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New Butene Dimerization Technology: 17th Saudi Arabia-Japan Joint Symposium Dhahran, Saudi Arabia, November 11-12, 2007
New Butene Dimerization Technology: 17th Saudi Arabia-Japan Joint Symposium Dhahran, Saudi Arabia, November 11-12, 2007
Abstract
Ne w bute ne di me ri zation tec hnol ogy with hi gh di mer se l ectivit y has be en
devel oped at Ni ppon Oil . The obta ine d isoocte ne ha s be en us ed a s a ra w
mat erial of hi gh Res earc h Octa ne Number (RON) gasoline. The key
technology of the process i s a novel phos phoric aci d catalyst different fr om
prior sol id phosphoric aci d ( SPA) catal yst s. The a uthors found that
phosphori c aci d monome r ( ortho phosphori c acid) ha s excelle nt di mer
selecti vity, developed a nove l cata lyst that consists of only of phosphoric
acid monomer s upported on sil ica.
1. Int ro d uct i on
A mi xtur e of bra nched C8 ol e fi n is call ed isooctene. Isooct ene i s a di mer
of C4 fra c tion that c ontai ns is obut ene . I t is us e ful as a ra w mat erial of hi gh
RON gasoline and a ra w mat erial of chemical i ntermediates such as alkyl
phe nol a n d isonona noic a cid. The de mand for aromatic compounds i s rising
rapidl y. Aroma tic compounds s uc h as x yl e ne are t he ra w mat erials o f
chemicals. Ar omati c compounds have high RON value s, a nd ar e pr esent i n
gasoline today. Therefore, ar omati c c ompounds producti on coul d be
increased by extr act ion of the aromatic compounds fro m ga solin e. Ho we ver,
other mat erials of high RON value become n ec essar y t o mai nt ai n t he R O N
value of the gasoline . In addition, octa ne number i mpr ove me nt of
automotive gasoline is being studi ed, with t he goal of energy conservation.
Use of t he hi gh- RON methyl tert-but yl ether (M TBE) i s ba nne d or re stricted
[1-3], and so the search is on for materials of high RON values as substitutes
for M TBE. Mea n whi le, the de ma nd for propyle ne is ri sing r apidl y. Pr opyl ene
is the raw mat erial of pol ypropylene , a commodit y pl as tic. The vigorous
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de mand has led t o increa sed propyle ne producti on. ABB Lummus Global’s
OCT ( Ole fi n Conve rsion Te c hnol ogy), a pr oces s which pr oduces pr opyl ene
fr om n-butene and ethylene , has bee n installe d in var i ous pla ce s. Thi s
technology was also adopted by Nippon Oil Corporation. OCT is a
technology that manufactur es pr op yl ene by t he metat hesis rea ction of
n-butene and ethylene. Isobutene from the C4 fr action is unneces sa ry i n t he
metathesis reaction. On the other hand, the manufacturing process of
poly mer gasoline by oli gomeri zation of light ol efin has been researched
since the past . Concerni ng the di me riz ation pr oc ess usi ng FCC-C4 f eedst oc k,
whi ch is rich i n n- butene, t h ere ar e some examples of commercialization
such as UOP's I n Al k process [7-13] and the NExOCTANE proc ess develope d
by Neste Oil and Kell ogg Brown & Root [14-16]. However, there ar e no
examples of selective di merization using solid acid catalysts with high
conc entr a tion of is obut ene , whi ch has high rea c tivity. To use t he i s obut ene
in t he C4 fracti on effecti vel y, we de veloped new is obut ene di me r ization
technology. Pr oduc t is ooct e ne bec omes a ra w materi al for hi gh RON
gasoline. A commercial pl ant has been onstre a m sinc e 2006 in Kawa saki
Japa n ( Fi g. 1), a nd producti on of is ooc tene is 40,000 t ons per year.
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17th Saudi Arabia-Japan Joint Symposium
Dhahran, Saudi Arabia, November 11-12, 2007
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Dhahran, Saudi Arabia, November 11-12, 2007
with silica, and the phosphoric acid polymer is a compound that is condensed
by dehydration of phosphoric acid monomer. This is because the catalyst is
ma nufactured at a p proxi mate ly 300 de grees . There fore , it was not easy to
take an ester react ion me chanis m tha t ha d high di me r selecti vity. The
devel oped catal yst a chieves hi gh acti vit y a nd hi gh di mer s el ectivit y, because
it consist s onl y of phosphor ic acid monome r s upporte d on sili ca. In ot her
wor ds , we de vel oped a novel cat alys t that is different fr om prior SPA
catalysts.
100
High-yield
Dimer selectivity, %
>Δ20%
Developed catalyst
Sillica alumina catalyst
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17th Saudi Arabia-Japan Joint Symposium
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O OH
+ P O O
HO OH P
HO OH
isobutene phosphoric acid buthyl phosphate
O O O OH
P + P
HO OH HO OH
isobutene dimer
O O
P
HO OH
steric hindrance isobutene trimer
Fig. 3 Ester intermediate reaction mechanism
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Wit h moi sture , phosphoric a cid on the catal yst changes phosphori c aci d
states. When moist ure densit y is l ow, phosphor ic acid is conde nse d fro m
phosphori c aci d monomer to a phos phoric aci d poly mer by de hydrati on. The
change of phosphoric acid states can be deter mined by the P 3 1 -MAS NMR of
the catal yst ( Fig. 4). The chemi cal shift of phosphoric a cid monomer i s 0
ppm, and phosphoric acid polymer is below -20 pp m. When water of t he
necessary quantity is not added, it becomes a lower activity catalyst. Our
exami nati ons showed t hat when phosphori c acid st ates cha nge from
monomer to polymer, both activity and selecti vit y dec reas e. The phosphori c
acid state of the developed catalyst is phosphoric acid monomer. In order to
contr ol t h e de hydra tion condensati on of t he phos phor ic a ci d on t he c atalyst ,
the nece ss ary qua nti ty of wate r is added to the C4 feedstock in this process.
Fresh catalyst
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Yield of isooctenes, %
Target
2-2- 1. Reactor
Sinc e ol i gomeri zat ion of butene s is a consecutiv e reaction, di mer
selecti vit y i ncreases as but ene conv ersion is lowered in mild reaction
conditions.
Wit h a low select i vity catalyst, butene convers ion i s kept low in the first
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2-2- 2. Quench
Di meri zat ion of butenes i s an exot he r mic reac tion. Wit h convent ional
technology, the reaction heat is removed using the unreacted raffi n ate. This
is t he way that t he unreact ed r a ffinate separat ed from effl uents of the reactor
by distillation feeds to the catalyst beds. Therefore, reaction heat in the
upper bed is removed. With this technology it is di fficult to for m heav y
product s large r tha n tri mers beca use the rea cti on progre sses by t he est er
reaction mechanism. Therefore, it is pos sible t o re move the re acti on heat by
the fact that the reactor effl uent which is not distilled is circulated back t o
the react or top. There is no decreas e of dimer selectivity because it is
di fficult for di mers to form heavi er pr oducts. There fore, it was possible to
use an inexpensive adiabatic reactor. Thus, as shown in Fi g. 4, thi s process
becomes a si mple one invol ving one adiabatic reactor and t wo di stillation
towers.
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Isobutene fraction
Butane
Isooctene
Butane stripper
Heavy oil fraction
Dimerization reactor
Product stripper
Fig. 6 Develope d di merizati on proces s
3. Conclusion
We found that phosphoric acid monomer has excellent dimer selectivity,
and developed a novel cat alyst that consists only of phosphoric acid
monome r s upporte d on sili ca. Because the devel oped cat alyst can be
rege nerat ed, waste catalyst c an be re duced. BRON of isooctene i s 115, and it
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can cont ribute to the energy conservati on thr ough fuel economy
improvement for gasoline automobiles. In addition, the RON and distillation
chara cteri stics of i sooc tene rival t hos e of ar omatic comp ounds . Is oocte ne
can be used to repl ace ar omatic compounds in gasoli ne. I n ot her words, it
become s pos sible t o increa se pr oducti on of aromati c c ompounds indire ctly.
A c ommer cial pla nt has bee n onstr ea m since 2006, with annual production of
40,000 t o ns.
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[14] PEP Re vie w 2003- 12
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