AIChE PAPER 74b

ADVANCED CATALYTIC OLEFINS (ACOTM): FIRST COMMERCIAL

DEMONSTRATION UNIT BEGINS OPERATIONS

Michael J. Tallman
Manager, Catalytic Olefins Technology
Kellogg Brown & Root (KBR) LLC
Houston, Texas

Curtis N. Eng
Director, Olefins Technology
Kellogg Brown & Root (KBR) LLC
Houston, Texas

Sun Choi
Senior Vice President, Catalyst & Process R&D Center
SK Innovation Global Technology
Daejeon, Korea

D. S. Park
Principal Researcher
SK Innovation Global Technology
Daejeon, Korea

Prepared for Presentation at the 2011 Spring National Meeting

Chicago, Illinois, March 14-17, 2011

AIChE and EPC shall not be responsible for statements or opinions contained in papers or
printed in its publications

KBR Internal Reference Paper 2235

 ADVANCED CATALYTIC OLEFINS (ACOTM): FIRST COMMERCIAL
DEMONSTRATION UNIT BEGINS OPERATIONS

Michael J. Tallman
Manager, Catalytic Olefins Technology
Kellogg Brown & Root (KBR) LLC
Houston, Texas

Curtis N. Eng
Director, Olefins Technology
Kellogg Brown & Root (KBR) LLC
Houston, Texas

Sun Choi
Senior Vice President, Catalyst & Process R&D Center
SK Innovation Global Technology
Daejeon, Korea

D. S. Park
Principal Researcher
SK Innovation Global Technology
Daejeon, Korea

Abstract: With the number of new ethane-based crackers coming on line in the next few
years, it is anticipated that the traditional source of nearly two-thirds of the world’s propylene,
steam crackers, will fall short of demand. Thus, there is great interest in new propylene-on-
purpose technologies. One such technology is the Advanced Catalytic Olefins (ACOTM)
process, an FCC-type process which cracks straight run feeds such as naphtha (already the
feed source for approximately half of the world’s ethylene production) to large quantities of
propylene and ethylene. Compared to a traditional steam cracker, ACO produces significantly
more propylene (typical P/E production ratio is approximately 1:1) and more total olefins at
lower energy consumption and CO2 footprint. A description of the ACO process is provided,
along with an economic comparison to steam cracking when processing a typical naphtha
feed. A description of the ACO Demonstration Unit constructed by SK Global Chemical
(formerly SK Energy) at its site in Ulsan, Korea, the first commercial demonstration of ACO
technology, is also provided, including a summary of early operations which began in 4Q10.
 ADVANCED CATALYTIC OLEFINS (ACOTM): FIRST COMMERCIAL DEMONSTRATION
UNIT BEGINS OPERATIONS

Michael J. Tallman, KBR

Curtis N. Eng, KBR
Sun Choi, SK Innovation
D. S. Park, SK Innovation

Propylene is the second largest petrochemical used in the world by tonnage, with
demand of approximately seventy million metric tons per year. A majority of the propylene is
used to produce polypropylene, and, driven largely by increased usage of polypropylene,
annual worldwide growth in propylene demand is expected to approach 5% over the next
several years. Steam crackers currently produce approximately 60% of the world's propylene,
as a byproduct to ethylene production. However, steam crackers produce propylene by-
product only when cracking LPG and heavier liquid feeds such as naphtha and gas oil, and
even then production is limited to about half that of ethylene (typical weight ratio of
approximately 0.4 to 0.6 parts of propylene per part of ethylene). The balance of the world’s
propylene is primarily supplied from refinery sources, mostly as byproduct from FCC units
producing fuels (gasoline and diesel).

The ethylene market is expected to grow at a slower pace than that of propylene, and
since much recently added and planned new ethylene capacity utilizes ethane as a feedstock,
which does not produce any propylene, propylene supply from ethylene expansion will not
meet demand. Similarly, FCC operations are driven by fuel demands and, although some
refiners will gravitate toward higher severity operations to increase propylene production and
fill a portion of the need, new FCC units will not fill the demand either. Therefore, new
sources of propylene will be necessary to meet the expected future demand.

Unlike many such processes which have recently come into the marketplace for
propylene production, the Advanced Catalytic Olefins (ACOTM) process catalytically (rather than
thermally) cracks widely available, straight run material such as naphtha, to produce not only
increased overall quantities of olefins, but also substantially increased quantities of propylene.
The ACO process is similar to another commercially proven, catalytic process for olefins
production offered by KBR (and originally developed by LyondellBasell) known as
SUPERFLEXTM.

The Advanced Catalytic Olefins (ACOTM) Process

Why Naphtha Feed?

Naphtha is the predominate feed for steam crackers, as approximately half of the
ethylene currently produced world-wide is derived from cracking naphtha feed. In certain
regions of the world, naphtha cracking represents a significantly higher percentage of ethylene
production:

Figure 1
Ethylene Production from Naphtha

90
80
70
60
50
Percent
40
30
20
10
0
South W. Europe Central Baltic / CIS India NE Asia SE Asia
America Europe (incl.
China)

Source: CMAI

Steam cracking, or pyrolysis, the standard process for ethylene production used in the
petrochemical industry since its inception more than sixty years ago, has many drawbacks,
however, as follows:

• Cracking reactions occur at very high temperatures, typically greater than 850oC and
approaching 900oC for high conversion gas cracking
• Propylene production is limited to 0.4-0.6 parts by weight per part of ethylene
• Furnaces must be periodically removed from service to remove the coke which forms in
the furnace coils as a result of the high process temperatures
• Pyrolysis is an energy-intensive process, and greenhouse gas emissions are high

The ACO process is an alternative process which catalytically cracks naphtha feed rather
than thermally, and as such it addresses all of these drawbacks while also producing increased
total light olefins yields at much higher propylene-to-ethylene ratios.

While many of the new “propylene-on-purpose” technologies which have come into the
market in recent years use costly, niche, or less-prevalent feeds, the ACO process has been
developed specifically to use the most common feed currently used for olefins production:
naphtha.
The ACO Reactor

The ACO process combines a KBR fluidized catalytic cracking (FCC) reactor system with
a proprietary catalyst developed by SK Global Chemical in Korea which selectively converts
naphtha feed to large quantities of propylene and ethylene. The reactor section scheme is
shown in Figure 2:

Figure 2
TM
ACO Reactor System

To Flue
Gas System Reactor
Effluent
To Recovery
Catalyst Steam Fuel
Fines Oil
BFW
Oil Wash
ACO Tower
Orthoflow
Catalyst Storage
Reactor /
And Handling
Regenerator

Fresh Feed Recycle

Regeneration
Air

Similar to any refinery FCC, the ACO reactor (converter) is comprised of four sections:
riser/reactor, disengager, stripper and regenerator. The feed is introduced at the bottom of
the riser and mixed with hot regenerated catalyst. The feed is vaporized 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 then
flows to the regenerator, where air is introduced and coke which has formed on the catalyst
during the cracking operation is burned, regenerating the catalyst for re-use in the riser.
Accessory systems for the 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.

As can be seen in Figure 2 KBR’s FCC design uses a configuration known as

OrthoflowTM, in which the Disengager is stacked directly above the Regenerator. 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 type of unit. Foundation and
structural costs are also reduced. The Orthoflow configuration allows the unit to be fabricated
and dressed off-site and set into place with one lift, saving on construction costs and with less
welding required in the field. The stripper is submerged within the regenerator which reduces
the vertical height of the unit and thus the cost.

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 nearly 200 kta ethylene, or approximately 300 kta of total olefins. By
contrast, if sized similarly to existing large commercial FCC units the ACO reactor can be
designed to make about 5-6 times more olefins, or up to 1,700 kta ethylene + propylene
within a single reactor.

Relative to the refinery FCC, ACO employs some unique and innovative design aspects
which address the fact that the light straight run feeds used in ACO are so much lighter than
refinery FCC’s:

• Heat Balance – similar to refinery FCC the ACO (and the SUPERFLEX) process is
endothermic. A typical refinery FCC uses coke formed on the catalyst as the heat
source to maintain the unit’s heat balance. In ACO, however, the feed is substantially
lighter and far less coke is formed. As such, to maintain heat balance, fuel must be
imported into the reaction system. KBR’s patented (US#7,153,479) catalyst well design
with continuous fuel firing has now been commercially proven at the Sasol
SUPERFLEXTM unit and is applicable to both ACO and SUPERFLEX technology.

• Catalyst/Hydrocarbon Separation – Although the cyclones used in the disengager are

very efficient, invariably some catalyst fines will carry over with the reactor effluent
cracked gas. In refinery FCC these catalyst fines concentrate into the fuel oil by-
product stream (slurry oil). However, with ACO the quantity of fuel oil produced is
much smaller, and thus an alternative means of dealing with catalyst fines is necessary.
KBR’s patented (US#7,011,740) catalyst fines removal system has now been
commercially demonstrated and applicable to both ACO and SUPERFLEX technology.
The ACO Recovery Scheme

The ACO process produces both polymer grade ethylene and propylene. The process
flow scheme is almost identical to KBR’s typical ethylene plant recovery section design;
however, there are some unique features. For example, there are trace impurities present in
the cracked gas, such as nitrogen oxides, oxygen, and other trace impurities, by virtue of the
FCC-type reactor that must be removed to meet the polymer grade product specifications.
These and other issues are addressed in the ACO process flow scheme, which features a front
end depropanizer, same as KBR’s current ethylene plant design, as shown below:

Figure 3
Typical ACO Flow Scheme

Non-aromatic
Recycle to Reactor Cold Mix C4/C5 C6+
box
Light gas
C3 C2
Ref Ref
Ethylene
1-2 Drying 3
C2 C3 Propylene
Treating
Quenched Splitter Splitter
Gas
Dehex-
Deprop- anizer
anizer
BTX
Demeth- Deeth- Depent- +
anizer anizer anizer
Ethane/
Propane

ACO Performance

Figures 4 and 5 below compare the yields obtained from steam cracking and from ACO
for two grades of naphtha:
 Figure 4
Comparison of LSR Naphtha Cracking Yields

100

Wt% 75

Other
50
Gasoline
Propylene
Ethylene
25

0
Steam ACO
Cracker

Figure 5
Comparison of FRN Cracking Yields

100

75
Wt%

Other
50
Gasoline
Propylene
Ethylene
25

0
Steam ACO
Cracker
 The ACO process makes about 10-25% more ethylene plus propylene on a relative
basis, depending on the operating conditions and feed quality. In the examples above, the
total ethylene plus propylene product yields are about 25% and 11% higher than the steam
cracker for LSR and FRN, respectively. However, as clearly illustrated from the red portions of
the graphs above the propylene yield is much higher, with a resultant P/E ratio of
approximately 0.9. Further, the ACO process has a higher concentration of BTX in the
gasoline fraction, resulting in about 50% higher absolute aromatics yield from the ACO
process.

The ACO process is also advantageous over the steam cracker from an energy
consumption, and thus greenhouse gas emissions, perspective. This is an important
consideration given the current increased focus on CO2 emissions. The primary benchmark for
energy consumption in the industry is “specific energy”, or the overall energy consumed in the
plant per unit of product made. Specifically for olefins plants, the major ISBL utilities including
fuel, steam import / export and electrical power are converted to a fuel equivalent (based on
typical boiler and power generation efficiencies) and divided by the production rate. On this
basis, the specific energy per unit of olefins produced for ACO is about 10% and 7% lower
than steam cracking for the LSR and FRN cases above, respectively.

All of this leads to an improvement in the overall economics for naphtha cracking.
Based on current values for naphtha and the various products, an ACO unit cracking the same
quantity of naphtha as a new steam cracker designed to produce 700 kta of ethylene at a 0.5
P/E production ratio has a gross margin improvement of $115MM/yr and $111MM/yr for the
LSR and FRN cases above, respectively. This results in much improved IRR and profitability of
the plant.

ACO Commercialization

SK Global Chemical is a division of SK, a Korean-based conglomerate with 2009 sales

over US$29 billion. SK Global Chemical owns and operates two naphtha crackers in Ulsan with
a total ethylene capacity of about 800,000 MTY and its sister company, SK Energy, also
operates several refinery units in Ulsan including two FCC’s.

SK Global Chemical has recently begun commercial operations in a new demonstration-

sized ACO converter system integrated with SK’s existing facilities in Ulsan. This unit began
operations in 4Q10 and thus SK Energy has become the first commercial adopter of the ACO
process.

KBR completed basic engineering for this demonstration unit in 2008. The unit has a
capacity of 40 kta of olefins (ethylene plus propylene); thus, the unit is of sufficient capacity to
demonstrate the anticipated conversion and yields of the ACO reactor system. During 2009
and 2010, SK Global Chemical completed the detailed engineering for the project and procured
the equipment on a world-wide basis. The ACO reactor system was fabricated at a shop in
Ulsan, Korea and arrived on site and lifted into place 2Q2010, with mechanical completion of
the unit in 3Q2010.

The ACO demonstration unit includes the installation of the ACO converter system,
fresh / spent catalyst handling facilities and reactor effluent heat recovery facilities. The
effluent from the reactor is sent directly to the existing #2 RFCC Main Column section and the
flue gas from the ACO regenerator is sent to the existing #2 RFCC CO Boiler system. The
combustion air needed in the ACO regenerator is also supplied from the existing #2 RFCC
Main Air Blower. A recent photograph of the unit is shown below:

ACO Commercial Demonstration Unit

Ulsan, South Korea

To date, operations of the Demonstration Unit have met expectations. Various grades of
naphtha are being fed to the ACO unit during its early operations, and process variables are
being varied to determine the impact. The effluent is processed in the existing refinery. Early
yield data is promising, with performance of the Demonstration unit cracking LSR consistent
with pilot plant results, as shown in the figure below (in which the actual yields obtained in the
commercial unit are added to those shown from the earlier comparison in Figure 4).

Figure 6
LSR Naphtha Cracking Yields

100

75

Other
50
Gasoline
Propylene
25 Ethylene

0
Steam ACO Demo
Cracker Unit
Ethylene yield is slightly less than the pilot plant tests but propylene yield is slightly better,
with overall olefins yield comparable to expectations per the pilot plant tests.

FRN is now being fed to the unit, and while full analysis of the yields for FRN is underway and
not yet complete the expectation is that performance will be similar to that shown for LSR
naphtha.
Who should consider ACO?

While the economics described above are based on comparing ACO technology with
steam cracking technology for a new grassroots facility, ACO can also be used as part of a
revamp strategy by current producers. Based on the performance described herein, ACO
should be of interest to producers who already use naphtha feeds to produce ethylene or who
have desire to expand capacity using naphtha. ACO also represents an alternative to
producers who may be facing extensive furnace revamps or upgrades for efficiency or
environmental reasons. Rather than replace old, high OPEX pyrolysis furnaces with new
furnaces some or all can be replaced with a new ACO reactor as part of a revamp project for
increased propylene production.

Summary

Steam cracking and refinery sources will not keep pace with future propylene demand
and so “on-purpose” technologies are becoming more prevalent. KBR offers several such
technologies, with the use dependent on the type of feed available. The ACO process uses
commonly available, straight run paraffinic feeds and cracks them to produce more total
olefins than conventional pyrolysis, with P/E ratios near 1/1 and at lower energy consumption.
SK Global Chemical successfully began operating the world’s first commercial ACO unit in
Ulsan, Korea, which came into operation in 4Q2010, with all performance expectations met to
date.