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production of olefins
A FCC technology and catalyst formulation selectively crack a wide range of feeds,
including residue, to yield high quantities of light olefins
T
he primary purpose of the fluid drawbacks of a longer contact time.
Timeline of the use of zeolites in
catalytic cracking (FCC) process higher FCC olefins production Short contact time produces less dry
historically has been to convert gas and coke, and provides a higher
low-valued, heavier petroleum selectivity to light olefins. However, it
Year Event
streams into gasoline, alkylation feed 1970 ZSM-5 in FCC invented requires a catalyst formulation that
(eg, isobutane and butene) and, to a 1974 USY in FCC invented can deliver the desired levels of
1983 ZSM-5 commercialised in cracking
lesser extent, other distillate products. conversion and yield for light olefins.
1986 Zeolite Beta in FCC invented
While other light olefins were always 1990 First on-purpose olefins production Recracking cracked material such as
produced, the low volumes did not via ZSM-5 naphtha can yield incremental light
attract much attention because of 1995 Indmax FCC process invented olefins. This recracking can be done in
2003 Indmax process commercialised
separation costs and modest product the same or a separate riser reactor.
margins. Injecting in the same riser reactor has
In the last decade, production of Table 1 been used for upgrading visbreaker or
propylene from FCC units (FCCUs) coker naphtha in FCC risers. Recycling
has grown significantly and is now from the FCCU and the approaches FCC naphtha to the same riser reactor
approaching 20–30% of all propylene employed. Specifically, the Indmax has also been applied, but the yield of
produced worldwide.1 Key drivers of FCC (I-FCC) process will be addressed, dry gas increases.
this surge in production include the including its benefits, the underlying In the partial catalyst recycle
price spread between propylene and concepts, the chronology of its approach, part of the spent catalyst is
gasoline, and increased demand for development and commercialisation. recycled back to the reaction section
propylene. To maximise the propylene to increase the catalyst-to-oil ratio.
yield from FCCUs, significant Approaches to production of The drawback is that the catalyst’s
improvements have been made in increased olefins dynamic activity is lower than when a
catalyst formulation and process Process variables higher catalyst-to-oil ratio is achieved
technology. This relatively new Some of the variables of the FCC with all-regenerated catalyst. This
strategy for the on-purpose process employed in the production may result in lower levels of
production of FCC propylene will of olefins include a higher severity conversion and selectivity to light
help meet approximately 5% of the operation, recracking of cracked olefins.
annual growth rate in worldwide material and partial catalyst recycle. A
demand for propylene.1 high severity operation is achieved by Catalyst variables
Early attempts to increase a high reaction temperature, with or Since the 1960s, the refining industry
production of light olefins from the without a higher residence time. The has used various X and Y zeolites as
FCCU were based primarily on general concept for a higher severity the primary cracking catalyst in FCC.3,4
process variables, but the poor operation is to overcrack (beyond the Benefits of greater stability and better
selectivity of this approach resulted in maximum gasoline mode) and selectivity quickly led to the exclusive
excess production of dry gas and coke. produce increased quantities of light use of Y zeolites. The phase-out of
By the 1970s, researchers found that olefins.2 The length of contact time lead in fuels convinced researchers to
non-Y zeolites could also co-produce depends on the type of catalyst seek alternative routes to increase
light olefins (C2= to C5=), often at the employed. A longer contact time gasoline octane. Several versions of Y
expense of gasoline. Table 1 shows the results in excessive production of dry zeolites were used, and these are listed
chronology of development for gas and coke, and may also result in in Table 2.
catalysts and additives to enhance the reduced selectivity for light olefins Many methods were applied to
production of light olefins in FCCUs. due to hydrogen transfer reactions. dealuminate Y zeolite in order to
This article discusses the growth of A high severity operation with a balance activity, stability, gasoline
on-purpose production of light olefins short contact time overcomes the yield and octane. The use of Y zeolite
for increased production of olefins increased their reliance upon ZSM-5, Table 3
focused on Ultrastable Y (USY), to the point where it is now used in
achieved mainly through its reduced almost 20% of FCC capacity be easily achieved. This approach also
zeolite unit cell size and decreased worldwide. This approach has proven does not offer the flexibility to change
framework Al content.5,6 At constant to be a relatively inexpensive route the percentage of ZSM-5 in the total
conversion, USY catalysts yield more to propylene. catalyst inventory in the event of
C3-C4 olefins, higher octane gasoline, ZSM-5 can be used as a separate changes in feedstocks or fluctuations
and less gasoline and coke. One additive or as an integral part of the in market demand.
patent7 showed that the olefin yield FCC catalyst. Each approach has its The generally accepted mechanism
reached a maximum at a unit cell size benefits and drawbacks. Since the two for ZSM-5’s utility is the secondary
of 24.15–24.20 Å. Figure 1 shows the conversion of heavier gasoline olefins
olefin yield as a function of unit cell
size. Unfortunately, USY is less active
The process uses to lighter (C3 and C4) olefins as well
as isobutane.10,11,12 The gasoline
and stable than its REY counterpart. a catalyst that is paraffins have been shown to be 100-
RE-USY can achieve benefits similar fold less reactive than the olefins.13
to USY, but with about 35% higher selective in cracking Feedstock plays a key role in the
activity than USY.8 abundance of gasoline olefins. For
Currently, the popular approach to molecules of different example, highly paraffinic crudes
olefin production is the use of ZSM-5
additive.s ZSM-5 was first explored
shapes and sizes to such as Minas are the most responsive
to ZSM-5, while aromatic crudes such
as a stand-alone FCC catalyst, but yield light olefins as San Joaquin are significantly less
was found to be lacking in conversion effective for octane boost and olefin
activity — not surprising for a zeolite production.
of medium pore size. It was later zeolites (Y and ZSM-5) age at different
proved that ZSM-5 enhances gasoline rates, the separate additive method Indmax FCC (I-FCC) process
octane when used as an additive to can adjust better for this effect. The Indmax process, developed by
the main FCC catalyst, due to the However, the additive can build up in Indian Oil Corporation (IOCL), is a
ability of ZSM-5 to produce more the FCC inventory to the point where breakthrough in FCC technology for
olefins. this dilution can reduce the overall converting heavy feeds, including
While early use of ZSM-5 focused conversion performance of the catalyst residue, to light olefins.14 This process
on octane enhancement, the use of mix. Using the integral, single particle overcomes the drawbacks or
larger quantities of ZSM-5 for on- approach, Y zeolites need to have limitations of just adding ZSM-5.
purpose propylene production started some extra activity — so-called The Indmax process employs a riser
in the 1990s. Refiners have since activity giveaway — which may not reactor system along with a catalyst
stripper and catalyst regenerator, just
like a conventional FCCU. The
process uses a proprietary catalyst
# formulation that is very selective in
# cracking molecules of different shapes
and sizes to yield high quantities of
# n # OLEFINS $ WT
light olefins.
The catalyst formulation is unique
and very different from what has
previously been used in FCC or RFCC
operations. This approach provides
the flexibility to tailor the formulation
5NIT CELL SIZE Í
to meet the challenges of market
fluctuations in feedstock properties or
Figure 1 Incremental olefin yields for various USY catalysts product demand. The catalyst