Metathesis: refinery and ethylene plant

applications
Integration of the metathesis process in FCC units and steam crackers is a low
capital cost way of increasing propylene production and reducing C4s product

Ronald M Venner and Stephen I Kantorowicz

ABB Lummus Global

T
he future of the olefins industry will be
shaped by product flexibility, low capital
investment and energy efficiency of larger
capacity plants. As propylene demand continues
to grow, the impact of integrating proprietary
olefins conversion technology (OCT) in existing
or grassroots ethylene and/or refinery applica-
tions becomes evident. OCT implementation
results in improved overall economics through
low capital investment, excellent energy effi-
ciency and improved gross margins.
OCT provides an excellent vehicle for varying
product slate to cope with fluctuating demand
of downstream operations. For example, in Figure 1 World propylene sources
ethylene applications, propylene-to-ethylene
ratios can increase from the typical 0.5 ratio to • Downstream product prices (particularly poly-
greater than 1.0. In refinery applications, FCC ethylene and polypropylene)
fuel gas and excess butylenes are converted to • Butadiene demand
propylene. • Gasoline prices and plant operating rates.
The demand for ethylene and propylene light As shown in Figure 1, the majority of propyl-
olefins will increase at different rates. Global ene is currently produced in steam crackers and
propylene demand is forecast to increase 6 to 8 FCC units. In these processes, propylene is
per cent per year, which exceeds the global ethyl- produced as a byproduct of ethylene production
ene demand growth forecast of 4 to 6 per cent or transportation fuels. Historically, FCC units
per year. The four commercially proven routes to balanced the propylene demand fluctuations by
propylene production are: varying severity. The other technology routes will
• Steam cracking start playing a greater role in fulfilling the
• Fluid catalytic cracking (FCC) increasing demand for propylene. Propylene via
• Propane dehydrogenation propane dehydrogenation is typically considered
• Metathesis of ethylene and butylenes. in areas where there is ample low-cost propane
Some of the reasons for the dynamic and available as feedstock.
constantly fluctuating propylene and ethylene Metathesis is emerging as a low capital/low
demand and pricing seen throughout various energy production option that can stand alone or
regions of the world include: be integrated with FCC units or steam crackers
• NGL and crude prices for improved flexibility and performance. With

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 Figure 2 OCT process flow schematic
the demand for propylene outpacing the demand
for C4s, the metathesis process offers the poten-
tial for significant improvement in a steam
cracker’s or FCC unit’s operating margins by
reducing C4 product and increasing propylene
production.
Olefins conversion technology
Proprietary OCT converts normal butylenes and
ethylene to polymer grade propylene via metath-
esis. The two main equilibrium reactions taking
place are metathesis and isomerisation.
Propylene is formed by the metathesis of ethyl-
ene and butene-2, and butene-1 is isomerised to
butene-2 as butene-2 is consumed in the metath-
esis reaction.
In addition to the main reactions, numerous
side reactions between olefins also occur.
Ethylene feed can be polymer grade ethylene
or a dilute ethylene stream. Any saturated hydro-
carbons, such as ethane and methane, do not
react. The technology can be used with a variety
of C4 streams, including mixed C4s produced by
FCC or steam cracking or C4 raffinate from buta-
diene extraction or MTBE production. Based on
the reaction stoichiometry, three tons of propyl-
ene are produced from two tons of butylene and
one ton of ethylene.
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Figure 2 is a simple process flow diagram of
the Lummus OCT process. Fresh C4s (plus C4
recycle) are mixed with ethylene feed (plus recy-
cle ethylene) and sent through a guard bed to
remove trace impurities from the mixed feed.
The feed is heated prior to entering the vapour
phase fixed-bed metathesis reactor where the
equilibrium reaction takes place. The reactor is
regenerated in-situ on a regular basis.
As mentioned previously, the catalyst promotes
the reaction of ethylene and butene-2 to form
propylene and simultaneously isomerises butene-
1 to butene-2. The per-pass conversion of
butylene is greater than 60 per cent, with over-
all selectivity to propylene exceeding 90 per cent.
The product from the metathesis reactor is
primarily propylene and unreacted feed.
Reactor effluent is sent to the ethylene recov-
ery tower where the unreacted ethylene is
recovered and recycled to the reactor. The C2
tower bottoms is processed in the C3 tower to
produce propylene product and a C4 recycle
stream. Purge streams containing non-reactive
light material and C4s and heavier are also
produced.
Depending on the quantity of isobutylene in
the C4 feed, the unit design may include a
deisobutaniser to extend reactor run-length
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between regenerations and reduce
OCT unit throughput, resulting in an
overall lower capital cost plant. The
deisobutaniser is a catalytic distilla-
tion tower that isomerises butene-1 to
butene-2 (CDIsom) to maximise
recovery of OCT feed. The deisobu-
taniser option is evaluated on a
case-by-case basis. Ultra-high purity
propylene exceeding polymer grade
specification is produced without a
propylene fractionation system, since
the only source of propane is that
contained in the C4 and ethylene Figure 3 FCC propylene: OCT results
feeds.
OCT was originally developed by Phillips flexibility to operate at higher propylene produc-
Petroleum and was first commercialised in 1965. tion rates and recoveries. It is currently feasible
Due to the propylene demand at that time, this to double or triple FCC propylene yields by utilis-
unit processed propylene to produce ethylene ing combinations of customised catalysts, higher
and butylenes. A second unit, which is still oper- severity operation, enhanced FCC design features
ating at Lyondell Petrochemical in the USA, was and improved recovery facilities (Figure 3).
commissioned in 1985 to produce propylene. Proprietary selective component cracking
ABB Lummus Global engineered both of these (SCC) maximises olefins production from the
units. In 1996, Lummus acquired the technology catalytic cracking process. In this high olefin
from Phillips. Currently there is a unit under production mode, though the yield of gasoline
construction by Lummus for BASF Fina in the decreases, the octane number increases. As the
USA as part of the world’s largest single train yield of propylene increases, the ethylene yield
olefins plant. also increases. Ethylene recovery followed by
butylene/ethylene metathesis to propylene can
Refinery applications improve overall FCC plant economics.
In current market conditions, FCC unit profita- A low cost, low-pressure-recovery (LPR) flow
bility is significantly enhanced by the increased scheme has been patented for ethylene recovery

Figure 4 Low pressure recovery block flow diagram

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Figure 5 Refinery offgas olefin recovery: effect of propylene and ethylene Most refineries with operating
prices on IPR
in cat cracking units that does not sacrifice relia-
bility, flexibility or safety (Figure 4). In this
process, typically greater than 95 per cent of the
ethylene is recovered from the FCC offgas stream
that is normally used as fuel gas.
There are a number of offgas contaminants
that need to be removed when recovering cat
cracker ethylene; the presence and quantity of
these contaminants will vary with crude source
and FCC design and operation. Some typical
impurities and their concentration range are
shown in Table 1. The impurities are removed by
a combination of proven processing steps,
including caustic/water wash, adsorption, hydro-
genation or fractionation.
Adding the LPR unit results in simple payouts,
typically less than two years, with excellent
returns over the historical range of ethylene
prices. LPR upgrades ethylene in FCC offgas
Figure 6 Steam cracker propylene: OCT results
4 PTQ Q3 2001
Offgas impurities
Typical range
CO, mol% 0.5–1.1
H2S, ppm 50–100
Acetylene, ppm 3–100
Water –
Arsine, ppb 0–100
Mercury, ppb 0–300
Ammonia, ppb 5–10
Nitriles, ppb 0–100
Nitrogen oxide –
Table 1
from fuel value to product value.
FCCs have the infrastructure in
place for handling propylene prod-
uct but not ethylene product. So the LPR process
can also be used to recover ethylene for further
processing via metathesis with refinery C4s to
maximise propylene.
The LPR/OCT combination further improves
the economics over the LPR unit alone. Figure 5
illustrates the IRR over a range of product values
for ethylene recovery only and propylene produc-
tion via LPR/OCT. Adding the OCT to the LPR
unit increases IRR 10 to 20 per cent, even after
considering that, historically, propylene price
ranges from 0.8 to 0.85 of ethylene price. This is
because the major feed in producing propylene
is butylene, which is significantly lower in price
than either ethylene or propylene. The OCT unit
combined with FCC maximises high propylene
production flexibility.
Steam cracker applications
OCT combined with a steam cracker can
significantly vary the propylene-to-
ethylene product ratio and improve
overall plant economics. The most
recent project is the BASF Fina
Petrochemicals plant in Port
Arthur, Texas. The steam cracker
is designed to produce over
950000 tonnes/year ethylene and
over 544000 tonnes/year propyl-
ene. The OCT unit will add more
than 300000 tonnes/year addi-
tional propylene.
Typical steam crackers with
liquid feedstocks operate with a
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propylene-to-ethylene ratio range of
0.45 to 0.65, depending on cracking Material balance comparison
severity. The mixed C4 product stream
Case 1 2 3
contains butadiene, butylenes and
Case description Standalone Standalone Steamcracker
butanes. Butylenes can be reacted with steam cracker steam cracker integrated with
ethylene via metathesis to increase the Exported C4s No exported C4s an OCT unit
propylene-to-ethylene ratio. Feedstock, kta
Naphtha feed 2088 1810 2213 + 403*
If butadiene is not required as a
Products, kta
product, it can be selectively hydrogen- Methane fuel gas 389 393 437
ated to butenes to provide additional PG ethylene 750 760 760
butylene feed for metathesis. The steam PG propylene 418 418 713 + 295*
Mixed C4s 263 0 0
cracker/OCT combination can result in
Pygas 196 181 235
propylene-to-ethylene ratios exceeding Fuel oil 60 56 66
1.1 as determined by the quantity of Acid gas 2 2 2
butylenes available for conversion in Total 2088 1810 2213
the OCT unit (Figure 6).
*73% of incremental naphtha converted to propylene
Table 2 illustrates three operating
scenarios. Case 1 recovers C4s as a
mixed C4 product. This is typical of an Table 2
operation where butadiene is a desired
product for recovery. depending upon whether butadiene is recovered
Case 2 hydrogenates and recycles the C4s to as product or selectively hydrogenated to
cracking. The naphtha feed requirement is produce more OCT unit feed.
reduced. This operating scenario has become Addition of the OCT unit results in a lower cost
more popular in recent years as butadiene complex with lower specific energy consumption
demand has not kept pace with ethylene growth that in turn results in improved gross and net
rates. However, this option reduces the quantity margins for the steam cracker/OCT combination.
of hydrogen available for product sales. A more Since the OCT unit produces propylene, the
economic variation of Case 2 is to selectively steam cracker can operate at higher cracking
hydrogenate the butadiene to butylenes to severity while maintaining the same overall P/E
produce metathesis feed. ratio. The higher cracking severity processes less
This is shown in Case 3. The propylene/ethyl- feed and produces fewer byproducts, resulting in
ene product ratio increase from 0.55 for Cases 1 a smaller ethylene plant. Since the ethylene plant
and 2, to 0.94 for Case 3. This option requires is the major cost and energy component, the
more naphtha feed, but 73 per cent of the incre- overall result is that the steam cracker/OCT unit
mental naphtha feed is converted to propylene combination outperforms the low severity steam
via metathesis. The IRR improves by 3–5per
cent, depending upon product price scenarios. Naphtha steam cracker options
In addition to maximising the propylene-to-
ethylene (P/E) ratio of a steam cracker, OCT can Case 1 Case 2
also be utilised to optimise steam cracker Feedstock Naphtha Naphtha
complexes operating in the conventional P/E Naphtha severity Low High
range. P/E 0.65 0.65
Naphtha feedrate Base 2–5% lower
Table 3 illustrates different naphtha steam C3 from OCT – 15–28%
cracker options that produce an overall P/E ratio TIC Base 5–8% reduction
of 0.65. In Case 4, the P/E ratio is controlled by Gross margin Base <1–3% improvement
the cracking severity; the 0.65 P/E ratio repre- Net margin Base 2–6% improvement
Energy Base 8–9% lower
sents a typical low severity operation on naphtha BD Base 17% less
feed. In Case 5, the severity is increased and the Benzene Base 25–50% more
OCT unit is added to react butylenes and ethyl- Pygas Base -2–12% less
ene to attain the same 0.65 ratio. A range of
values is shown in Case 5 to reflect the results Table 3

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 cracker. The addition of the OCT unit to the Triolefins – The Bridge to Profitability; European Petrochemical
steam cracker improves capital and operating Technology Conference, London, 21-22 June 1999.
expenses as compared to larger plants operating 2 McCarthy F D and Krumins A E, Low Pressure Recovery of Olefins
in the traditional low severity range. from Refinery Offgases; Lummus 8th Ethylene Seminar.
3 Kantorowicz S and Shreehan M, Olefins Conversion Economics;
In addition to the advantages discussed for
Lummus 9th Ethylene Seminar.
grassroots complexes, the OCT unit can also be
4 Edwards S M, Olefins Conversion Technology; Lummus 9th
used as an effective debottlenecking tool. It can Ethylene Technology Seminar.
be applied to plants currently operating at low
severity and looking to increase capacity without
sacrificing P/E ratio, or for plants operating at
high severity and looking to debottleneck for
higher capacities and P/E ratios. Links

References More articles from: CB&I

1 Kantorowicz S I, Innovative Technologies for Capacity Expansion More articles from the following category:
and Product Flexibility of Steam Crackers; 11th Ethylene Petrochemicals
Conference, Maoming, China, 20-23 Nov 2000, Venner R M,

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