INDUSTRIAL APPLICATIONS OF OLEFIN METATHESIS

J. C. MOL
Institute ofMolecular Chemistry, Faculty ofScience,
Universiteit van Amsterdam,
Nieuwe Achtergracht 166,1018 WV Amsterdam, The Netherlands
E-mail:j [email protected].

1. Introduction

Olefin metathesis opens up new industrial routes to important petrochemicals,

oleochemicals,polymers, and specialty chemicals. Industrial applications of the olefin
metathesis reaction known until 1997 have been described elsewhere, including
processes that have not been commercialized and processes that are no longer
commercial [1]. Here we will discuss the present situation
.

2. IndustrialProcessesfor theProductionof Normal Olefins

2.1. PRODUCTION OF PROPENE

Propene is obtained mainly from naphtha steam crackers (globally about 65%) as a
coproduct with ethene, and from fluid catalytic cracking (FCC). Relatively
units small
amounts are produced by propane dehydrogenation and by coal gasification via
Fischer-Tropsch chemistry
. Strong global demand for propene, however, presently
outpaces supply from these conventional sources.

2.1.1. The Phillips triolefin pro cess.

An alternative route to propene is by applying the metathesis reaction for the
conversion of a mixture of ethene and 2-butene into propene. This process, called the
Phillips triolefin process, was originally developed by Phillips Petroleum ., USA,
Co
and was commercialized in 1966 for the conversionofpropene into ethene and butene,
due to less propene demand at that .time
The Phillips proces
s in the reverse direction,
equation(1), is now offered by ABB Lummus Global, Houston (USA) , for license as
olefins conversion technology(aCT) for the production of propene.

(1)

Figure 1 shows a simple process flowiagramof

d the aCT process. Fresh 4C's plus
C 4 recycle are mixed with ethene feed plus recycle ethene and sent through a guard bed
to remove trace impurities from the mixed feed. The feed is heated before entering the

313
Y.lmamoglu and L Bencze (eds.), Novel Metathesis Chemistry: Well-Defined Initiator Systems/or Specialty
Chemical Synthesis, Tailored Polymers and Advanced Material Applica tions, 313-322.
© 2003 Kluwer Academic Publishers.
314

o Ethene Recycle Ethene Lights

o Feed
Purge

C. Recycle
Purge
Feed
Guard Metathesis Ethene Propene
Bed Reactor Column Column

Figure 1. The a CT Process (ReversedPhillips TriolefinProces s)[3].

metathesis reactor. The reaction takes place in a fixed-bed reactor over aof mixture
WOiSiO z (the metathesis catalyst) and MgO (an isomerization catalyst) >260°C
at and
30-35 bar [2]. 1-Butene in the feedstocks isomerizedto
i 2-butene sa the original
2-buteneis consumed in the metathes is reaction. The conversion of butene is above
60% per pass and the selectivity for propene>90%. is The reactor is regenerated on a
regular basis [3]
.
At the end of 1985 Lyondell Petro chemicalCo. started to operate a 136,000 t/yr (tons
per year) OCT plant in Channelview, Texas (USA) for the productionof
polymerizat ion-gradepropenevia cross-met athesisbetween ethene and 2-butene . In
their process, part of the etheneromf cracking units is dimerized to 2-butene , using a
homogeneous nickel catalystdeveloped by Phillips, which reacts with the rest of the
ethene to produce propene [4]. The process has been retrofitted company'ssteam
to the
cracker in Channelview [5].
In particular, naphtha steam crackers with an integrated metathesi s unit are an
interesting alternative for producing more propene. In December , 2001 BASF Fina
Petrochemicals (a 60 -40 joint venture between BASF and Atofina) brought on stream a
world-scale steam cracker plant in Port Arthur , Texas (USA), which will integrate the
OCT process to enhance the production of propene in relation to .ethene This plant
produces 920,000 t/yr of ethene and 550,000 t/yr of propene , but when the metathe sis
unit is added (at the endof2003),it will adjust the output to 830,000t/yr of ethene and
860,000 t/yr of propene [6]. Raw Cz and C4 feedstocks are supplied directly by the
steam cracker, but additional 4'sCwill be taken from the Sabena Chemicals'C 4 splitter
being planned by a joint venture of Shell Chemicals, BASF and Atofina; by-products
are recycled to the cracker.

Mitsui Chemicals will install the OCT technology to increase the propene capacity at
it's olefins plant at its Osaka works in Japan by ,000140 t/yr to 420,000 t/yr.
 315

Completion of the project is expected in August 2004 [7]. The OCT process will also
be used at Shanghai Secco Petrochemical, a joint venture of BP Chemical, Sinopec and
Shanghai Petrochemical Corporation, which is building a 900,000 t/yr naphtha cracker
integrated with an OCT unit to produce a total of,000t/yr
590 of propene at Caojing,
China. The complex is scheduled for start-up in the first
half of 2005 [8]. PCS
(Petrochemical Corp
. of Singapore), a joint venture between Shell Chemicals and
Sumitomo Chemical, is studying an increase in propene capacity at its olefin units by
200,000-300,000t/yr using the OCT technology [9]
.

2.1.2. The Meta-4 Process.

The Institut Francais du Petrole (IFP) and the Chinese Petroleum Corporation
(Kaoshiang, Taiwan) have jointly developed a process for the production of propene ,
called Meta-4. In their process, ethene and 2-butene react with each other in the liquid
phase in the presence ofRe207/Alz03
a catalyst at 35°C and 60 bar
. The (equilibrium)
conversion is 63% per pass.
The process features semi-continuous countercurrent contact between catalyst and the
liquid reactant medium . The feed stre
am enters the bottom of the metathesis reactor
and leaves at the top. As the catalyst descends through the reactor, it becomes less
active and must be regenerated . A small fraction of the catalyst is withdrawn
periodically from the bottom of the reactor and transferred to the top of a regenerator
.
The fully regenerated catalyst leaves at the bottom of the regenerator and is returned to
the top of the metathesis reactor. Unconverted ethene and butene are recycled to the
reactor [10,11].
The process is not yet commercialized , mainly because of the cost of the catalyst and
the requirement of a high purity of the feed stream . This metathesis technology is
presently offered by France'sAxen, a subsidiary of IFP , formed in 2001 through the
mergerofIFP's licensing division with Procatalyse Catalys is & Adsorbents.

2.2. PRODUCTION OF I-HEXENE

A semi-works unit using the OCT process for butene metathesis to produce
-hexeneis
l
under construction at
Sinopec'sethene plant in Tianjin, and will be started up in early
2003 [12].

2.3.PRODUCTION OF NEOHEXENE

Neohexene(3,3-dimethyl-l-butene) is an important intermediate in the synthesis of

Tonalide", a synthetic musk perfume.It is also used to make Terbinafine", an anti-
fungal agent. A neohexene unit located within Chevron Phillips Chemical Company
LP's Houston Chemical Complex was built in 1980 with a capacity of 1400 t/yr [13].
The process is based on the dimer of isobutene, which consists of a mixture of
2,4,4-trimethyl-2-penteneand 2,4,4-trimcthyl-l-pentene. Cross-metathesis of the
former with ethene yields the desired product
; equation (2). The latter is not wasted
since a dual catalyst can be used to ensure that it is isomerized to 2,4,4-trimethyl-2-
pentene as this gets used up by metathesis
.
316

o Eth
Ethene Isobutene
recycle

DIB
recycle

I OIB Reactor &

.<;p.nArAfnr

Figure 2. The Neohexene process. D1B

= di-isobutene [11].

+ (2)

With a 1:3 catalystmixture of W0 3/Si02 and MgO an average conversion of the

di-isobuteneof 65-70% and a selectivityto neohexeneof approx. 85% is achievedat
370°C and 30 bar(molar ratio ethene /di-isobutene= 2). The coproductisobuteneis
recycledto anisobutenedimerizationreactor.
Figure 2 shows theprocessschemeoftheneohexeneprocess. Commercialdi-isobutene
is firstfractionatedto remove anoxidationinhibitor,which would otherwisepoisonthe
dual catalystsystem. The fractionateddi-isobutenealong with the ethene streamenters
the topof the reactorcontainingthe catalysts. The ethene,consistingof make-upand
recycledethene, iscompressedto therequiredpressurebeforeit enters thereactor.The
separationof reactantsand productsis achievedby strippingand fractionation . The
of air and inert gas to
catalystis reactivatedfrom time to time, using a mixture control
thetemperature o fthe cokebum-off.

2.4. THE SHELL HIGHER OLEFINS PROCESS (SHOP)

A large-scaleindustrialprocess incorporatingolefin metathesisis the Shell Higher

Olefins Process (SHOP) for producinglinear higherolefins from ethene. The process
takes place in three stages.
 317

In the tirst step, ethene is oligomerized in the presence of a homogeneous Ni-phosphine

catalyst (at 90-100°C and 100-110 bar) in a polar solvent (l,4-butanediol)to give a
mixture of linear even-numbered alpha oletins ranging from 4 to CC40 with a
Schulz-Flory type of distribution; equation (3). The catalyst is prepared
in situ from a
nickel salt, e.g., nickel chloride, and a chelating phosphorous -oxygen ligand by
reduction with sodium boron hydride .

(n + 2) CH 2=CH 2 (3)

n = 0 - 36

The oletins formed are immiscible with the solvent; product and catalyst phases are
thereby readily separated so that the Ni catalyst can be recycled repeatedly
. The C6-C 18
l-alkenesare separated from the product ixtureby
m distillation. This fraction can be
further fractionated into individual compounds, which can be used as comonomer in
polyethene production or converted into products such as synthetic lubricants,
plasticizer alcohols, detergent alcohols, synthetic fatty acids
. Theetc
remaining lighter
«C 6) and heavier >C
( 1S) alkenes go to puritication beds
, which remove catalyst and
solvent residues that would otherwise deactivate the isomerization catalyst.
In the second step, these lighte r and heavier alkenes undergo double-bond
isomerization over a solid potassium metal catalyst to an equilibrium mixture of
internal alkenes; equation .(4)
R-CH=CH2 ~ R1-CH=CH-R2 (4)

In the third step, this mixture is passed over an alumina-supported molybdate

metathesis catalyst
, resulting in a statistical distribution of linear internal alkenes with
both odd and even numbers of carbon atoms via cross-metathesis reactions such as
. This yields about 10-15wt%of the desiredC WC 14 linearinternal alkenes
reaction (5)
per pass, which are subsequently separated by normal distillation
.

CH3CH=CHCH3 + CH3(CH2)7CH=CH(CH2)9CH3 ' •

CH3CH=CH(CH2)7CH3 + CH3CH=CH(CH2)9CH3 (5)

The isomerization and metathesis catalysts operate lOO-125°C

at and 10 bar. The
remaining lower« C II ) and higher >C
( I4) alkenes are recycled. The product consists of
>96% of linear internalC WC l4 alkenes. These can then be converted into detergent
alcohols, via a hydroformylation process, or into detergent alkylates [14.15].
Shell Chemicals operates a SHOP unit at Stanlow (UK) with a capacity of270,000t/yr
and two large-scale SHOP units at Geismar, Louisiana (USA) with a total capacity of
600,000 t/yr of higher oletins
. In 2002 Shell has brought on stream a third SHOP unit
at their Geismar location for the production of another 320,000
t/yr of higher oletins
.
This expansion brings Shell Chemicals' total worldwide production capacity to
318

1,190,000 tonsof linear alpha and internal olefins per year

; these are sold under the
trade nameNeodene" [16].

3. IndustrialProcesses for theProductionof Polymers

In the polymerfield ring-openingmetathesispolymerization(ROMP) of cycloalkenes

is an attractiveprocess for makingpolyalkenamerswhen based on cheap
monomersor
possessing special propert ies compensatingfor a high price. Several industrial
processes involving homogeneously catalyzed ROMP have been developed and
broughtintopractice. See also the bookofDragutanand Streck [17].

3.1.POLYOCTENAMER

Since 1980 Degussa-Huls has been producing Vestenamer" 8012, themetathetical

polymer of cyclooctene. This polymer also goes under the name TOR
(trans-polyoctenamer) . The polymerizationis performedin hexane as a solvent in the
presenceofa WCl 6-basedcatalyst, giving almost 100% yield . The polymerconsists of
two distinct parts:high-molecular-weight
a fraction(molecularweight> I 05) and a low-
molecular-weightfraction consisting of a series of cyclic oligomers. This is readily
explainedin terms of a competitionbetween apropagationreaction (6a) and an
intramolecularbackbitingmetathes is reaction (6b).

M=CHR r-.
M CHR HC=CH
+ 11 11
H .. MTtytCHR (6a)
HC=CH HU
~

RH~:t~:)ln ~ M=CHR + HC=fcQfcH

I nI
(6b)

The product has a purity of99.5%. The cis to trans ratio, whichdeterminesthe degree
of crystallinity,is controlled by thepolymerizationconditions. The trans double bond
contentof Vestenamer " 8012 is 80%, thecrystallinity30%, and themolecularweight
75000. Used as a blending material, it offerspossibilitiesfor the improvementof
propertiesof rubbercompoundsand for use inrubberizedcement. Anadditionaltype,
Vestenamer " 6213, with a lowertrans content (60%) and, therefore, lower crystallinity
(10%) , has been developedto provide for low-temperatureapplicationswhere the
admixtureofthestandardtype would lead to exce ssive stiffening[18].

3.2. POL YNORBORNENE

The firstcommercialmetathesispolymerwas polynorbornene,which was put on the

market in 1976 byCdF-Chimie in France, and in 1978 in the USA and Japan
, underthe
® [ 19].
trade name Norsorex
The polymeris obtained by ROMP of 2-norbornene(bicyclo[2.2.I]-2-heptene),which
is made fromdicyclopentadieneand ethene, and gives a 90 t%rans polymerwith a
very high molecularweight (> 3.106 glmol) and a glasstransitiontemperature(Tg) of
 319

37°C; eq. (7). The process uses a RuCI3 catalyst in butanol, operates in air, and
produces a useful elastomer, to be used for oil spill recovery, as a sound barrier, or for
damping.

ndJ ROMP
RuCl3 / butanol
.. ~n (7)

Norsorex® is presently produced in France Elf

by Atochem, and developed worldwide
by the Japanese company Nippon Zeon.

3.3. POLYDICYCLOPENTADIENE

Much interest has been shown in the ROMP of endo-dicyclopentadiene (DCPD),

obtained as a by-product from naphtha crackers. If only the highly strained norbomene
ring opened, a linear polymer should be formed; . (8a).
eq However, under certain
conditions the double bond in the disubstituted cyclopentene ring may also undergo
metathesis, thereby giving rise to cross-linking,
. (8b).
eq

a
•

Equation (8)

The product is a tough, rigid, thermoset polymer of excellent impact strength

. Quite
large objects can be produced via a reaction injection molding (RIM) process. The
commercial production of molded objects from DCPD-based feed using RIM
320

technologyhas beendevelopedmainly by theBFGoodrich Co., under the trade name

Telene®, and by Hercules Inc . under the trade name Metton ®. The latter is now
producedby Metton America, Inc. at La Porte (USA), who have also licensedtheir
process to theTeijin-MettonCo. in Japan.
In the RIM technique,two monomerstreams are used . In the Metton" liquid molding
resin (LMR) system developedby Hercules, one stream contains DCPD monomer,
catalyst(WCI 6 + WOCI 4) , nonylphenol(to solubilizethe tungstencompoundsin the
monomer),additives (such as antioxidants),and fillers. The other stream contains
DCPD monomer, eocatalyst(EtAIClz), retarder,additivesand fillers. The two streams
pass first into a mixingchamber and then into the mold, where exothermic an
polymerizationtakes place at a high rate after a short
inductionperiod. Thesolutionsof
the individualcatalystcomponentsin the monomerare stable, and the length of the
inductionperiodcan becontrolled[20].
In the Telene " process the procatalyst is a tetrakis(tridodecylammonium)
octamolybdate , activatedwith a mixtureof Et2AICI, propanoland SiCl4 Up to 10%
trimer of cyclopentadieneis added to themonomerto increasecross-linking in the
polymer, while the trimer also lowers the melting
pointofDCPD . The Tg oftheproduct
is typically 150°C.BFGoodrich Co. have licensed their process Nippon
to Zeon, which
produces it under the trade name Pentem" , In the USA Telene® RIM polymers are
presentlyproducedby Cymetech,LLC.
Poly(DCPD) has won several marine, recreationalvehicle andoff-roadutility vehicle
applicationsaround the world, such as tonneaucovers, snowmobile hoods, tractor
fenders, and heavy truck panels
.

3.4. HYDROGENATED POLYMERS

producingthepolymerZeonex", ofthe general type

Since 1991 Nippon Zeon has been
1, obtainedby ROMP of norbomeneand related (multi-ring) monomers, followed by
partial or total
hydrogenation.

Equation (9) gives an example

startingwith tetracyclododecene(TCD). Zeonex" is an
amorphous,colorless andtransparentpolymerwith a high Tg (l40°C) and lowmoisture
absorption. These propertiesmake it very suitable for optical applications(disks,
lenses, and camera prisms).

ROMP
.. .. n

(9)
 321

Zeonor" (2) is an amorphoushydrogenatedco-polymerand has beencommercialized

since 1998. It has been acceptedfor use in optical,electronic
s, and automobile
applications
.

n m

(2)

4. Conclusions

In the chemicalprocess industry, olefinmetathesishas now become aprocess with

large-scale applications using heterogeneousas well as homogeneous catalysts
systems. More commercialapplicationsare to beexpected , in particularconsidering
the recentdevelopmentof highly activerutheniummetathesiscatalyststhat are more
tolerantto functionalgroups andresistanttowardsmoistureand oxygen. In the areaof
fine chemicals, interestingproducts will be synthesized in the (near) future via
metathesisreactions,such as biologically active compounds (e.g. pharmaceuticals,
insectpheromones , prostaglandins,etc) andadvancedpolymericmaterialsvia ROMP .
Moreover, the metathesis reaction has also favourable perspectives for the
oleochemicalindustry[21].

5. References

I. Ivin, KJ. and Mol, J.C, (1997) Olefin Metathesis and Metathesis Polymerization, Academic Press,
London, Chapter17.
2. Parkinson, G. (2001) Chemical Engineering. 108 (8) August, p. 27.
3. Kantorowicz, S.l. (2002) C4 Processing Options to Upgrade Steam Cracker and FCC Streams,
Lecture
presentedat the 2nd A sian PetrochemicalsT echnologyConference,7-8 May, Seoul, Korea.
4. Chemical Week (1985), 20 November, p. 54.
5. Scott,A. (1999) Chemical Week, 3 November, p.41.
6. European Chemical News (2002), 25 March, p. 20.
7. Chemical Week (2002), 16 October,p. 16.
8. Wood, A. (2002) Chemical Week, 27 February, p. 40; News Release, ABB Lummus Global, 15
April, 2002.
9. N. Alperowicz (2002)Chemical Week, 6 M arch,p. 16.
10. Amigues,P., Chauvin, Y .,Commereuc, D .,Lai, C .C., Liu, Y .H.and Pan,l. M. (1990) Hydrocarbon
Process., 69, October, p. 79;
11 Cosyns, J., Chodorge, J., Commereuc,D . and Torck, B. (1998) Hydrocarbon Process., 77, March,
p.61.
12. Wood, A .(2002) Chemical Week, 13 February, p. 32.
13. Banks, R.L.,B anasiak,D .S., Hudson, P.S. and Norell, J.R. (1982) J. Mol. Catal. 15,21.
14. Freitas, E.R. and Gum, C.R. (1979) Chem. Eng. Progr. 75 (I), 73.
15. Sherwood, M . (1982) Chem. Ind. (London), 994.
16. Shell Chemicals Information Handbook (2002). Shell Chemicals Limited .
322

17. Dragutan, V . and Streck, R.(2000) Catalytic Polymerization of Cycloolefins, ElsevierScienceB.Y.,

Amsterdam,The Netherlands.
18. Diedrich, K.M . (1993) in Ullmann's Encyclopedia ofIndustrial Chemistry, 5th ed. Vo!. A23, YCH ,
Weinheim,p. 302.
19. Marbach,A .and Hupp, R. (1989) Rubber World, June,p. 30.
20. Breslow,D.S. (1993) Prog. Polym. Sci. 18, 1141.
21. Mol, i.c .(2002) Green Chemistry 4,5.