of 20+ peer-reviewed journal articles
and a book chapter. Chris’ research interests span the
breadth of inorganic and catalytic technologies ranging
from materials synthesis to characterization to catalyst and process development. He has
also served in multiple roles for the Chicago section of the North American Catalysis
Society. Prior to joining UOP, Chris earned a B.A. from Kalamazoo College, and a Ph.D.
from Northwestern University.