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Naphtha cracking for light olefins

production
As an alternative to steam cracking, an FCC-type process provides on-purpose
production of propylene
Michael J Tallman and Curtis Eng KBR
Sun Choi and Deuk Soo Park SK Energy

nnual worldwide growth in


the demand for propylene is
expected to exceed 5% over
the next several years. Steam crackers currently produce approximately
60% of the worlds propylene as a
by-product of ethylene production.
The amount of propylene available
to be produced, however, is
limited to a typical weight ratio of
approximately 0.4 to 0.6 parts of
propylene per part of ethylene, and
only when cracking heavier feeds
such as naphtha and gas oil. The
balance of propylene is primarily
supplied from refinery sources,
mostly as a by-product from FCC
units producing fuels (gasoline and
diesel).
Since the ethylene market is
expected to grow at a slower pace
than that of propylene, and since
many of the new steam crackers
being built utilise ethane as a feedstock (mostly in the Middle East),
which does not produce any
propylene, propylene supply from
ethylene expansion is not expected
to meet demand. Similarly, FCC
operations are driven by fuel
demands, and new FCC units will
not fill the demand either, although
some refiners will gravitate toward
higher severity operations to
increase production and fill a
portion of the need. Therefore, new
sources of propylene will be needed
to meet expected future demand.

Catalytic processes for propylene

Currently, steam cracking and


refinery operations account for
approximately 94% of the propylene produced today. Refinery FCC
units can boost propylene production through the use of catalyst

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Assessment approach and date of sample


Process
Feed
Comments
Commercialised
Superflex
C4-C8 olefinic feeds


2nd and 3rd units licensed
Advanced Catalytic Olefins (ACO) Paraffinic naphtha, light distillates
Catalyst from SK


Demo unit in 2010
Maxofin
Gas oil or resid
High-severity FCC

Table 1

additives and by higher severity


operations.
KBR has a suite of technologies
that target propylene as a primary
product; the technology of choice is
dependent on the type of feed available. These include Superflex
technology, a commercialised proc-

Currently, steam
cracking and
refinery operations
account for
approximately 94%
of the propylene
produced today
ess
originally
developed
by
LyondellBasell for increasing propylene production from olefinic
by-product streams from steam
crackers or refinery processes;
Maxofin, a high-severity FCC process
for
increased
propylene
production from traditional refinery
sources such as gas oils and resides;
and the Advanced Catalytic Olefins
(ACO) process for enabling increased
propylene production from straight-

run paraffinic feeds. This article will


focus primarily on the ACO process.

Features of KBR FCC

KBRs catalytic olefins processes,


such as ACO, utilise hardware similar to the companys refinery FCC
units. These units catalytically crack
heavy feeds such as gas oil and
resid in a riser to lower molecular
weight products, such as gasoline,
diesel and kerosene.
The reactor (converter) comprises
four sections:
Riser/reactor, where the cracking
reactions take place in the presence
of catalyst
Disengager, where catalyst is
separated from product gas through
the use of cyclones
Stripper,
where cracked gas
contained in catalyst pores is
removed via stripping with steam
or nitrogen and routed with the
other product gas
Regenerator, where coke formed
on the catalyst during the cracking
process is removed by combustion
with oxygen, supplying heat of
reaction for the cracking process.
Although mechanical modifications to KBRs FCC system are
made to accommodate the particular operating conditions for ACO,
the functionality is not changed.

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Figure 1b KBRs
proprietary
closed cyclone
enhances yields

Figure 1a The KBR Orthoflow converter,


a stacked, inline reactor and regenerator,
with two risers

Figure 1 FCC unit

Note that no feed pretreatment is


required because of the nature of
the feed utilised and the catalyst
system
employed.
Accessory
systems for the reactor are standard
FCC systems and include catalyst
storage, air supply, flue gas
handling and heat recovery.

The feed is introduced at the


bottom of the riser and mixed with
hot, regenerated catalyst. The feed
is vapourised and the reactions take
place as the feed gas and catalyst
flow upward in the riser. At the
end of the riser, the product gas
and catalyst are separated in
cyclones, housed in the disengager.
The catalyst is then routed to the
stripper, where product gases still
entrained in the catalyst pores are
stripped with steam or nitrogen
and routed with the reactor effluent. Stripped catalyst is then routed

Capacity

Ethane

Propane

Butane

Naphtha

Gas oil

Others
Source: CMAI

Figure 2 World ethylene production by feedstock

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Figure 1c The third-stage separator


reduces catalyst fines emissions

to the regenerator, where air is


introduced and coke that has
formed on the catalyst during the
cracking operation is burned, regenerating the catalyst for reuse in the
riser and supplying the heat of
vapourisation and heat of reaction
in the riser. Accessory systems for
the FCC unit include air supply,
flue gas handling, and heat recovery and catalyst storage. Reactor
overheads are typically routed to
the primary fractionator and subsequent product separation and
recovery.
KBRs FCC units use a stacked
configuration known as Orthoflow.
In this configuration, the disengager
is stacked above the regenerator
rather than side-by-side as with
other designers units. The advantages of the Orthoflow configuration
are several: first of all, the plot
space required is much smaller for
this configuration compared to the
side-by-side unit. Foundation and
structural costs are also reduced.
The
Orthoflow
configuration
enables the unit to be fabricated
and dressed off-site and set into
place with one lift, saving on
construction costs and requiring
less welding in the field. The stripper is submerged within the
regenerator, which reduces the
vertical height of the unit and thus
the cost. A schematic of a typical
FCC unit is shown in Figure 1.
There are several other features of
KBRs FCC reactor system that can
also be used in the ACO process,
including the dual riser, closed
cyclones and third-stage separator:
Dual risers The use of dual risers

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was quite common during the early


stages of FCC development. The
primary reason for dual risers at
that time was one of scale-up; that
is, to design commercial risers that
had similar flow characteristics as
tested in the pilot plant. For several
process reasons, dual risers can be
used in ACO and Maxofin
applications
Closed cyclones Closed cyclones
minimise the residence time of
hydrocarbon vapour and catalyst in
the disengager, thereby eliminating
post-riser thermal and catalytic
cracking. Less valuable products
are destroyed, leading to more
valuable products
Third-stage separator In regions
where there is a stringent requirement
to
control
particulate
emissions, the third-stage separator
has proven to be effective.

ACO process
Why straight-run paraffinic feeds?

Naphtha is the predominant feed


for steam crackers, as more than
half of the ethylene currently
produced worldwide is derived
from cracking naphtha feed (see
Figure 2).
However, propylene production
by steam cracking these feeds is
limited to 0.40.6 parts by weight
per part of ethylene. ACO produces
greater quantities of propylene and
total light olefins, and nearly the
same quantity of ethylene, and uses
the most common feedstock available: straight-run naphtha (see
Figure 3). Thus, ACO should be of
interest to producers who already
use naphtha feeds to produce
ethylene.
The predominance of naphtha
feed is particularly the case in
Europe and Asia. In Western
Europe, approximately 72% of the
ethylene produced is derived from
naphtha feedstock, while in Central
Europe and China the figure is
approximately 80% from cracking
naphtha feed.

ACO performance

Figure 3 shows a comparison of the


yields obtained from steam cracking and from ACO.
The ACO process makes about
1525% more ethylene plus propyl-

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ene on a relative basis, depending


on the operating conditions. In the
example shown in Figure 3, the
total ethylene plus propylene product yield is about 17% higher than
from the steam cracker. Further, the
ACO process has a higher concentration of BTX in the gasoline
fraction, resulting in about 2025%
higher absolute aromatics yield
from the ACO process.
One means of comparing the
process to a steam cracker is to
compare the cost of production
(COP) of ethylene. In this type of
analysis, the feed and operating
costs are offset by the by-product
revenue. Other costs include indirect and overhead costs, and
depreciation (10%) and profit (10%)
are added to arrive at an overall
COP. Based upon a constant feed to
either a steam cracker or an ACO
unit, the ACO process is favoured
by a lower COP of about $90/t of
ethylene.

Reactor

The ACO process combines the


Orthoflow fluidised catalytic cracking
reactor
system
with
a
proprietary catalyst developed by
SK Energy in Korea, which selectively converts naphtha feed to
large quantities of propylene and
ethylene. The ACO reactor system
includes the Orthoflow configuration, the dual riser, closed cyclones,

100

75

50

25

Steam
cracker
Ethylene

Propylene

Gasoline

Other

Figure 3 Comparison of naphtha cracking


yields

third-stage separator, patented catalyst well for continuous fuel firing,


and patented catalyst removal
system (see Figure 4).
One significant advantage of the
ACO converter is economy of scale
regarding olefins capacity. The
maximum commercially demonstrated capacity in a single-cell
liquid-feed pyrolysis furnace is
approximately 200 000 t/y of ethylene, or approximately 300 000 t/y
of total olefins. By contrast, the

To flue gas system

Catalyst
fines

ACO
orthoflow
reactor/
regenerator

Fresh feed

ACO

CW

Reactor
effluent
to recovery

Fuel oil
Steam

Oil wash
tower

BFW
Catalyst storage
and handling

Recycle

Regeneration
air

Figure 4 ACO reactor system

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89

Recycle to reactor
Mix C4/C5

Non-aromatic
C6+
Light gas

Cold
box

1-2
Drying
Treating

C3 ref.

C2 ref.

Ethylene

Quenched
gas

Dehexanizer

Depentanizer

C3 splitter

C2 splitter

Deethanizer

Demethanizer

Depropanizer

Propylene

BTX+
Ethane/propane

Figure 5 Typical ACO flow scheme

worlds largest ACO reactor (if


similarly sized to the worlds largest commercial FCC unit today) can
make about 45 times more olefins,
or up to 1.5 million t/y of ethylene
and propylene in a single reactor.
Although in many ways the ACO
reactor system is very similar to the
refinery FCC unit, there are some
features that highlight the differences between a light olefins cracker
and a heavy oil refinery cracker.
Some of these features, all of which
are commercially demonstrated,
include:
Quench exchanger Reactor overheads are cooled similar to a
cracking furnace, generating highpressure steam and thus improving
the energy efficiency of the process.
This type of exchanger is not possible in an FCC unit, where the large
amount of heavy fuel oil by-product would lead to severe fouling
Heat balance The ACO process is
endothermic and, since the feeds
are light, the amount of coke
produced on the catalyst is insufficient to supply the necessary heat
of reaction. As a result, to maintain
heat balance, fuel must be imported
into the reaction system. KBRs
catalyst well design with continuous fuel firing has now been
demonstrated commercially.
Catalyst/hydrocarbon
separation
Although the cyclones are quite

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efficient, invariably some catalyst


fines will carry over with the reactor effluent cracked gas. KBRs
catalyst fines removal system has
been commercially demonstrated
and
is
applicable
to
ACO
technology.

Recovery scheme

The ACO process produces both


polymer-grade ethylene and propylene. Much of the process flow
scheme is similar to typical olefins
plant recovery sections. However,
there are some distinctive features.
For example, there are trace impurities that must be removed, such as
nitrogen oxides, oxygen and other
trace impurities, by virtue of the
FCC-type reactor. These and other
issues are addressed in the ACO
process flow scheme, which features
a front-end depropaniser (see
Figure 5).

ACO catalyst

The key to the performance of the


ACO process is the catalyst that has
been developed by SK Energy
specifically to convert naphtha with
high yields of propylene and ethylene in a fluid-bed-type reactor. As a
result of seven years collaboration
with Korea Research Institute of
Chemical Technology, the latest
ACO catalyst exhibits higher
mechanical
and
hydrothermal

stability, as well as light olefins


selectivity.
SK Energys R&D facility located
in Daejeon, Korea, has fully covered
the development programme from
laboratory catalyst preparation to
pilot tests. KBR also owns an FCC
pilot plant in its Technology
Development Center in Houston,
Texas, and was able to replicate SK
Energys pilot plant results via
independent tests. This KBR FCC
pilot plant is the same one used by
KBR in the development of
Superflex technology, another FCCtype
process
for
propylene
production. Yields obtained at the
first commercial Superflex facility
built by Sasol in Secunda, South
Africa, are similar to if not slightly
better than those expected according to the pilot studies. Thus, the
pilot plant results obtained by SK
Energy and KBR are expected to be
directly indicative of the results that
would be obtained in a commercial
ACO unit.
In accordance with the startup
schedule of the ACO demonstration
unit, commercial supply of catalyst
is also in progress with an FCC
catalyst company as a form of toll
manufacturing. Based on SK
Energys recipe, more than a years
scale-up tests have been performed
to finalise a commercial recipe, and
demonstration unit operation in

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2010 will be another opportunity to


confirm the performance of commercially manufactured catalyst.

Commercialisation

Plans are currently under way to


integrate a demonstration-sized
ACO converter system with SKs
existing facilities in Ulsan, Korea,
with
anticipated
mechanical
completion in August 2010. Thus,
SK Energy will be the first commercial adopter of the ACO process.
KBR completed basic engineering
for this demonstration unit in 2008.
Since that time, SK Energy has been
progressing the detailed engineering for the project and procuring
the equipment on a worldwide
basis.
The scope of work for the ACO
demonstration unit includes the
installation of the converter system,
fresh/spent catalyst handling facilities and reactor effluent heat
recovery facilities. The effluent from
the reactor will be sent directly to
an existing RFCC main column
section and the flue gas from the

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regenerator will be sent to the


existing RFCC CO boiler system.
The combustion air needed in
the regenerator is also supplied
from the existing RFCC main air
blower.
Once in operation, naphtha that
is fed to SK Energys ethylene
crackers will be fed to the ACO unit
and the effluent processed in the
existing refinery. The unit will be of
sufficient capacity to demonstrate
the anticipated conversion and
yields of the ACO reactor system.

Summary

Steam cracking and refinery sources


will not keep pace with future
demand for propylene, and so onpurpose technologies will become
more prevalent. The ACO process
uses straight-run paraffinic feeds
and cracks them to produce more
total olefins than conventional
pyrolysis with P/E ratios up to 1/1.
SK Energy is building the worlds
first ACO unit, which will come
into operation in the final quarter
of 2010.

Michael J Tallman is Manager, Catalytic


Olefins Technology, with KBR, responsible
for developing, marketing and licensing KBR
proprietary catalytic technologies for the
production of olefins. He has a BS in chemical
engineering from Rose-Hulman Institute of
Technology, Terre Haute, IN.
Email: michael.tallman@kbr.com
Curtis N Eng is Director for Olefins with
KBR, responsible for marketing, selling, and
developing KBR proprietary technologies for
the production of olefins. He has a masters in
chemical engineering from the University of
Massachusetts, a BS in chemical engineering
from the University of California.
Email: curtis.eng@kbr.com
Sun Choi is Vice President of the Catalyst &
Process R&D Center of SK Energy, in charge
of developing, marketing and licensing SKs
proprietary process and catalytic technologies
in oil refining and the chemical industry. He
has a BS in chemical engineering from Korea
Advanced Institute of Science and Technology,
Seoul. Email: schoi@skenergy.com
Deuk Soo Park is Senior Manager of the
Chemical Process Lab in SK Energys Catalyst &
Process R&D Center, responsible for developing
and applying SKs proprietary process and
catalytic technologies for the production of
olefins. He has a BS in chemical engineering
from Chungang University, Seoul.
Email: parkds@skenergy.com

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