Special Edition:

Propylene
Opportunities
Technologies
Markets
A Message from the Editors
The next two to three years will see a significant growth in the demand for propylene derivatives,
particularly polypropylene, which will lead to structural tightness in the global propylene market.
Since steam cracker capacity expansion, which is tied to a lower growth rate in the demand for eth-
ylene, is forecast to lag propylene demand, the petrochemicals industry is looking to operators of
FCC processes to fill the propylene supply gap. In the short term, this will lead to opportunities for
refiners to further increase margins by using ZSM-5 based additive technologies to produce incre-
mental propylene for sale into the petrochemicals market. In the long term, a number of refiners
are considering either revamping their FCC units to operate in "petrochemicals mode" or are con-
sidering investing in grass roots "on purpose" propylene production facilities that utilize ZSM-5
based FCC catalyst technologies.

This special edition of the Catalagram focuses on the important role FCC-type processes play in
the propylene market. The lead article by Davison Catalysts describes the commercial performance
of the industrys most widely used ZSM-5 additive for enhanced light olefins production, Olefins-
Max , as well as the performance of the new generation, ultra-high activity additive, OlefinsUl-
tra, now being used with excellent results in 17 FCC units around the world. In addition, data
is presented from our APEX project for propylene maximization that has led to the introduction of
a new generation of catalysts that will take FCC propylene production to a new level.

Then we feature articles by experts from Dow Chemicals, a leading net consumer of propylene;
ExxonMobil, a major player in the petroleum refining and petrochemicals industries; Kellogg
Brown and Root, ABB Lummus, Stone and Webster, all leading engineering companies with FCC-
type processes designed to produce propylene as a primary product; and the research group at
KFUPM who, together with Nippon Oil, JCCP and Saudi Aramco, have developed a process to
maximize propylene from the FCC unit. Experts from the industry consultants CMAI and Nexant
provide commentary on the dynamics of propylene and polypropylene markets, respectively. Fi-
nally, we introduce our new Davison 8500 Series Polypropylene Catalysts for superior PP resins.

We are delighted to bring together a compilation of articles that provide a broad overview of the
propylene value chain and the opportunities that exist for refiners to increase participation in the
petrochemicals market. We hope that you find this special edition of the Catalagram informative
and look forward to receiving your comments.

Finally, we wish to thank all the authors not only for their articles, but also for the many stimu-
lating discussions we had while compiling this special edition.

Jim Nee, PhD Markus Lesemann, PhD

James.Nee@grace.com Markus.Lesemann@grace.com
In this issue.

Propylene Production in the FCC Unit.................................................................page 3

By J.R.D. Nee and M. Lesemann, Davison Catalysts, USA
This paper highlights the important role of the FCC unit as a producer of propylene for
the petrochemicals market and describes the commercial performance of Davisons
OlefinsMaxTM and OlefinsUltraTM ZSM-5 additive technologies. Data from our APEX
propylene maximization catalyst project are also presented. This technology will take
propylene production in the FCC to a new level.

Global Propylene: Feast or Famine? A Dow Chemical Perspective................page 12

By Stephen J. Markovich, Dow Hydrocarbons and Resources, Inc.
A 1.1 million metric ton shortfall in propylene supply will position Dow as one of the
largest buyers of propylene. How does Dow see the supply/demand dynamics in the global
propylene market?

Propylene Supply for the Global Petrochemical Markets................................page 14

By Stephen J. Zinger, Chemical Market Associates, Inc.
Industry expert Steve Zinger of CMAI explains how the FCC unit is becoming increasing-
ly important as a source of propylene supply to meet future demand growth into the
world petrochemical markets.

Global Polypropylene Market Dynamics.............................................................page 21

By Pamela Giordano, Nexant/Chem Systems
Polypropylene accounts for over 60 percent of global propylene consumption. Thus, an
analysis of the polypropylene market dynamics is a prerequisite for understanding com-
ing developments in propylene markets.

Meeting Propylene Demands with SUPERFLEXTM Technology.......................page 27

By Curtis Eng, Ray Orriss and Michael Tallman, KBR Olefins Technology
The SUPERFLEX process is a fluidized catalytic cracking process that converts olefinic
streams from petrochemical or refinery sources to significant amounts of propylene and
ethylene. The authors discuss the technology as well as the status of the first commercial
SUPERFLEX unit that SASOL will commission in 2005.

On-Purpose Propylene from Olefinic Streams...................................................page 33

By Michael W. Bedell, ExxonMobil Process Research Laboratories; Philip A.
Ruziska, ExxonMobils Chemical Company; and Todd R. Steffens, ExxonMobil
Research and Engineering Company
ExxonMobils new PCC Process converts olefin molecules in naphthas to high value ethyl-
ene, propylene, and (optionally) butylene. This article discusses the characteristics of
PCC and the integration with FCC.

continued on page 2

1
Advanced Catalytic Cracking Technologies for Production of Light Olefins from
Low Cost Refinery Based Feedstocks...................................................................page 37
By Dilip Dharia, Warren Letzsch and Lark Chapin, Stone & Webster
Engineering Corporation
The authors give an overview on how Deep Catalytic Cracking (DCC) and the new
Catalytic Pyrolysis Process (PCC) can enable refiners to extend their product slate into
higher margin petrochemicals.

A New FCC Process Upgrades Gasoline and Maximizes Propylene...............page 45

By T. Ino and Y. Fujiyama, Nippon Oil Corporation, H. Redhwi, A. Aitani and
M. R. Saeed, King Fahd University of Petroleum & Minerals
King Fahd University of Petroleum & Minerals, Saudi Aramco, Japan Cooperation
Center-Petroleum and Nippon Oil have developed a novel high-severity fluid catalytic
cracking (HS-FCC) process that is claimed to increase the yield of light olefins to 40 wt.%
of fresh feed.

Make Propylene the FCC/SCC Way.......................................................................page 51

By Dalip Soni, ABB Lummus Global
The paper describes how Selective Component Cracking (SCC) can provide very high
propylene yields by recycling certain components of the FCC product slate into the
process.

ZSM- 5 FCC Additive Development: A Brief History..........................................page 57

By Girish K. Chitnis and Thomas F. Degnan, ExxonMobil Research and
Engineering Company
The authors describe key challenges in the development of ZSM-5 based FCC additives,
which go back to R&D work by Mobil and were then first commercially introduced by
Davison in 1986.

Davison 8500 Series Polypropylene Catalysts for Superior Resins................page 61

By Kyle Lorton, Davison Catalysts
The author describes the performance of commercially proven Ziegler-Natta catalysts
that are now produced by Davison.

Cover photo: Wrapped Reichstag, Berlin 1971-95

Christo & Jeanne-Claude
(100,000 square meters (1,076,000 square feet) of thick woven
polypropylene fabric and 15,600 meters (51,181 feet) of
blue polypropylene rope)
http://christojeanneclaude.net
Photo: Wolfgang Volz
1995 Christo

2
 Propylene Production
in the FCC Unit:
An Opportunity to Increase
Refinery Profitability
by
J.R.D. Nee and M. Lesemann
Davison Catalysts, USA
The fluid catalytic cracking (FCC) unit is an impor-
tant source of propylene for the petrochemicals
industry. However, substantial changes are taking
place within the industry that will result in an even
greater emphasis on the FCC unit as a source of
propylene, as the demand growth rate outpaces sup-
ply from its primary source, the steam cracker. This
structural shift in propylene supply dynamics will
present operators of FCC units with opportunities to
further boost revenues by making and selling incre-
mental propylene into the petrochemicals market.
This article will highlight the important role of the
FCC unit in the production of propylene and present
state-of-the art catalyst technologies supplied by
Davison to meet the demands of the modern, petro-
chemicals-oriented refinery.
Regional Propylene Supply Dynamics
The demand growth for petrochemicals is driven by
economic expansion primarily in Asia and the Indian
sub-continent. Steam crackers in this region operate
with heavy feedstocks (naphtha, gas oil) that gener-
ate a significant amount of by-product propylene
(0.5-0.6 lbs/lb ethylene). However, the region is gen-
erally long on gasoline and consequently there is a
3
greater tendency for FCC units there to operate with
ZSM-5 catalyst additives to increase propylene pro-
duction. Indeed, during the next two years, several
FCC units will be revamped in order to operate in
"propylene maximization mode" (propylene yield >
10 wt.% of fresh feed).
A substantial amount of steam cracker capacity is
expected to come on stream in the Middle East by the
end of the decade. This capacity will be based on cost-
advantaged ethane feedstock that will generate little
by-product propylene. Much of the Middle Easts eth-
ylene derivatives will be imported into Asia and this
will have an immediate impact on the profitability of
local steam cracker operators. As more ethylene
derivatives pour into the region, steam cracker oper-
ators may be forced to operate their units to maxi-
mize propylene. However the impact on the propy-
lene market of, for example, processing heavier feeds
such as gas oil, will not be significant. Thus, propy-
lene production from FCC units in Asia will continue
to increase and the region could also see some growth
in on-purpose propylene processes, such as those
described in this edition of Catalagram.
In North America the petrochemicals industry is
under extreme pressure to generate profits, as high
(and volatile) gas prices, in combination with a
relentless shift in manufacturing to low cost regions,
erode margins as well as North Americas petro-
chemicals export position. Steam crackers in this
region are generally based on ethane feedstock that
up until 2001 was relatively cheap. However, there
are a number of units that can process either gas- or
crude-based feedstocks, providing this region with a
high degree of feedstock flexibility.
The refining industry in North America is gasoline-
driven. Not surprisingly, almost half of the worlds
FCC capacity is located in this region, and almost
half of this is concentrated in the U.S. Gulf Coast
the heart of the U.S. petrochemicals industry. Of
those refiners that use ZSM-5 technologies to
increase the yield of light olefins, many do so to fill
their alkylation units. Several refiners with access to
petrochemical facilities use ZSM-5 additives on an
ongoing basis, usually to fulfill long-term supply con-
tracts. There are, however, "opportunistic" users of
ZSM-5 technologies that will make incremental
propylene for sale to the petrochemicals market
(domestic and export) when economics are favorable.
Thus, with so much FCC capacity at its disposal, the
U.S. is well positioned as a "swing" producer of refin-
ery-sourced propylene.
Steam crackers in Europe, as in Asia, operate with
heavy feedstocks (e.g. naphtha) where by-product
propylene is significant. Typically, FCC units that
Figure 1
Incremental Expected RG Propylene Supply From FCC Units
RG Propylene Supply over 2001, WW
10,000
9,000 Production from new units
8,000
Production from existing units
7,000
1,000 MT
6,000
5,000
4,000
3,000
2,000
1,000
0
2002 2003 2004
use ZSM-5 additives, as in the U.S., do so to fill their
alkylation units. Nevertheless, several refiners,
notably those located adjacent to petrochemicals
facilities, operate with ZSM-5 additives to maximize
propylene production.
Europe is generally characterized as "diesel orient-
ed and there is a greater tendency to utilize ZSM-5
additives compared to the U.S. As in Asia, low cost
imports of ethylene derivatives from the Middle East
could impact steam cracker operating rates in the
long term and create more demand for FCC sourced
propylene.
Naphtha feedstocks are largely processed in steam
crackers in South America though much of the new
and planned capacity is based on ethane. FCC units
are expected to increase volumes of propylene sold to
the petrochemicals market; therefore, the use of
ZSM-5 additive technologies in this region will con-
tinue to increase. Much of the growth is expected in
Mexico, Brazil and Argentina.
Compared with 2001, FCC units worldwide are
expected to provide an additional nine million MT of
refinery grade (RG) propylene by the year 2008. Very
little of this propylene will actually come from new
FCC units, as only limited capacity expansions are
expected. Most of the additional propylene will be
produced by existing FCC units employing ZSM-5
based additives or catalysts (Figure 1).
2005 2006 2007 2008
4
Furthermore, the percentage of FCC produced propy-
lene that is upgraded in splitters to polymer or chem-
ical grade (PG and CG) will increase. Currently,
about 83% of all refinery grade (RG) propylene pro-
duced worldwide is upgraded to PG or CG in propy-
lene splitters, and this is forecast to increase to 86%
by 2007. Although the fraction of RG propylene that
is upgraded varies significantly between different
regions, e.g. 79% in North America vs. 96% in
North East Asia, the same trend towards higher
upgrading rates can be expected in most regions of
the world [1, 2].
Propylene price volatility
Besides the structural increase in demand for propy-
lene from FCC units, price volatility in propylene
markets is expected to continue. According to a
recent report by CMAI, the volatility of RG propylene
prices in the U.S. has increased significantly since
the beginning of 1999. The main cause is the under-
lying volatility of energy prices, as well as changed
dynamics in the RG propylene market. In particular,
supply shortages are occurring more frequently,
Figure 2
Volatility in RG Propylene Markets (Source: CMAI)
Historical CMAI Reported Spot RG Prices
Range/Delta
(Cents Per Pound)
6.0
5.0
4.0
3.0
2.0
1.0
0.0
01/16/95 01/31/96 02/14/97 02/27/98
Delta Between High and Low Reported Prices
year-end inventories are constantly being reduced by
cash-strapped companies, and additional speculative
trading of RG propylene is increasing as reported by
CMAI. Furthermore, refineries that are located fur-
ther away from the U.S. Gulf Coast are increasingly
participating in the propylene spot market with the
production of incremental propylene.
The graph below (Figure 2), provided by CMAI,
shows that until the fall of 1999, the range of report-
ed spot RG propylene prices within a two-week peri-
od was well below one cent/lb. Then from 2000,
propylene prices fluctuated sharply in the U.S. with
price fluctuations of more than three cents/lb, and
later in 2003 more than four cents/lb with a maxi-
mum of 6 cents/lb in February of 2003. [3]
These price swings in the U.S. propylene market are
largely due to substantial changes in oil and gas
prices and moreover the relative pricing of these two
commodities in North America. However, other fac-
tors mentioned above, such as supply disruptions,
serve to aggravate these price swings.
Absolute Price
(Cents Per Pound)
30
25
20
15
10
5
0
03/15/99 03/28/00 04/16/01 04/29/02 05/15/03
Absolute High and Low Prices
5
It is clear that this trend towards higher price
volatility will lead to economic opportunities for FCC
operators who are not only well informed about mar-
ket conditions but are also willing and positioned to
utilize ZSM-5 additives at short notice.
Propylene Consumers and the Propylene
Supply Gap
Faced with a potential propylene supply gap, propy-
lene consumers, especially polypropylene producers,
(the main consumers of propylene) are examining
opportunities to secure propylene supply through
backward integration. Sunoco, for example, recently
expanded its polypropylene position with the acqui-
sition of Equistars Bayport facilities but fundamen-
tal to their business plan is a 15-year, 700 million
pounds per year propylene supply contract with
Equistar Chemicals [4]. Sunocos own refineries
account for some 35% of their propylene require-
ment.
Several large propylene producers and consumers
agree that incremental propylene will need to be
sourced from refineries to meet the demand growth
forecast. Dow Chemicals is one of the largest net buy-
ers of propylene and they believe that some refiners
will make the necessary investments to upgrade
hardware so that they can produce and recover high
yields of propylene (see Dows article in this issue of
Catalagram). Of course, propylene prices will need to
increase to a level that justifies such investments.
Enterprise Products Partners, the leading provider
of propylene upgrading technology in the U.S. Gulf
Coast, reports that propylene demand growth will be
Figure 3
Worldwide ZSM-5 Additives Segmentation by Activity
High Activity
63%
Moderate
Activity
Low Ultra - High Activity
22%
Activity 11%
4%
2003
6
met primarily by fractionating refinery-sourced
propane/propylene mixes, i.e. RG propylene [5].
Reliance Industries, India, Asias largest polypropy-
lene manufacturer and number seven in the world,
plans to increase its polypropylene capacity by 40%
to a total of 1.4 million metric tons per annum.
Reliance sees its own cracker, started up only in
1997, as having strategic importance during this
expansion, since the cracker can provide petro-
chemical feedstocks while eliminating Reliances
exposure to volatility in international petrochemi-
cals markets [6].
Davison Catalysts: Propylene Maximization
Technologies
The use of ZSM-5 based additives is the most cost
effective way to increase propylene production in the
FCC unit. Demand for these additives has increased
steadily over the years and the industry has contin-
ued to move to higher activity grades.
Davison Catalysts was the first catalyst manufactur-
er to supply ZSM-5 based additives for use in FCC
units back in 1984 (see article "ZSM- 5 FCC Additive
Development - A Brief History" in this issue) where
their primary role was to enhance gasoline octane.
Since then, the role of these additives has changed to
that of optimizing the yields of high value C3= and
C4= olefins, while at the same time capturing the
boost in gasoline octane. Through continuous R&D
efforts Davison has maintained its position as the
worldwide leading provider of ZSM-5 based FCC cat-
alyst technologies.
High Activity
55%
Moderate
Activity
12%
Low
Activity Ultra - High Activity
2% 31%
2006 Forecast
 Figure 4
Additives Containing 25 wt.% ZSM-5 Crystal - Segment Share
Competitive 26%
Products
with 25%
ZSM-5 crystal

Grace Davison
OlefinsMax
74%

Developments by Davison Catalysts over the years duction of OlefinsMax, the first such additive to con-
have focused on increasing the intrinsic activity of tain 25% ZSM-5 crystal, which at the time was the
ZSM-5 additives to enable refiners to more cost-effec- maximum allowable under license. This additive rap-
tively maximize yields of light olefins. Figure 3 idly established itself as the benchmark for high
shows that the vast majority of refiners currently activity ZSM-5 additives and is still the most widely
using ZSM-5 additives have chosen high- or ultra- used ZSM-5 additive in the refining industry,
high activity ZSM-5 additives to meet their light accounting for nearly half of all ZSM-5 users. In fact,
olefins needs. With the upturn in the next petro- an analysis of refiners that employ additives con-
chemical cycle, a further increase in the demand for taining 25 wt.% ZSM-5 crystal confirms that
ultra-high activity ZSM-5 additives (>>25 wt.% crys- OlefinsMax is by far the additive of choice (Figure 4).
tal) is expected as more FCC units operate to maxi-
mize propylene production. The reason for the wide acceptance of OlefinsMax is
its performance relative to competitive products.
OlefinsMax Commercial data shows OlefinsMax has higher activ-
ity per pound of additive compared with competitive
The first real breakthrough in the development of products that also contain 25 wt.% ZSM-5 zeolite.
high activity ZSM-5 additives came with the intro- One recent example is shown in Figure 5. This activ-

Figure 5
Commercial Example of OlefinsMax Application
OlefinsMax Shows Higher Activity Per Unit of Crystal Versus Competitive Product (25% ZSM-5)
120
Relative Activity per unit of ZSM-5 Crystal %

110

OlefinsMax
100

90

80

70

Competitive ZSM-5
60
70 72 74 76 78 80
Conversion

7
 Figure 6
Davison Additives Show Linear Activity Response
as a Function of ZSM-5 Crystal Input

7.0

4
6.0 Grace Davison

4
ZSM-5
Additives
5.0
Relative Activity

4.0
Competitive
3.0 Additives

2.0

There are significant performance differences

1.0 between competitive additive suppliers' products!

0.0
0 1 2 3 4 5 6
Relative ZSM-5 Concentration

ity difference is attributed to the proprietary ZSM-5
zeolite stabilization process employed by Davison
Catalysts that ensures maximum ZSM-5 activity
over a wide range of ZSM-5 levels in the additive
(Figure 6). Stabilization of the ZSM-5 zeolite with
phosphorus is a critical process in the manufacture of
ZSM-5 additives.
Refiners that utilize OlefinsMax typically add it to
the unit in the range of 3-5 wt.% of fresh catalyst
additions. However, several refiners have increased
OlefinsMax additions to levels well above 5 wt.% and
are getting as much as 16 vol.% (9 wt.%) propylene
from their FCC units. Those refiners that have
already made the decision to switch to the ultra-high
activity ZSM-5 additive, OlefinsUltra are benefit-
ing not only from industry leading propylene yields
but also from reduced dilution of the circulating cat-
alyst inventory, allowing them to reduce fresh cata-
lyst consumption.
OlefinsUltra
The intrinsic activity of OlefinsUltra far exceeds
even that of OlefinsMax and it provides the highest
activity per pound of any commercially proven ZSM-
5 additive. The unique matrix system in OlefinsUltra
not only ensures maximum activity per unit of ZSM-
5 crystal but also provides excellent attrition resist-
ance properties. In fact, a major European refiner
was able to reduce by almost half the addition of
ZSM-5 additive and still achieve the desired yield of
propylene (Figure 7a). This enabled the refiner to
reduce fresh catalyst consumption by more than 10%
(Figure 7b).
OlefinsUltra is the ideal choice for refiners wishing
to maximize the production of propylene and
butylenes from the FCC unit where high levels of
conventional additives would be required that would
otherwise result in dilution of the circulating catalyst
inventory. OlefinsUltra is currently being used suc-
cessfully in 17 refineries around the world.
Davisons APEX project: New Propylene
Maximization Technology
Davison Catalysts has also been actively working on
a propylene maximization project with the aim to
produce catalysts that give yields in excess of 15
wt.% from the FCC unit. A new family of catalysts
has subsequently been developed that will allow
refiners to take propylene production to a new level.
Using proprietary shape-selective zeolite and matrix

8
 Figure 7
Commercial Application of OlefinsUltra:
European Refiner Reduced Fresh Catalyst Addition Rate and
Maintained High Propylene Yield Following a Switch to OlefinsUltra

7a
Propylene Selectivity (C3=/Conversion)

4 4
4 OlefinsMax
4 OlefinsUltra
Propylene Selectivity, (%)
4

Propylene yield >14vol % (8 wt.%)

Time 4

7b
OlefinsMax
Fresh Catalyst Addition Rate

4
4

ca 10 wt.% Reduction in
Fresh Catalyst Addition Rate
4

OlefinsUltra

70 4 75
Equilibrium Catalyst Microactivity

9
 Table I
APEX Project: Propylene Maximization Catalyst Technology

Typical Yields (wt.%)

Conventional FCC Conventional FCC AP pmc-140 AP pmc-150 AP pmc-200
+ZSM-5 Additive
Feed Type Heavy Heavy Heavy Heavy Light
Ni+V/ppm 5000 5000 5000 5000 <100
Reactor (C) 535 535 550 565 565
Temperature
Conversion (wt.%) 80 80 80 85 85
Propylene (wt.%) 5 9 15 18 22
Butylenes (wt.%) 8 10 14 12 17
C5+gasoline (wt.%) 52 46 36 32 28
LCO + HCO (wt.%) 20 20 20 15 15

technologies, the catalysts developed within the
APEX project not only produce exceptional yields of
propylene (Table I) but also demonstrate low coke
make and good bottoms cracking activity in the pres-
ence of contaminant metals. Propylene yields of more
than 20 wt.% are of particular interest to refiners
who are considering revamping their FCC units to
operate in a "petrochemicals mode". This new cata-
lyst technology reaffirms Davisons commitment to
developing leading edge technologies that offer refin-
ers cost-effective solutions to meet or exceed their
expectations.
This propylene maximization technology is currently
in the commercialization stage, and a first applica-
tion in an FCC unit is expected to take place in 2004.
Davison Catalysts is the leading supplier of high per-
formance ZSM-5 FCC additives. OlefinsMax is the
most widely used additive in the industry today by
virtue of its performance versus competitive prod-
ucts. To meet the industrys need for additives with
even higher activity, Davison introduced
OlefinsUltra which is now being used in 17 FCC
units around the world.
For those refiners that are considering revamping
their FCC units to operate in a "petrochemicals
mode", Davison in its APEX project is introducing
new catalyst technology that will take the production
of propylene in the FCC unit to a new level.
References

Conclusion [1] CMAI World Light Olefins Analysis 2003. CMAI, Houston,
2003.
The demand for propylene from FCC units will
[2] Steve J. Zinger, CMAI, CMAI World Petrochemical
increase significantly over the next few years to fill Conference 2003.
the supply gap that is developing as a result of a lag
in steam cracker capacity expansion and an increase [3] Monomers Market Report 552, CMAI, Houston, 2003.
in the processing of light feedstocks (e.g. ethane in
[4] Press release by Sunoco, Inc., March 27, 2003.
steam crackers.) This will lead to opportunities for
refiners to boost revenues by producing incremental [5] Enterprise Products Partners L.P., http://www.epplp.com
propylene for sale into the petrochemicals market
[6] Speech by Mukesh Ambani, Chairman & Managing Director,
through the use of ZSM-5 additive technologies.
Reliance Industries, India (June 16, 2003)

10
Davison Automatic Injection Systems
Accurate & Reliable Easy to Install
Full Service Support
Designed to inject additives or catalyst
into FCC units with unsurpassed reliability.
Proven worldwide!

For more information please contact our regional offices:

Al Jordan Matthias Scherer John Haley

Americas Europe Asia Pacific

W. R. Grace & Co. Grace GmbH W. R. Grace (Singapore) Pte Ltd.

7500 Grace Drive In der Hollerchecke 1 501 Orchard Road
Columbia, MD 21044, U.S.A. 67545 Worms, Germany #07-02A, Wheelock Place, Singapore 238880
+1 (410) 531-8299 +49 (6241) 403 585 65-737-5488
alfred.jordan@grace.com matthias.scherer@grace.com john.haley@grace.com
 Global Propylene:
Feast or Famine?
A Dow Chemical Perspective
by
Stephen J. Markovich
Dow Hydrocarbons and Resources, Inc
Houston, TX
The Dow Chemical Company with its subsidiaries
has a worldwide presence in the propylene and
propylene derivatives industry, with global produc-
tion capacity of 3.2 million metric tons per year and
global propylene derivative demand of over 4.3 mil-
lion metric tons per year. Dow uses propylene to
manufacture polypropylene, propylene oxide/glycol,
acrylic acid, and oxo alcohols. This 1.1 million met-
ric ton shortfall will position Dow as one of the
largest buyers of propylene, the majority of which is
purchased in North America for propylene derivative
production. As a large consumer of propylene, Dow
maintains a keen interest in the U.S. supply dynamics
of propylene including current supply from ethylene
steam crackers and refineries, and developing supply
from on-purpose production and catalyst technologies.
12
Global propylene applications have seen increased
price volatility as the world enters the twenty first
century. Although much of this volatility has been
caused by increased volatility in the underlying ener-
gy industry, an increasing amount of the volatility
can be attributed to propylene supply/demand
dynamics. There are some concerns as to whether
supplies of propylene will be adequate to allow for
continued growth at historical rates. While some
industry consultants predict potential shortages in
industry supply, there are others that believe that
tightness in the industry will incent and enable
refinery propylene to become more available to the
chemical industry and thereby offset any potential
shortages.
Over the last ten years propylene derivative demand
growth has historically outstripped that of ethylene
derivatives. If propylene prices continue to stay
lower than ethylene prices, this trend will continue.
But as ethylene and propylene prices converge, the
demand for propylene should decrease. According to
leading industry consultants, global propylene deriv-
ative demand is expected to grow at a rate of five per-
cent for the next five years. However, because propy-
lene is a co-product of ethylene and, to a lesser
extent, refinery fluidized catalytic cracking (FCC) for
the production of gasoline and distillates, the pace of
additional propylene capacity has not been in sync
with the demand growth. An additional factor for the
U.S. propylene industry is its presence in global
regions as an exporter of propylene monomer. It is
estimated that the U.S. Gulf will export 450,000 tons
of polymer grade propylene primarily to Asia, Europe
and Latin America in 2003. This will put additional
demand on the future propylene supply picture on
the U.S. Gulf, particularly if growth in Asian propy-
lene derivative production creates additional growth
in export demand.
In some areas of the world this has created the
opportunity for new on-purpose propylene technolo-
gies to become economically feasible supply alterna-
tives. Current on-purpose production of propylene
accounts for less than three percent of total global
propylene production. Propane dehydrogenation and
metathesis facilities have been built and announced
for Europe and Asia within recent years due to this
phenomenon. Metathesis is a technology in which
ethylene and butene are reacted to produce propy-
lene. Propane dehydrogenation uses propane feed-
stock to produce propylene through a dehydrogena-
tion process.
The U.S., however, has been more reluctant to par-
ticipate in on-purpose production facilities with the
notable exception of some existing and announced
metathesis production facilities. Industry consult-
ants project that heavier feedstock cracking at U.S.
Gulf steam crackers and the use of catalyst technolo-
gies at refineries are the most likely incremental
sources of supply to fill future demand.
13
The increase in natural gas pricing over the last cou-
ple of years has brought into question the competi-
tiveness of the U.S. Gulf as a light olefin (ethylene
and propylene) producer, thereby decreasing the like-
lihood of any additional light olefin capacity from the
construction of steam cracking capacity. However, as
ethane feed to flexible steam crackers is replaced by
heavier feeds such as propane and naphtha, the
propylene yield from steam crackers will increase
providing additional supply for the chemical indus-
try. Propylene yields from ethane are typically 3-4%
of total production of the steam cracker by weight,
yields from propane approximate 40%, and yields
from naphtha can range from 50-60%. The propylene
capacity generated by the flexibility of the U.S. Gulf
steam crackers can vary by 300-400 MM pounds of
production per month when switching from light feed
slates (ethane) to heavier ones (naphtha, conden-
sate).
There is, however, some refinery catalyst technology
that may fill the potential propylene supply void in
the U.S. in future years and help to support contin-
ues strong propylene derivative growth. Zeolite
based catalyst technology, referred to as ZSM-5, was
introduced into U.S. Gulf FCC units in the 1980s pri-
marily to increase octane numbers in gasoline. The
effect of the catalyst was to increase light olefins pro-
duction from FCC production from the normal 3-5
wt.% to as high as 10-15 weight% while reducing
total gasoline production volume by 5-6%. This cre-
ates an optimization for the refinery to balance the
value of additional propylene production against lost
gasoline production. There are several reasons why
this catalyst technology has not yet been fully uti-
lized. The most pervasive of these is the likelihood
that most refineries would have to spend capital of
$20-30 million to increase light ends recovery sys-
tems at these refineries. This capital must compete
with other refinery capital projects including those
that result from regulatory and environmental com-
pliance.
The U.S. propylene industry will likely experience
substantial movement in supply/demand balance
and price volatility in the future. Refineries are like-
ly to invest capital necessary for the use of propylene
production enhancing catalyst technologies.
 Propylene Supply
for the
Global Petrochemical Markets
by
Stephen J. Zinger
Chemical Market Associates, Inc.
Houston, TX
The market for propylene as a basic intermediate
petrochemical continues to grow at average rates of
4.0-5.0% per year. The largest source of propylene
supply to the petrochemical markets is steam crack-
ers (as a by-product of ethylene); the second largest
source of propylene supply to the petrochemical mar-
kets is refinery FCC units (as a by-product of gaso-
line and distillates). However, the FCC unit is
becoming increasingly important as a source of
propylene supply to meet future demand growth into
the world petrochemical markets.
Propylene Market Overview
Like most petrochemicals, propylene is ultimately
derived from the basic fundamental energy com-
modities of either crude oil or natural gas. These two
fundamental commodities are processed in an oil
14
refinery or gas separation/fractionation plant in
order to make the basic feedstocks for steam crackers
(ethane, propane, butane, naphtha, gas oil, or con-
densate) and to make the basic feedstocks for an oil
refinery FCC unit (gas oil or residue). The primary
purpose of a steam cracker is to produce ethylene,
while the primary purpose of the refinery FCC (flu-
idized catalytic cracking) unit is to produce gasoline
and distillates. Therefore, propylene is generally
considered a by-product from steam crackers and
FCC units.
In 2003, the estimated size of the world poly-
mer/chemical grade propylene markets was 56.2 mil-
lion metric tons. About 67% of the worlds propylene
production originates from steam crackers as a by-
product of ethylene.
About 30% of the worlds propylene production is
 Figure 8
World PG/CG Propylene Demand Forecast
Million Tons
80.0
70.0
60.0
50.0
40.0
30.0
20.0
10.0
0.0
90 91 92 93 94 95 96 97 98 99 00 01 02 03 04 05 06 07
Polypropylene 7.9 / 5.7* Cumene 3.0 / 4.6*
Oxo Alc. 3.1 / 4.0* Propylene Oxide 3.7 / 4.3*
*%AAGR 90-03 / %AAGR 03-08
from refinery FCC units as a by-product of motor
gasoline and distillates. Less than three percent of
the worlds propylene production comes from "on-
purpose" production such as propane dehydrogena-
tion, metathesis, olefin cracking, and methanol-to-
olefins. Except under unique circumstances, these
processes are generally not competitive with the
by-product processes of producing propylene by
steam crackers or refinery FCC units.
Propylene is typically recovered from steam crackers
as "chemical grade" at 93-97% purity or "polymer
grade" at 99.5% purity and from FCC units as "refin-
ery grade" at 65-80% purity. Refinery grade propy-
lene is often upgraded to polymer or chemical grade
propylene through distillation.
The most significant propylene consumer is
polypropylene resin production, consuming about
63% of global propylene production. Most polypropy-
lene resin is formed into injection-molded plastic
goods (caps and closures, containers, cups, auto
parts), fibers (carpet face yarn, agricultural bags), or
film/sheet (snack packaging). Other major, yet less
significant propylene consumers, include the produc-
tion of acrylic acid (for superabsorbent polymer used
in diapers and acrylates used in paints, coatings, and
adhesives), acrylonitrile (for acrylic fibers used in
clothes and blankets and for ABS polymers used in
appliances), cumene (for polycarbonate used in com-
pact discs and phenolic resins used in plywood), oxo-
alcohols (for plasticizers used in flexible PVC goods
08
Acrylonitrile 2.5 / 2.1*
Others 3.6 / 4.1*
such as garden hoses or shower curtains), and propy-
lene oxide (for polyurethanes used as car seat foam
or insulation and for propylene glycol used in
antifreeze)(Figure 8).
Steam Cracker Propylene Supply
Since propylene is produced as a by-product of ethyl-
ene in steam crackers, existing steam crackers are
usually optimized and new steam crackers are usu-
ally built in order to meet ethylene demand. Over
the past 12 years, global ethylene demand growth
has averaged 4.4% while global propylene demand
growth has averaged 5.8%. Propylene demand
growth is faster than ethylene demand growth,
because propylenes largest consumer, polypropylene,
grows at faster rates than ethylenes largest con-
sumer, polyethylene. CMAI expects that this trend
of faster propylene demand growth will continue in
the near future. Since new steam cracker invest-
ments are primarily made to meet new ethylene
demand and since propylene demand is growing
more quickly than ethylene demand, not enough new
steam cracker investments will be completed to meet
new propylene demand(Figure 9).
Average propylene yields from steam crackers are
also expected to decline in the future as a result of
investment activity in the Middle East. Over the
past 12 years, Middle East producers have nearly
doubled ethylene capacity, while propylene capacity
additions have been relatively minor. Most steam
15
 Figure 9
Global Propylene and Ethylene Annual Demand
Annual Demand Growth
12%

Ethylene
10%
Propylene

8%

6%

4%

2%

0%
1990 1992 1994 1996 1998 2000 2002 2004 2006 2008

cracker feedstocks in the Middle East are based on
low-cost ethane supplies (with insignificant propy-
lene yields), and most ethylene produced is sent to
Asia in the form of ethylene equivalent exports (eth-
ylene contained in polyethylene or ethylene glycol).
Over the past 12 years, the Middle East has con-
tributed very little to global propylene supplies and
has actually been a net importer of propylene equiv-
alents (propylene contained in polypropylene or acry-
lonitrile).
Over the next eight years, the Middle East producers
will again double ethylene production and equivalent
exports based mostly on low-cost ethane feedstocks,
with only minor increases in propylene production
(Figure 10). The Middle Easts global market share

Figure 10
Middle East Ethylene/Propylene Capacity & Trade
Million Tons
25.0

20.0

15.0

10.0

5.0

0.0

-5.0
1990 1992 1994 1996 1998 2000 2002 2004 2006 2008 2010

Propylene Derivative Exports Ethylene Derivative Exports

Propylene Capacity Ethylene Capacity

16
of ethylene production is expected to increase from
seven percent in 2000 to 18% in 2010, while the
Middle Easts global market share of propylene pro-
duction is expected to increase from two percent in
2000 to five percent in 2010. Since most of the new
Middle East ethylene will be exported in the form of
ethylene derivatives to Asia, fewer steam crackers
will be built in Asia to meet new ethylene demand
than otherwise would have been built without the
additional ethane-based Middle East capacity. In
contrast to the Middle East, steam crackers in Asia
are naphtha-based and the lack of new Asian projects
consequently will reduce propylene production
growth in Asia.
Steam cracker operators are currently implementing
several options to enhance propylene yields. Based
on the expectation for future tighter propylene mar-
kets, investors are more likely to consider heavy feed
(naphtha, condensates, gas oil) crackers or at least
light/heavy flexible crackers unless there is an
extremely cost-advantaged source of ethane avail-
able. In some instances, investors are even calculat-
ing expected production costs and revenues based on
the "cost of light olefins ethylene and propylene"
rather than just the traditional method of the "cost of
ethylene". For existing facilities, steam cracker
operators are considering lower severity and heavier
feedstock operations. Some cracker operators
throughout the world have already increased their
feedstock flexibility from the traditional full-range
naphthas (with propylene-to-ethylene ratios of 0.5-
Figure 11
Global Propylene and Petroleum Growth
Annual Demand Growth
12%
10%
8%
6%
4%
2%
0%
1990 1992 1994 1996 1998
0.6) to more field condensates and gas oils (with
propylene-to-ethylene ratios of 0.6-0.7). Finally,
steam cracker operators are considering the auxil-
iary use of novel technologies to further enhance
propylene yields, including metathesis and higher
olefin cracking.
FCC Unit Propylene Supply
Due to the aforementioned constraints of propylene
supply growth from steam crackers, additional
emphasis has been placed on recovering propylene
from refinery FCC units. Like steam crackers, refin-
ery FCC units are not operated or built to make
propylene, but some other primary product. FCC
units primarily produce motor gasoline or other dis-
tillate heating or transportation fuels.
Like ethylene from steam crackers, the primary
products from FCC units (petroleum-based products)
are growing at even slower rates than the by-product
propylene. Over the past 12 years, global petroleum
demand growth has averaged one to two percent,
while global propylene demand growth has averaged
5.8%. Propylene demand growth is faster than petro-
leum demand growth, because propylenes largest
consumer, polypropylene, grows at faster rates than
the more mature markets of transportation and
heating fuels. CMAI expects that this trend of faster
relative propylene demand growth will continue in
the near future (Figure 11). Since new FCC invest-
ments are primarily made to meet new gaso-
Petroleum
Propylene
2000 2002 2004 2006 2008
17
 Figure 12
FCC Supply Geographic Location (North America)
line/distillate demand and since propylene demand is
growing more quickly than gasoline/distillate
demand, not enough new FCC investments will be
completed to meet new propylene demand.
Even though new FCC units will not be constructed
quickly enough in order to meet new propylene
demand, there is tremendous potential for existing
FCC units to recover propylene that is currently not
utilized in petrochemicals. Globally, the recovery of
propylene for chemical uses from FCC units in 2003
is expected to be 20.0 million tons. However, FCC
units actually produced an estimated 14.5 million
tons for non-chemical uses and could even potential-
ly produce an estimated additional 19.3 million tons
with the use of practical levels of high activity cata-
lyst additives (ZSM-5).
Therefore, global "reserves" of FCC propylene exist
that could be tapped for petrochemical use, but sev-
eral issues limit the ability to access these "reserves".
First, the supplies of FCC propylene are often locat-
ed in areas far away from the existing infrastructure
for petrochemical production and consumption.
Historically, demand for transportation and heating
fuels has extended to almost every geographic region
of the world and oil refineries (and FCC units) have
been built throughout the world to meet this
demand. However, the major demand for basic
petrochemicals has been limited to the most econom-
ically developed countries, and basic petrochemical
18
production units are often concentrated in these
areas in order to take advantage of efficiencies relat-
ed to common infrastructure and economies of scale.
North America is one of the largest transporta-
tion/heating fuel and petrochemical consumers in the
world and provides an example of the geographic
variation in the locations of FCC units and existing
petrochemical infrastructure. About 85% of steam
cracker capacity (basic petrochemical production) is
located on the U.S. Gulf Coast of Texas and
Louisiana, while only 29% of refinery FCC unit
capacity is located in Texas and 18% of refinery FCC
capacity is located in Louisiana. Other areas of high
FCC unit capacity concentration are the heavily pop-
ulated areas of California (11%), the Northeast
(10%), and the Midwest (16%) (Figure 12). Since
most existing petrochemical infrastructure is located
on the U.S. Gulf Coast, this poses a challenge to
propylene consumers who seek to access the
"reserves" of propylene located in other areas. As
consumers seek this propylene in the future, the
price of propylene will either incur additional deliv-
ery costs to the existing infrastructure in the U.S.
Gulf Coast or the dislocated propylene supplies will
be consumed by the construction of new derivative
plants and associated infrastructure in areas with
high concentrations of FCC units.
The second issue that limits access to global
"reserves" of FCC propylene for petrochemical use is
the volatility of the underlying alternative internal
values for refinery-based propylene. Although some
newer refineries were built with the intention to sell
propylene to a petrochemical consumer, most refiner-
ies have been designed to be self-sufficient on their
capability to consume by-product propylene either as
feed to a gasoline production unit (alkylate or
dimate) or to be blended with other light hydrocar-
bons to make a saleable heating/cooking fuel (LPG or
propane). The values of these internal uses for
propylene as an automobile or heating/cooking fuel
are quite volatile and chemical consumers must
effectively compete with these values in order to
secure propylene feedstocks.
In the U.S., the most common alternative refinery-
internal use for FCC-sourced propylene is as feed-
stock in the alkylation process. Propylene is com-
Figure 13
U.S. Propylene Prices & Alkylation Impact
Cents Per Pound
30
bined with isobutane to produce a relatively clean,
high-octane C7 motor gasoline blending component.
The netback value of propylene in the refinery alky-
lation process is defined as the price of refinery grade
propylene that a refiner would be willing to pay for
propylene in order to break-even (zero profit) on
making an alkylate gasoline. The propylene alkyla-
tion netback value effectively sets a floor for refinery
grade propylene prices. (If refinery grade propylene
prices fall below the alkylation netback, then refiners
will consume incremental propylene supplies in alky-
lation. Conversely, if refinery grade propylene prices
are above the alkylation netback, then refiners will
seek to sell more propylene production to petrochem-
ical consumers). The difference between refinery
grade and polymer/chemical grade propylene prices
effectively represents the cost of purification.
Dollars Per Ton
660
Forecast

25 550

20 440

15 330

10 220

5 110

0 0
'90 '91 '92 '93 '94 '95 '96 '97 '98 '99 '00 '01 '02 '03 '04 '05

Texas Alky Value Spot Refinery Grade Contract Polymer Grade

The volatility of the underlying alkylation netback
values for propylene is very much related to the
motor gasoline markets, which experience seasonal
demand (and price) peaks in the summer months and
are greatly impacted by crude oil prices (Figure 13).
As more and more "reserves" of refinery-based propy-
lene supplies are accessed, alternative valuations
for refinery propylene (alkylate, dimate, propane,
or LPG) will become more important to propylene
pricing, and propylene producers will have to
either absorb the volatility associated with this
alternative valuation or pass this volatility on to
their customers.
Refinery FCC operators are currently implementing
several options to enhance propylene yields. For
existing units, FCC operators are considering recov-
ering propylene that is currently being consumed
internally in alkylation, dimate, or LPG. This usual-
ly requires investments in separation, storage, and
logistic facilities, especially if there is not an on-site
petrochemical consumer. Some refiners are being
"courted" by petrochemical companies to allow for
the construction of on-site derivative plants.
Existing refiners are also examining the use of high
activity catalyst additives (ZSM-5) to essentially dou-

19
 Figure 14
World PG/CG Propylene Supply Forecast
Million Tons
80.0

70.0

60.0

50.0

40.0

30.0

20.0

10.0

0.0
90 91 92 93 94 95 96 97 98 99 00 01 02 03 04 05 06 07 08

Stm. Crackers 4.6 / 3.1* Dehydrogenation FCC/Splitters 8.3 / 6.1* Others

*%AAGR 90-03 / %AAGR 03-08

ble or triple their existing propylene yields; however,
this usually requires not only additional catalyst cost
but also investment in expansions of light ends han-
dling systems. Finally, existing refiners are consid-
ering the auxiliary use of novel technologies to fur-
ther enhance propylene yields, including metathesis
and higher olefin cracking. For new units, some
refiners are considering the novel technology of "deep
catalytic cracking" or "high olefin cracking" that
severely over-cracks gas oil feedstock, producing
propylene yields up to 20-25 wt.% versus the tradi-
tional FCC propylene yield of 3-6 wt.%. The growing
importance of refinery-sourced propylene is shown in
Figure 14.
Conclusions
The global demand for propylene as a petrochemical
intermediate continues to grow at quite strong rates
(5.8% per year) relative to other chemical and refin-
ing commodities, mainly due to strong growth rates
for propylenes primary derivative, polypropylene.
Steam crackers currently produce most of the worlds
propylene for petrochemical uses, but growth in
propylene supplies from this source will be limited
due to slower relative ethylene demand growth and
associated steam cracker investments and due to the
use of lighter steam cracker feedstocks (with lower
propylene yields) mainly in the Middle East.
FCC units are currently the second largest source of
propylene for petrochemical uses. Like steam crack-
ers, growth in propylene supplies available for petro-
chemicals from new investments in FCC units will be
insufficient because motor gasoline/distillate
demand grows at much slower rates than propylene.
However, significant profit-enhancing opportunities
exist for refining companies with existing invest-
ments in FCC units that can upgrade propylene pro-
duction from internal fuel uses (alkylation, LPG,
etc.) to petrochemical uses and also increase propy-
lene yields for petrochemical uses through the use of
high activity catalyst additives.

20
 Global Polypropylene Market
Dynamics
by
Pamela Giordano
Nexant/Chem Systems
White Plains, NY

Recovery is Now Underway In the post-2005 period, the degree of over-supply

As 2003 came to a close, it was clear that the expect-
ed recovery for the polyolefin industry had been
delayed yet again. The industry downturn has been
prolonged by a variety of unforeseen events that
had significant impact on global polyolefins markets.
The tragedy of September 11th, successive wars in
Afghanistan and Iraq, political problems in
Venezuela, natural gas shortages, and the SARS epi-
demic combined to keep feedstock and energy prices
high while polyolefin demand and prices were low.
Historically, cycles in commodity petrochemicals like
polypropylene have been about eight years long
peak-to-peak, but this one is expected to be close to
ten years long as seen in Figure 15, with the next
peak forecast for 2005.
will be smaller than it has been historically, due to
the stabilizing effect of industry consolidation. The
key drivers for future profitability will be consolida-
tion, lower energy prices, and under-investment.
Energy prices are projected to remain low in the
post-2005 period ($21/bbl base case). The next cycle
may be the best in 25 years, with the peak in 2005
forming a gradually declining plateau, followed by a
relatively high trough.
In North America, polypropylene has also suffered
from severe over-supply. The result has been the
longest period of poor performance in the history of
the industry. The history of margin decline can be
traced directly to the 1995 to 2001 timeframe, when
producers added five billion pounds of new

21
 Figure 15
U.S. Petrochemical Industry Profitability
Cash Cost Margins - Constant Dollars - Cycle Case

4 4 4
450
400
4 9 Years 4 7 Years 4 10 Years
Peak-to-Peak Peak-to-Peak Peak-to-Peak
Index, 1982 = 100

350
300
250
200
150
100
50
0
1975 1980 1985 1990 1995 2000 2005 2010
polypropylene capacity to a 14 billion pound North strong growth in some markets. But since approxi-
American market. Cash cost margin for U.S. Gulf mately 65% of polypropylene consumption goes into
Coast polypropylene producers can be seen in Figure durable products like appliances and automotive
16. parts, economic downturns have a direct impact on
demand growth. With global economies now improv-
Over the past few years, the sustained lower pricing ing, a strong recovery for polypropylene is expected
and versatile properties of polypropylene versus cer- in 2004 and 2005. Global demand for polypropylene
tain competing materials have helped bolster very is expected to grow between six and seven percent

Figure 16
Polypropylene
Cash Cost Margin
20

15
Leader
Cents per Pound

Laggard
10

-5
'90 '91 '92 '93 '94 '95 '96 '97 '98 '99 '00 '01 '02 '03

22
 Figure 17
Global Polypropylene Demand by Region
60,000
Thousand Metric Tons

50,000

40,000

30,000

20,000

10,000

0
2000 2001 2002 2003 2004 2005 2006 2007 2010

North America South America

Western Europe Central and Eastern Europe
Middle East/Africa Total Asia

per year from 2003 through 2010 as seen in Figure global polypropylene leaders have exerted greater
17. This growth forecast has been lowered slightly influence on supply/demand dynamics by closing
from earlier estimates to reflect propylene shortages capacity when margins were unacceptable. Nearly
and the resulting impact on polypropylene pricing 1.6 billion pounds of polypropylene capacity was
and supply dynamics. closed in North America alone over the past two
years, and little new capacity has been announced.
The Impact of Producer Consolidation Producers have also begun to partially "uncouple"
polypropylene and propylene prices, increasing the
Consolidation in the polyolefin industry over the past influence of industry operating rates on market
few years has resulted in improved discipline among prices. With operating rates now climbing, some
suppliers, particularly in North America and idled capacity will be restarted in 2004 and 2005,
Western Europe. Over 20 major polyolefin compa- but with North American demand growing over 5%
nies have merged into seven leading global producers per year, a new world-scale polypropylene plant will
with increased market influence; be needed in 2004 and 2005. Suppliers could poten-
tially be sold out in 2005. Figure 18 demonstrates a
Basell: Elenac, Targor, BASF, changing global pattern for new polypropylene
Hoechst, Montell, Shell capacity:
BP: Amoco, Arco, BP, Solvay
ChevronPhillips: Chevron, Phillips Fewer new plants are being planned;
Dow: Dow, Union Carbide Most are outside North America - lower cost
Equistar: Lyondell, Millennium, and fastest growth is in developing regions
Occidental
ExxonMobil: Exxon and Mobil Polypropylene production will increase in regions
Borealis: Borealis, PCD with low-cost feedstock, and product focus will be on
commodity polymers for domestic and export mar-
Other mergers and acquisitions have occurred as kets. Producers in regions with higher feedstock
well, including Sabic and DSM, NOVA and DuPont costs will continue to limit expansions and differen-
Canada, and there is major restructuring underway tiate process and polymer technology to supply more
in the Japanese petrochemical industry. The new profitable markets.

23
 Figure 18
Global Polypropylene Capacity Additions by Region
(1000 Metric Tons/Year)
1800
1600
1400
1200
1000
800
600
400
200
0
2001 2002 2003
North America Latin America
The limited number of polypropylene expansions
over the next few years will be driven by:
Leading producers determination to keep supply
and demand in balance to improve profitability;
Limited capital for expansions as debt is
refinanced;
Propylene supply constraints in most regions
beyond 2004.
The Propylene Issue
Propylene derivative demand growth will begin to
outpace propylene availability by 2004, mainly driv-
en by high growth in global polypropylene markets.
Many regions continue to experience higher growth
for propylene than for ethylene, which has caused
supply/demand imbalances in propylene and increas-
ing propylene-to-ethylene(P/E) demand ratios as
seen in Figure 19. The propylene-to-ethylene price
ratios will also continue to increase.
U.S. refineries have been able to bridge the propy-
lene supply gap for the most part by using new zeo-
lite fluid catalytic cracking (FCC) catalysts, but the
availability of propylene from FCC units outside the
U.S. is limited as seen in Figure 20. Brazil, China,
and the U.S. are among the few countries with refin-
ery propylene currently available for petrochemicals.
Given what appears to be a structural problem with
the propylene supply side, new innovations are
expected to enhance supply from refineries, as well
2004 2005 2006 2007
Europe Asia Mid East
as force the development of alternative on-purpose
technologies. Propylene yields of 20% or more from
FCC units are becoming possible with catalyst tech-
nology from Davison Catalysts (APEX project). The
new technology is currently in the commercialization
stage, and a first application in an FCC unit is
expected to take place in 2004.
On-purpose routes include propane dehydrogenation
(PDH), olefin metathesis, olefin inter-conversion (e.g.
SUPERFLEXTM by KBR), deep catalytic cracking,
and gas-based routes like methanol-to-propylene
(MTP) and methanol-to-olefins (MTO). Only PDH,
olefin metathesis, and deep catalytic cracking have
been commercially tested, while Statoil and UOP are
testing the MTO route in pilot scale. MTO produc-
tion is very capital intensive because it requires con-
struction of a "mega-methanol" plant. Propane
dehydrogenation is particularly attractive in regions
with large quantities of low-cost propane like the
Middle East, where government incentives are
aggressively promoting production of
propane/propylene derivatives. Many integrated
PDH and propylene derivative plants will be con-
structed in the Middle East over the next few years.
Most of the propylene produced in the region will be
consumed captively for polypropylene. Due to rela-
tively low demand for polypropylene in the region,
and excellent logistics for supplying Europe and fast-
growing Asian markets, the Middle East will become
a huge net exporter of polypropylene resin over the
next decade as seen in Figure 21.
24
 Figure 19
U.S. Ethylene and Propylene Growth Comparison
40,000 0.7

u
0.61
u u
35,000
Thousand Metric Tons

u
0.6
u u u u u
u
30,000
u u u u u
u u u
u u u u u u
25,000

P/E Ratio
0.5
20,000 0.52
15,000 0.4

10,000
0.3
5,000

0 0.2
80 982 984 986 988 990 992 994 996 998 000 002
19 1 1 1 1 1 1 1 1 1 2 2

Ethylene Propylene u P/E ratio Linear (P/E ratio)

Figure 20
Propylene Sources by Region, 2002

100%

80%

60%

40%

20%

0%
North Latin EMEA Japan East Asia
America America

FCC Propane Dehydro Steam Cracker

25
 Figure 21
Global PP Trade in 1990, 2000, and 2010
2,000

1,500
Thousand Metric Tons

1,000

500

(500)

(1,000)

(1,500)
United Canada Latin Western Eastern Middle Africa Japan East Oceania
States America Europe Europe East Asia
Country/Region

1990 2000 2010

Conclusions supply on polypropylene growth in the future, since

New technology continues to play a major role in
polypropylene market development. Research work
on new polypropylene catalysts and polymers
remains strong despite the polymers maturity, and
new, enhanced polypropylene resins continue to
make inroads in non-traditional markets. In
essence, the value in use for polypropylene, which
has been historically undervalued, keeps expanding.
Of major concern is the impact of limited propylene
polypropylene accounts for over 60% of global
propylene consumption. New propylene supply from
alternate sources implies higher propylene prices to
make these routes economically viable. This will
push polypropylene prices up, reducing its partici-
pation in low-end commodity market sectors, but
increasing its value in differentiated applications.
Changing feedstock costs and demand in different
regions will result in a shift in global polypropylene
production and trade patterns in the future.

26
 Meeting Propylene Demands
with
SUPERFLEX Technology
by
Curtis Eng, Ray Orriss and Michael Tallman
KBR Olefins Technology
Houston, TX
Polypropylene continues to drive the need for addi-
tional propylene, especially in developing countries.
Most of todays propylene is a result of byproduct
recovery from either steam crackers or from refinery
conversion processes such as FCC operations. As
such, the byproduct propylene from these sources
can grow only as fast as the growth for ethylene or
transportation fuels. Ethylene growth rates have
lagged propylene growth rates and will continue to
do so in the future. Similarly, the growth rate of
transportation fuels is several times lower than
propylene. In addition, the shifting of steam cracker
feedstocks to lighter feeds produces less propylene
byproduct, which could result in a regional propy-
lene shortages requiring alternative on-purpose
propylene technologies.
Feed Sources For Propylene
Very simplistically, significant amounts of propylene
can be made from feeds as light as methane to heavy
oils from atmospheric tower bottoms (ATB). In most
cases, it is unrealistic for the existing propylene pro-
ducer to import large amounts of new feedstocks for
propylene production, rather the best source may be
with low value or problematic internal streams with-
in the producers refinery or steam cracker. Table II
27
gives a summary of major propylene production tech-
nologies as a function of feed source.
Currently, steam cracking and refinery operations
constitute over 97% of the propylene produced today.
Clearly, alternative routes to propylene will gain
prominence as producers seek to leverage their exist-
ing assets and available internal streams to find an
optimum solution for meeting the demand for propy-
lene. SUPERFLEX technology can be a solution to
meeting the propylene gap in the future.
SUPERFLEX Overview
SUPERFLEX is a fluidized catalytic cracking tech-
nology which converts olefinic streams from petro-
chemical or refinery sources to significant amounts
of propylene and ethylene. Ideal streams can be:
Mixed C4s from a refinery or steam cracker,
Raffinate 1 or Raffinate 2;
Mixed C5s from a refinery or steam cracker,
amylenes, TAME feed or raffinate;
Light cracked naphtha from a steam cracker, FCC
unit, coker or visbreaker;
Olefinic streams from Fischer Tropsch or other
processes
 Table II
Propylene Production Technologies
Feed Process Status Ultimate C3H6
Yield % of Feed

Methane Indirect, Methanol To Olefins, No commercial units yet 25-40%

methanol over custom catalyst

Ethylene Metathesis, requires clean, high Commercialized at Lyondell 90-95%

+ Butene purity olefins for reaction
Propane Dehydrogenation Several plants, but key is 80-85%
cost-effective propane pricing
Paraffins Conventional steam cracking Propylene recovered as a 13-16%
byproduct, the primary source
of propylene
C4-C10 Olefins inter-conversion over SASOL SUPERFLEX unit 40-50%
Olefinic proprietary ZSM-5 based will startup in late 2005
catalyst
Gas oil Conventional FCC unit 2nd major source of propylene 4-7%
but fairly low fuels growth
Gas oil High severity FCC unit with Many variations, including 15-25%
proprietary ZSM-5 based KBRs MAXOFINSM
additives
ATB High severity resid FCC with No commercial units, although 25-30%
specialized catalyst additives quite a bit of research by many

Lyondell Chemical Company (formerly Arco
Chemical Company) is the developer and owner of
SUPERFLEX technology. In 1998, KBR became the
exclusive worldwide licensor of SUPERFLEX. In
this role, KBR is entirely responsible for supporting
the technology, including the marketing, sales, devel-
opment, engineering and commercial aspects of
SUPERFLEX.
SUPERFLEX uses a fluid riser type reactor, quite
similar to a FCC reactor, to convert hydrocarbon
feeds, typically in the C4-C8 carbon range, to pre-
dominately propylene. Generally, the higher the
olefin content of the feed, the higher the propylene
yield. The original intent of the technology was to
convert available, low value streams to high value
petrochemical light olefins. In addition to propylene,
the major byproducts are ethylene and a highly aro-
matic gasoline stream. Figure 22 gives typical over-
all yields as a function of feedstock type. Overall,
ultimate propylene plus ethylene yields between 50-
70% can be achieved with olefinic feedstocks and the
recycle to extinction of unconverted C4/C5s from the
reactor.
A simplified flow sheet for the SUPERFLEX process
is shown in Figure 23. The reactor system employs
elements of KBRs FCC technology, backed by 65
years of experience and over 120 commercial units.
After feed preheat, the feed is converted in the riser
before the gas is separated from catalyst fines in the
upper disengager. Heat is recovered from the gas,
and the catalyst fines removed in an oil wash col-
umn. The cooled gas is then sent to the recovery sec-
tion for the production of polymer grade olefins.
Catalyst from the upper disengager is stripped and
regenerated in the lower section of the KBR convert-
er, and the catalyst returned to the riser reactor.

28
 Figure 22
Typical SUPERFLEX Ultimate Yields
Ultimate Yield, Wt.%
100%
80%
60%
40%
20%
0%
Mixed Mixed Light Cat
C4 C5 Naphtha
Compared to similar inter-conversion processes from
others, SUPERFLEX is clearly differentiated with
several process advantages, as follows:
The reaction temperature is high, leading to high
conversions with a higher propylene and much
higher ethylene yields;
Further, at these high temperatures, there is
significant conversion of both paraffins and
naphthenes in the feed, as well as olefins;
With a substantial conversion of most species in
the feed, SUPERFLEX can truly operate in a total
recycle mode, returning unconverted olefins,
paraffins and naphthenes in the effluent back to
the reactor.
SASOL SUPERFLEX Unit
In October 2002, Kellogg Brown & Root (KBR)
announced the award of a basic design engineering
package for a high-capacity propylene and ethylene
production facility for Sasol Technology Pty (SASOL)
in Secunda, Republic of South Africa. This facility is
part of SASOLs Synfuels Catalytic Cracker Project.
The heart of this new production facility is the
SUPERFLEX reactor technology licensed by KBR.
The technology meets SASOLs ethylene and propy-
lene needs and provides solutions to SASOLs clean
fuels requirements, as well as supplying other valu-
able by-products. With this project, SASOL will
become the first operator of the new SUPERFLEX
process when the unit starts up in late 2005.
C6+
C2 -
Propane
Ethylene
Propylene
Light
Coker
Naphtha
In the SASOL facility, the feed to the SUPERFLEX
reactor will be a Fischer-Tropsch derived hydrocar-
bon fraction in the C4 C11 range containing paraf-
fins, olefins, and oxygenates. The olefin cut further
includes a mixture of n-olefins and iso-olefins with
off-cuts of varying composition including both alpha
and internal olefins. The feed also contains an appre-
ciable amount of oxygenates which is processed in
the SUPERFLEX reactor without any prior separa-
tion or purification, and converted to valuable light
olefin products.
The reactor will have a production capacity of
approximately 250,000 metric tons per year of propy-
lene and approximately 150,000 metric tons per year
of ethylene. The reactor effluent will be combined
with other olefins streams for the ultimate produc-
tion of approximately 500,000 metric tons per year of
propylene and approximately 200,000 metric tons
per year of ethylene using a KBR proprietary recov-
ery scheme.
The SUPERFLEX cracking process will produce
other byproduct streams that meet SASOLs needs.
The C4 cut from the plant will be rich in iso-buty-
lene and used as a feed stream for SASOLs exist-
ing Cat Poly Unit. The C5+ gasoline product will be
a valuable high-octane (RON+MON)/2 > 100)
blending component. Finally, significant amounts
of ethane (cracked for additional ethylene produc-
tion), and propane (recovered and sold as LPG
product) are produced.
29
 Figure 23
Simplified SUPERFLEX Flow Scheme

Feed
C4/C5 Recycle R
E
SUPERFLEX Light gas
Converter C
O
Ethylene
V
To

E
stack Fuel
Flue Gas Oil Propylene
System
R
Y C6+
Catalyst

Oil
Wash
Regn Air

SUPERFLEX Applications However, coupling the SUPERFLEX concepts with

MAXOFIN technology leads to a patented process
In addition to stand-alone units, SUPERFLEX can that increases propylene yields to as much as 25
play an important role when integrated in ethylene wt.%, or about ten percentage points above high
plants or refineries: severity FCC units from others;

Steam Cracker Integration: Integration of SUPER-
FLEX in a steam cracker can lead to a shift in the
propylene/ethylene ratio from about 0.5 to at least
0.6. This is achieved by selectively hydrogenating
the mixed C4 stream and sending this and the mixed
C5s to the SUPERFLEX reactor. There is an added
benefit of making additional ethylene. Or if the
added ethylene is not needed, then the feed to the
steam cracker can be reduced significantly, as
SUPERFLEX makes substantial amounts of ethyl-
ene;
Upgrade Refinery Streams: Should mixed C4s or
light cracked naphtha have a low internal value,
SUPERFLEX can be added to convert these streams
to higher value products;
Petrochemical Refinery: Many producers are con-
sidering moving into higher value petrochemicals as
opposed to low margin transportation fuels. There
are conversion technologies such as a high severity
gas oil FCC technology (KBR MAXOFIN) that could
deliver large amounts of propylene from a refinery.
Aromatics Production: The SUPERFLEX gasoline
is quite rich in BTX. This can be recovered sepa-
rately as another high value product;
Conclusions
SUPERFLEX technology will continue to play a
strategic role in meeting future propylene demands
in a cost effective manner. Both refiners and ethyl-
ene plant owners will benefit from the conversion of
low value or problematic internal streams to high
value light olefins. Because of the robust and flexi-
ble nature of the technology, SUPERFLEX will
enable the producer to convert a wide variety of low
cost feeds into higher margin propylene and ethyl-
ene.
Acknowledgments
The authors graciously acknowledge the permission
and support of SASOL, especially Sias Swart and
Francois Moeller, in the preparation of this informa-
tion.

30
 TM
L E X
P E RF
Propylene S U

Solutions SCORETM

Your Keys

MA
XO
to success.

FIN
SM
F or over 50 years, KBR has provided solutions for the olefins
and refining industries. With recent technological innovations,
KBR is uniquely positioned to help you meet your propylene
production requirements. Your keys for achieving efficient routes to
and high yields of propylene are with KBRs proprietary technologies:

*SUPERFLEXTM Convert C4-C8 olefinic streams in a fluid riser bed

reactor to predominately propylene.

SCORETM Make significant amounts of propylene via steam cracking.

MAXOFINSM Use gas oil and heavy oils in an enhanced, high-olefins

FCC unit for maximum propylene yield.

These cost effective technologies combined with KBRs experience

and in-depth knowledge are your keys to success in the propylene
market.

*SUPERFLEXTM is a trademark of Lyondell Chemical Company.

Technology Worldwide Headquarters

601 Jefferson Ave. 4100 Clinton Dr.
Houston, TX 77002 Houston, TX 77020
Tel: 713.753.2000 Tel: 713.753.3011
Fax: 713.753.6644

www.halliburton.com KA036 2003 Kellogg Brown & Root, Inc. a Halliburton company All rights reserved
 ExxonMobil Chemical Licensing

A WISE INVESTMENT
IN YOUR FUTURE
Available for licensing
State-of-the-art technology
tested and demonstrated in
many ExxonMobil Chemical
and licensee plants around
the world
Olefins Leading steam cracking
technology, combining the highest
ethylene yield with low investment
and operating costs

Aromatics Industry-recognized,
leading-edge technologies for the
production of paraxylene, benzene,
ethylbenzene and cumene will keep
you at the forefront

Polymers The most flexible high-

pressure process for the production of
low-density polyethylene in autoclave or
tubular reactors

Catalysts Cutting-edge catalyst technology

for unique applications in refining and petro-
chemical processes

Licensed technology from ExxonMobil Chemical.

A wise investment for your future.

IT WORKS FOR US.

IT WILL WORK FOR YOU.

For a complete overview, visit the Technology section of our web site
at www.exxonmobilchemical.com or call (281) 834-5710.
Certain technologies are licensed through cooperations with other leading companies like
Univation Technologies, KBR, Stone & Webster, Axens and others.
2004 Exxon Mobil Corporation. The terms corporation, ExxonMobil, ExxonMobil Chemical, our and its, as used in this advertisement, some-
times refer not only to ExxonMobil Chemical Company, a division of Exxon Mobil Corporation, but collectively to all of the companies affiliated
with Exxon Mobil Corporation or to any one or more of them or their employees. License terms subject to final agreement.
 On-Purpose Propylene from
Olefinic Streams
by
Michael W. Bedell
ExxonMobil Process Research Laboratories
Baton Rouge, LA

Philip A. Ruziska
ExxonMobil Chemical Company
Baytown, TX

Todd R. Steffens
ExxonMobil Research and Engineering Company
Fairfax, VA

Abstract Propylene Needs

ExxonMobil recently completed development of a
new, on-purpose propylene technology based on cat-
alytic naphtha cracking, called the ExxonMobil
PCCSM Process. This process offers significant advan-
tages over prior systems. The development of this
technology was driven by the need for increased vol-
umes of propylene to supplement supplies of propy-
lene currently produced as co-products in steam
cracking and fluid catalytic cracking. The PCC
Process provides a means of converting olefin mole-
cules in naphthas to high value ethylene, propylene,
and, optionally, butylene. In addition, hydrogen con-
sumption and octane loss are reduced in subsequent
hydroprocessing of the naphtha required to meet low
sulfur mogas regulations.
Propylene is one of the fastest growing petrochemi-
cals, driven primarily by the high growth rate of
polypropylene (Figure 24). Polypropylene demand
currently is growing in the U.S. at 5%/year, and in
some regions of the world, the growth rate is consid-
erably higher.
While steam cracking continues to supply most of the
world's propylene, there is an increasing need for
propylene from other sources. The growth in steam
cracker capacity is driven by the need for ethylene,
and co-product propylene production is not keeping
up with propylene demand growth. Furthermore,
much of the new steam cracking capacity is based on
ethane feed, which produces little propylene.

33
 Figure 24
50M Ton Propylene Market Driven by Polypropylene
Propylene Oxo-Alcohol
Oxide 9%
7%
Acrylonitrile
10%
Polypropylene
64%
Propylene production from FCC units is the second
most important source of worldwide petrochemical
propylene supply. As demand has increased, refiners
have been able to increase propylene production in
FCC units (FCCU) by optimizing catalyst, ZSM-5
additive and operating conditions. In the U.S., FCC
propylene has, in fact, surpassed steam cracker
propylene as the largest source of U.S. petrochemical
propylene supply. However, the potential for addi-
tional production of propylene in existing FCC units
(FCCU) is limited by the capacity of the units and
the cost to debottleneck.
New on-purpose propylene technologies will be
required to provide the additional supplies of propy-
lene needed to meet the growth projections. Several
on-purpose propylene technologies are available,
such as propane dehydrogenation and metathesis,
but have seen only limited applicability. Propane
dehydro requires high investment and both technolo-
gies require opportunistic feedstock economics. A
newly emerging technology involving catalytic crack-
ing of olefinic naphthas and/or C4's can now be con-
sidered as well.
Olefin Cracking for Propylene
Catalytic cracking of olefinic streams to produce pri-
marily propylene along with ethylene and butylenes
has been described by several companies in recent
years. These processes are characterized by the use
of specially designed ZSM-5 catalysts to convert
higher molecular weight olefins and paraffins to
lighter olefins, with propylene being the olefin prod-
uct having highest yield (Figure 25).
34
Other
10%
source: CMAI
Production of such large volumes of propylene from
olefinic naphtha and C4 cracking requires large vol-
umes of olefinic feedstock. By far, the largest source
of olefinic feedstock molecules is cat naphtha from
FCCU, an order of magnitude larger than that avail-
able from steam cracking. Depending on the FCC
feed, processing conditions, and naphtha cut range,
cat naphtha may contain as much as 60% olefins,
which makes it ideal for catalytic conversion to
propylene. Figure 26 illustrates the relationship of
an integrated process scheme. Catalytic conversion
of cat naphtha olefins to propylene before hydrotreat-
ment converts most of the contained olefins to light
olefins, thereby further minimizing the potential for
octane loss in hydrotreatment. Concentration of the
higher octane aromatics, plus paraffin isomerization,
provides an increase in octane level of the residual
naphtha.
ExxonMobil PCC Process
ExxonMobil now is pleased to announce the develop-
ment of a new fluid solids naphtha cracking process
called the ExxonMobil PCC Process (Propylene
Catalytic Cracking). The PCC Process employs an
optimum catalyst, reactor design, and patented com-
bination of optimum operating conditions to achieve
a high degree of reaction selectivity and provide PCC
with economic advantages over prior fluid solids con-
figurations. These patented conditions and process
configuration are designed to minimize the down-
grade of gasoline molecules to fuel components.
 Figure 25
Reaction Equilibration in Catalytic Naphtha

Wt.% of Total Non-Cyclic Olefins 3 Product Feeds

3 4 5 6 7 8 9 10 11
Carbon Number

These conditions also produce product C2 and C3
streams that are highly concentrated in olefin con-
tent, resulting in lower investment for product recov-
ery. Specifically, the PCC reactor produces propylene
at the concentration required for chemical grade
propylene (95%), thereby avoiding costly product
fractionation. In addition, the optimized conditions
minimize the production of aromatics, which will be
an important consideration in meeting future gaso-
line regulations. These characteristics provide PCC
with economic advantages over prior fluid solids con-
figurations, as well as alternate on-purpose propy-
lene technologies, and are summarized in Table III.
ExxonMobil recently has completed the development
of this new PCC Process. The development program
has involved extensive testing in ExxonMobils pilot
facilities.

Figure 26
PCC Integration with FCC

Fluid Catalytic Cracker Propylene Catalytic Cracker

FCC: Primarily catalytic C4- minus

cracking of side chains
and saturated rings Chemical
Grade
PCC: Selective catalytic Naphtha
PCC Propylene
cracking of olefins
provides advantage
Distillate Improved
Improved Mogas to meet Mogas
emerging regulatory Blendstock
environment VGO
Feed Bottoms

ExxonMobil PCCSM Process

35
 Table III
Characteristics of PCC vs. Other Naphtha Cracking Processes

ExxonMobil Other Fluid Fixed Bed Propane

PCC Bed Processes Dehydro

Robust Reaction
Environment Yes Yes No Yes
Feed Flexibility Yes Yes Limited No
Selective Olefin
conversion Yes No Unknown n/a
Propylene
recovery cost Low High Unknown High
Residual naphtha
aromatics content Moderate High Unknown n/a

Conclusions References

Fluid solids processing has been found to be prefer-
able for on-purpose production of large volumes of
propylene from a wide variety of olefinic streams.
ExxonMobil has developed and optimized the design
of its new PCC Process in order to provide a cost
effective, best-in-class on-purpose propylene process.
PCC technology builds upon ExxonMobil's extensive
FCC and light olefin production background.
ExxonMobil Chemical currently is developing plans
to implement this technology at one of its own petro-
chemical sites, as well as evaluating making the
technology available for licensing.
[1] Chang, T., "Worldwide Ethylene Capacity Grows in Spite of
Warnings", Oil & Gas Journal, March 30, 1998, 41-55.
[2] Chem Systems Report, "Ethylene/Propylene", 96/97-6, March
1997.
[3] Chem Systems Report, "Routes to Propylene", 97/98S3,
February, 2000.
[4] Ladwig, P.K., et.al. "Process for Selectively Producing Light
Olefins in a Fluid Catalytic Cracking Process", U.S. Patent
6,069,287.
[5] "Propylur Route Boosts Propylene Production", European
Chemical News, March 27 - April 2, 2000, 47.

[6] Richards, D., "Ethylene Producers Wary as Economy Slows",

Chemical Market Reporter, Dec. 11, 2000, 5.

[7] Stell, J., "2000 Worldwide Refining Survey", Oil & Gas Journal,
Dec. 18, 2000, 110 - 119.

[8] "U.S. Polypropylene Demand to Expand 6%/Year",

Hydrocarbon Processing, October, 2000, 23.

[9] Ware, R. A., "Mobil Olefins Interconversion Technology (MOI)

- A Flexible Propylene Production Alternative", presented at Chem
Systems' Annual U.S. Chemical Conference, Jan. 27 - 28, 1999.

[10] "Wasted or Wanted - Who Values Propylene?", European

Chemical News, November 6-12, 2000, 56-59.

36
 Advanced Catalytic Cracking
Technologies for Production of
Light Olefins from Low Cost
Refinery Based Feedstocks
by
Dilip Dharia, Warren Letzsch and Lark Chapin
Stone & Webster Engineering Corporation
Houston, TX
The changing supply and demand situation for
propylene, as described in detail by CMAI (1, and
article in this issue), will force refiners to put addi-
tional emphasis on recovering propylene from FCC
units. The two key approaches are:
Maximize recovery of propylene from existing units
and increase propylene production by using
additives and new catalysts.
Build new catalytic cracking units, such as Deep
Catalytic Cracking with high yields of propylene
(20 to 25 wt.%).
Deep Catalytic Cracking (DCC)
Deep Catalytic Cracking is a commercially proven
fluid catalytic process for selectively cracking a wide
variety of hydrocarbon feedstocks to light olefins,
particularly propylene and isobutylene (2, 3). DCC
was originally developed jointly by Sinopec and the
Research Institute of Petroleum Processing (RIPP) in
China. Stone & Webster (S&W) is the exclusive
licensor of the technology outside of China.
DCC Process & Product Yields
The DCC flow scheme is similar to that of a conven-
tional Fluid Catalytic Cracker (FCC) unit. The main
fractionator and light ends recovery use the same
basic configuration with the necessary adjustments
required for different yield structures. DCC opera-
tion is similar to FCC in the way the catalyst is han-
dled and regenerated. DCC is in fact an extension of
FCC technology, with more severe operating condi-
tions compared to FCC, but less severe compared to
steam cracking (SC) as summarized in Table IV.
Maximum typical yields for a DCC unit operating in
a propylene mode are shown in Table V. DCC pro-
37
 Table IV
Typical Operating Parameters

FCC DCC CPP SC

Reactor Temp., C 500-550 505-575 560-650 760-870

Residence Time, Seconds 1-3 1-10 1-3 0.1-0.2
Press., Atm. 1-2 0.7-1.5 0.8 1
Cat/Oil, (w/w) 5-10 7-15 15-25 -
Steam Dilution Rate, 1-6 6-30 30-50 30-80
wt.% of Feed
duces significantly less dry gas and more LPG than The lack of secondary exothermic hydrogen transfer
SC and more dry gas and LPG compared to FCC. reactions results in a much higher heat of reaction.
This is what would be expected, since the SC opera- The combination of the higher endothermic heat of
tion is predominantly thermal cracking while DCC is reaction with the higher reactor temperature leads to
mainly catalytic cracking. The ethylene content is a higher coke yield for the process.
three to four times greater in DCC than in FCC.
To meet polymer grade propylene specifications, a
The C5+ naphtha from the DCC has a high octane number of purification and processing steps need to
92.9 (R+M)/2, is rich in BTX components and is suit- be included. Typical contaminants which need to be
able for extraction, if desired. The naphtha may removed are mercaptans, sulfur, COS, arsine and
need to be selectively hydrotreated to improve its water. The ethylene contents are high enough to
stability. make recovery worthwhile in a nearby ethylene
plant.

Table V
TPI DCC Yields
Test date 1998 1997
Feedstock HT Arabian light VGO plus HT Arabian light VGO plus
6.5% DAO and 11% Wax 7% Wax
Catalyst CRP-1 20% CRP-1 and 80% CRP-S
Reactor temp/C 565 559
Yields/wt.%
C2- 11.6 10.3
C3+C4 41.5 40.0
C5+naphtha 35.7 31.9
RON 98.5 99.3
MON 85.3 85.3
Olefin Yields/wt.%
Ethylene 5.3 5.1
Propylene 18.5 17.4
Bytylenes 13.3 11.0
In which
Isobutylene 5.9 4.8

38
DCC Feedstock
DCC uses various types of heavy feeds such as: VGO,
hydrotreated VGO, deasphalted oil, lube oil waxes,
coker gas oils and atmospheric residue.
DCC Catalyst
these catalysts in 1997 and in 1998. The propylene
yield of both test runs exceeded the design value of
16.7 wt.%. The naphtha octane values are high due
to the high aromatics and iso-olefin content. The
isobutylene selectivity was excellent resulting in
near equilibrium concentrations (44 wt.% of the total
butylenes).

DCC catalysts are designed to possess the following
characteristics: high matrix activity for the primary
cracking of the heavy hydrocarbons; modified meso-
pore zeolite with a pentasil structure for the second-
ary cracking of gasoline; high skeletal isomerization
activity; and low hydrogen transfer. A series of DCC
catalysts has been formulated to meet DCC process-
ing objectives, such as low delta coke and high met-
als tolerance, required for processing resids.
DCC Commercial Experience
DCC is well proven commercially with seven DCC
units in operation with a total feed rate of more than
three million tons per year and over 50 years of com-
bined operating experience. The light olefin yields
that are consistently produced in these units are list-
ed in Table VI.
In mid-1997, the first Stone & Webster designed and
engineered DCC complex was successfully commis-
sioned in Thailand for Thai Petrochemical Industries
(4). CRP-S catalyst was developed with lower activ-
ity specifically for start-up operation. CRP-1 was
used for all subsequent makeup additions. Table V
shows the results of two test runs conducted with
Currently, the TPI plant is running at 120% of its
original design capacity with more than 30 wt.%
atmospheric residue oil in the feedstock. Although
the feedstock is much heavier, the propylene yield is
just below the design value.
Catalytic Pyrolysis Process (CPP)
Todays very competitive environment and the supply
and demand situation for light olefins and petroleum
products are forcing refiners and petrochemical pro-
ducers to integrate their facilities to improve profit
margins. If they have a choice, refiners would like:
A process that offers the flexibility to use heavier
and less expensive feedstocks to produce both
ethylene and propylene;
A process that enhances ethylene and propylene
yields, as well as provides control over the E/P ratio
of his product slate so profitability can be
maximized at all times.
A new catalytic cracking process has been developed
by RIPP and Sinopec that meets these requirements.
S&W in conjunction with RIPP/Sinopec is offering
this new process known as the Catalytic Pyrolysis

Table VI
DCC Light Olefin Yields

Refinery Daqing Anqing TPI Jinan Jinan

Operation Mode DCC-I DCC-I DCC-I DCC-I DCC-II
Feedstock Paraffinic Naphthenic Arabian Intermediate base
VGO+AR VGO VGO+DAO VGO+DAO
+WAX
Reaction temp/C 545 550 565 564 530
Olefin Yields/wt.%
Ethylene 3.7 3.5 5.3 5.3 1.8
Propylene 23.0 18.6 18.5 19.2 14.4
Butylenes 17.3 13.8 13.3 13.2 11.4
Isobutylene 6.9 5.7 5.9 5.2 4.8
Isoamylenes - - - - 5.9

39
 Table VII
CPP Commercial Test Operating Conditions and Product Yields

Table VIIa Feedstock Properties

Density(20C), g/cm3 0.9012

CCR, wt.% 4.7
Hydrogen, wt.% 12.84
Sulfur, wt.% 0.16
Nitrogen, wt.% 0.25
Nickel, ppmw 6.3
Composition, wt.%
Saturates 55.5
Aromatics 28.0
Resin 15.7
Asphaltene 0.8

Table VIIb Operating Conditions & Product Yields

OPERATING MODE MODE 1 MODE 2 MODE 3
Operating Conditions
Feed rate, t/h 9.73 8.00 5.90
Reaction temp. C 576 610 640
Reaction pres. MPa(g) 0.08 0.08 0.08
Regeneration temp. C 720 725 760
WHSV, h-1 2.5 4.0 no bed
Catalyst/oil ratio 14.5 16.9 21.1
Steam/oil ratio 0.30 0.37 0.51
Product Yield, wt.%
H2S 0.08 0.08 0.08
C2- 17.73 26.50 37.48
C3 C4 43.97 36.86 28.72
C5+ Naphtha 17.94 17.76 14.96
LCO 11.82 9.05 8.00
Coke 8.46 9.75 10.76
100.00 100.00 100.00
Olefin Yield, wt.%
Ethylene 9.77 13.71 20.37
Propylene 24.60 21.45 18.23
Butylenes 13.19 11.34 7.52

40
Process utilizing its expertise in both FCC and ethyl-
ene technologies.
CPP is an extension of FCC; it is actually a hybrid of
FCC and conventional steam cracking technology
with the following features (5):
Proprietary zeolite catalyst developed by RIPP that
promotes both free radical and carbenium ion
cracking mechanisms;
Specialized operating conditions in terms of
temperature, hydrocarbon partial pressure and
space velocity. The CPP process operates at a
higher temperature with more steam than that for
FCC or DCC, as shown in Table IV. However, they
are significantly less severe than steam cracking.
Of note is that the most severe CPP operation tested
to date can be tolerated in most modern RFCC units
as the upper regeneration limit is 760C and the
upper reaction temperature is 650C.
CPP Feedstock
CPP produces ethylene and propylene from VGO or
heavy oil feedstocks. In general, all feeds applicable
for FCC operation can be used in CPP. Blending
residua into the feed can help with the heat balance,
as the heat of reaction and severity of operation are
significantly elevated over a conventional FCC oper-
ation.
CPP Commercial Trial
Three test cases were conducted using a Daqing
crude feed blend of 45% VGO blended with 55% VTB.
The three modes of operation were as follows: maxi-
mum propylene (Mode 1), maximum ethylene (Mode
3) and an intermediate between the two (Mode 2).
The maximum propylene mode of operation (CPP-1)
operates at the lowest severity with the lowest steam
requirement. The maximum ethylene mode (CPP-3)
operates at the highest severity with reaction tem-
peratures as high as 650C and the highest amount
of dilution steam (50 %). The intermediate mode of
CPP operation (CPP-2), as expected, operates
between the two aforementioned modes. Major oper-
ating parameters and product distribution are shown
in Tables VII.
The commercial trial showed that the production of
ethylene and propylene was 20.37 wt.% and 18.23
wt.%, respectively, when producing maximum ethyl-
ene and was 9.77 wt.% and 24.60 wt.% when produc-
ing maximum propylene as shown in Table VII. This
process is unique because it gives the operator the
ability of changing the propylene to ethylene ratio by
changing the process operating conditions. The feed
cost of CPP is much lower for producing ethylene and
propylene compared with a steam cracker.
CPP Unit Integration with a Steam Cracker
CPP can be integrated with a steam cracker as
shown in Figure 27, offering very attractive econom-
ics. In this integrated scheme, only the front-end of a
CPP unit is required, consisting of the reac-
tor/regenerator section and the main fractionator.
CPP produces a gasoline and lighter product stream
from the overhead of the main fractionator that is
very similar in composition to the cracked gas stream
from the overheads of the primary fractionator in an
olefins facility that cracks primarily liquid feed-
stocks. Hence, the overheads of the CPP main frac-
tionator feed the olefins unit water quench tower.
The remainder of the olefins facility, i.e. the cracked
gas compressor and the product recovery systems, is
designed the same as an olefin plant to separate and
purify the gasoline and lighter gases into the desired
products.
This configuration is applicable for both expansion of
an existing olefins facility or as a part of a new
olefins complex. The scheme offers significant
advantages such as lower feedstock cost, feedstock
flexibility and control over P/E ratio.
41
 Figure 27
Ethylene/CPP Unit Integration
Stone and Webster World-Leading Olefin Technology

C4/C5 Fuel Gas

LSWR
CPP
Cracked Gas C2=

C3 =
Recovery
Naphtha Pygas
or Cracked Gas
C2/C3
SC Furnace
C2/C3

Conclusion References

The refining and petrochemical industries are seek-
ing lower cost routes for propylene production. DCC
is commercially well proven and offers a reliable low-
cost route to propylene using heavy, less expensive
feedstocks. The process enables the refiner to extend
his product slate into higher margin petrochemicals.
A new CPP process has emerged based on proven
FCC and DCC technologies to produce light olefins
from heavy feedstocks. This new process offers very
attractive economics coupled with feed and product
flexibilities when integrated with a steam cracker.
[1] Zinger, Stephen J., "Demanding Customers & Erratic Supply:
The Challenges of Managing C3 and C4 Olefin Business", CMAI
World Petrochemical Conference, March 2003, Houston, TX,
[2] Zaiting, Li, Fukang, Jiang; Chaogang, Xie; and Youhao, Xu;
"DCC Technology and Its Commercial Experience", China
Petroleum Processing and Petrochemical Technology, No. 4,
December 2000.
[3] Peiling, Zhou; "Integration of a DCC Unit into a Refinery",
Hydrocarbon Engineering, October, 1997.
[4] Fu, Andrew; Hunt, David; Bonilla, Jorge; and Batachari,
Andrew; "Deep Catalytic Cracking Plant Produces Propylene in
Thailand", Oil & Gas Journal, Jan. 12, 1998.

[5] Swaty, Tim; McCue, Dick; Chapin, Lark; Letzsch, Warren; and
Dharia, Dilip, "Catalytic Pyrolysis Process (CPP) and Its
Integration with a Refinery and a Petrochemical Plant", Fifth
International Petroleum Conference and Exhibition, January
2003, New Delhi, India.

42
 Stone

Stone & Webster We turn monumental challenges into magnificent solutions.

Some of the toughest projects become the most enduring achievements. At Stone & Webster, were known for exceeding
our Process customers expectations in the new economy. Using state-of-the-art practices, well generate a seamless
system that links engineering, procurement, fabrication, and construction
phases together into an impressive resultone that will have your competitors
staring in wonder. Visit us at www.shawgrp.com for more information.

43
ENGINEERING PROCUREMENT CONSTRUCTION FA B R I C AT I O N E N V I R O N M E N TA L MAINTENANCE C O N S U LT I N G
44
 A New FCC Process Upgrades
Gasoline and Maximizes
Propylene
by
T. Ino and Y. Fujiyama
Nippon Oil Corporation, Tokyo, Japan
H. Redhwi, A. Aitani and M. R. Saeed
King Fahd University of Petroleum & Minerals, Dhahran, Saudi Arabia
Introduction
The FCC unit continues to be the dominant conver-
sion process in the petroleum refinery, and increas-
ingly its desired product slate is being shifted toward
light olefins production. The product slate from the
fluid catalytic cracking (FCC) unit looks attractive
when propylene is desired. Despite the technologies
available to increase light olefins production in the
FCC unit, an intense research activity in this field is
still running. The conventional FCC process is being
modified in a joint research project between King
Fahd University of Petroleum & Minerals, Saudi
Aramco, Japan Cooperation Center-Petroleum and
Nippon Oil Corporation to a high-severity FCC
process suitable for an integrated refinery-petro-
chemical complex [1]. The technology provides an
olefin-driven process with the flexibility and per-
formance capabilities to make it a key driver to refin-
ery profitability. KFUPM and JCCP have piloted a
novel high-severity fluid catalytic cracking (HS-FCC)
process that can increase the yield of light olefins to
40 wt.% of the product, versus the normal 10wt.%.
The process combines mechanical modifications with
changes in process variables and catalyst formula-
tions [2-5]. The main operating regime of this novel
refining process is high reaction temperature, short
contact time, high catalyst/oil ratio and a special
down-flow reactor system.
45
Process features of HS-FCC
The process scheme of the HS-FCC process consists
of several steps such as reaction, stripping, regener-
ation, and separation. Oil feedstock is dispersed with
steam and fed to the system, then contacted with the
hot regenerated catalyst in a downer reactor and is
catalytically cracked. Coke deposited on the catalyst
is stripped with steam and transferred to the regen-
erator where air is introduced and coke on the cata-
lyst is removed by combustion. The hot regenerated
catalyst is returned to the reactor via a catalyst hop-
per at a controlled circulation rate to achieve heat
balance of the system.
Down-Flow Reactor
A down-flow reactor system has been adopted for HS-
FCC process. The catalyst and the feed flow down-
ward along with gravity to minimize back mixing in
the reactor and to obtaining a narrower distribution
of residence time. The selection of an optimum resi-
dence time allows the maximization of intermediate
products such as gasoline and light olefins. The
down-flow reactor permits higher catalyst/oil ratio
because the lifting of catalyst by vaporized feed is not
required. As with most reactor designs involving
competing reactions and secondary product degrada-
tion, there is a concern over catalyst-feed contacting,
back mixing, and control of the reaction time and
 Figure 28
Benefits of Down-flow Reactor in FCC Operation
temperature. The down-flow reaction would ensure
plug flow without back mixing. Since the FCC
process involves successive reactions, the desired
products such as olefins and gasoline are considered
intermediate products. A suppression of back mixing
is the key to achieve maximum yield of these inter-
mediates. Figure 28 shows the benefits of operating
in a down-flow mode.
High-Reaction Temperature
Conventional FCC is typically operated at low to
moderate severity (510C to 530C riser outlet tem-
perature) with flexibility to swing between maxi-
mum gasoline and maximum distillate mode.
Attempts to operate the FCCU at high severity to
produce more light olefins are not economically
attractive because incremental light olefins will come
at the expense of secondary cracking of gasoline. The
secondary cracking of gasoline will result in exces-
sive dry gas (C2 and lighter) yields. While the FCCU
has the capability of running at very high reactor
temperatures, this approach is first being looked at
to improve the conventional FCC process. The HS-
FCC unit is operated under considerably higher reac-
tion temperatures (550 to 650C) than conventional
FCC units. Under these reaction temperatures, how-
ever, thermal cracking of hydrocarbons also takes
place concurrently with catalytic cracking, resulting
in increased undesirable products as dry gas and
coke.
Short Contact Time
The time-temperature relationship for the conven-
tional FCC suggests there is an optimum operating
window. If the residence time is too low, the bot-
toms cracking suffers while high reactor tempera-
tures and long residence times promote dry gas
production. The short residence time (less than 0.5
sec) of feed and product hydrocarbons in the down-
er should be favorable to minimize the thermal
cracking. Furthermore, undesirable successive
reactions such as hydrogen transfer reactions,
which consume olefins, are being suppressed. In
order to attain the short residence time, the cata-
lyst and the products have to be separated immedi-
ately at the reactor outlet. For this purpose, a high
efficiency product separator has been developed
capable of suppressing side reactions (oligomeriza-
tion and hydrogenation of light olefins) and coke
formation accelerated by condensation.
46
 Figure 29
Schematic Diagram of HS-FCC Pilot Plant with Downer Reactor
Dispersion
Stream
3
3
3
Gas Analysis Down Flow
3 Reactor
3
Wet Gas 3 Wet Gas
Meter
Air
Regenerator
High Catalyst/Oil Ratio
In order to compensate the decrease in conversion
due to the short contact time, the HS-FCC process
has to be operated at high catalyst to oil ratios (C/O),
in the range of 15 to 25. As mentioned earlier, the
other advantage of operation at high C/O is the
enhanced contribution of catalytic cracking over
thermal cracking. Catalytic and thermal cracking
proceed simultaneously in FCC reactions. It is well
known that the ethylene yield is lower and isobuty-
lene yield is higher in catalytic cracking compared to
thermal cracking at the same conversion. By increas-
ing the catalyst/oil ratio, the effects of operating at
high reaction temperature (thermal cracking) are
minimized. High C/O increases conversion and
decreases temperature drop during the endothermic
cracking reaction. Therefore, high C/O maintains
heat balance and helps minimize thermal cracking,
over-cracking, and hydrogen transfer reactions.
Pilot Plant Study
Experimental
Experiments were conducted in a downer-type pilot
plant with a capacity of 0.1 bbl/d. The pilot plant con-
sists of a downer reactor, stripper, regenerator, and
47
3
Catalyst
Hopper
3
Feed Oil
333
3
Meter
Stripper Stabilizer
3
catalyst hopper. Figure 29 presents a schematic flow
diagram of the HS-FCC pilot plant (Davison
Circulating Riser, modified to operate in "downer"
mode). Feed oil is charged into the upper part of the
downer reactor together with dispersion steam.
Regenerated catalyst is also charged to the top of the
reactor from the catalyst hopper. At the outlet of the
downer, product hydrocarbons are separated imme-
diately from catalyst in the stripper, where heavy oil
adsorbed on the spent catalyst is stripped by steam,
and then spent catalyst is sent to the regenerator.
Catalyst circulation rate is calculated from the delta
coke and coke yield. Typical design parameters of the
pilot plant test are presented in Table VIII. All tests
were conducted at 600C and a catalyst/oil ratio of 40
using a hydrotreated vacuum gas oil (VGO) of
Arabian Light origin. The base catalyst is a low
cracking activity catalyst containing H-USY type
zeolite with low acid site density. The catalyst was
modified with 10 wt.% of a high activity ZSM-5, sup-
plied by Davison Catalysts. The ZSM-5 additive is
widely used in the FCC process to increase octane
and light olefins yields. The base catalyst and addi-
tive were deactivated with 100% steam at 810C for
six hours in a fluid-bed steamer before evaluation.
 Table VIII
Reaction Conditions of Downer and Riser Pilot Plants

Parameter Type of Reactor

Downer Riser
Reactor Outlet Temperature C 600 600
Pressure (Stripper Top) kPa 98 98

Hydro treated VGO feed

Rate kg/h 0.4-1.2 0.7-1.0
Preheat C 280 280
Catalyst
Proprietary catalyst
Inventory L 8 2
Steam Pretreatment for 6h C 810 810
Circulation rate kg/h 13-40 13-18
Cat/Oil ratio kg/kg 13-40 13-30

Table IX
Comparison of ZSM-5 Addition in Conventional FCC and HS-FCC
Conventional FCC: Pilot Plant Data Generated in
Davison Circulating Riser (DCR)
HS-FCC: Pilot Plant Data Generated in DCR modified for "Downer" mode.

Conventional FCC HS-FCC

Base Base +10 wt.% Base Base +10 wt.%
Product Yields wt.% Catalyst high activity Catalyst high acitivity
ZSM-5 additive ZSM-5 additive
Dry Gas 5.3 6.4 4.6 5.5
Propylene 7.5 13.0 10.7 18.4
Butylenes 8.8 13.6 16.1 17.8
Total C3-C4 Olefins 16.3 26.6 28.7 39.3
LPG 20.7 29.3 30.9 40.5
Gasoline 43.4 34.1 45.4 34.0
Light Cycle Oil (LCO) 15.0 15.4 9.4 9.3
Heavy Cycle Oil (HCO) 14.3 13.4 6.6 7.1
Coke 2.3 2.1 3.1 3.5

48
Results of Pilot Plant Tests
The base catalyst has a low-hydrogen transfer activ-
ity which is preferred for light olefins production.
However, operating at high reaction temperature
and high C/O ratio compensated for the low cracking
activity of the base catalyst [6,7]. Short contact time
also suppressed hydrogen transfer reactions. Based
on the intrinsic features of HS-FCC, maximum light
olefins yield can be obtained by the combination of
optimized catalyst system and operating conditions.
The yields of light olefins, LPG, gasoline, LCO, HCO,
and coke make are presented in Table IX for conven-
tional FCC and HS-FCC. In conventional FCC, the
base catalyst yielded about 16 wt.% light olefins and
43.4 wt.% gasoline compared to 29 wt.% light olefins
and 45 wt.% gasoline in HS-FCC. In the case of ZSM-
5 addition, the yield of light olefins increased to more
than 37 wt.%, particularly propylene which showed
an increase of 72%.
The results showed that ZSM-5 is highly selective
toward propylene relative to Y-Faujasite containing
base catalyst. In both cases, the rise in light olefins
was accompanied with a drop in gasoline yield since
the addition of ZSM-5 accelerates the cracking of
gasoline to lighter products. The addition of ZSM-5 is
effective in catalytic systems where the base cata-
lysts have low-hydrogen transfer activity. The yield
of light olefins for the base catalyst (with and with-
out ZSM-5) increased with increasing conversion.
However, increasing ZSM-5 additive content to 25
wt. % showed a minor increase in the yield of light
olefins.
49
Concluding Remarks
With proper design and operation, the HS-FCC
process is in the best position to produce light olefins
for petrochemicals usage. As per process technology,
reactor configuration has a major impact on operat-
ing requirements, conversion and product selectivi-
ties. Catalytic cracking under high severity in a
downer-type reactor boosts overall conversion and
enhances the production of gasoline and light olefins.
The results of preliminary economic evaluation show
that the additional production of propylene and
paraxylene plays a major role in the economics of the
upgraded refinery with HS-FCC option.
References
1. A. Maadhah, M. Abul-Hamayel, A. Aitani, T. Ino, and T.
Okuhara, "Down-flowing FCC Reactor Increases Propylene and
Gasoline Make", Oil and Gas Journal, Aug 14, 2000, p. 66.
2. Y. Fujiyama, "Process for Fluid Catalytic Cracking of Oils", US
Patent No. 5,904,837, May 18, 1999.
3. T. Ino and S. Ikeda "Process for Fluid Catalytic Cracking of
Heavy Fraction Oil", US Patent No. 5,951,850, September 14,
1999.
4. Y. Fujiyama "Process for Fluid Catalytic Cracking of Heavy
Fraction Oils", US Patent No. 6,045,690, April 4, 2000.
5. T. Ino, T. Okuhara, M. Abul-Hamayel, A. Aitani, and A.
Maghrabi, "Fluid Catalytic Cracking Process for Heavy Oil", US
Patent No. 6,656,346, December 2, 2003.
6. T. Okuhara, T. Ino, M. Abul-Hamayel, A. Maghrabi, and A.
Aitani (2001) "Effect of ZSM-5 Addition on Product Distribution in
a High Severity FCC Mode", Petroleum Science and Technology,
19, p. 685.
7. Aitani, A., T. Yoshikawa and T. Ino (2000). "Maximization of
FCC Light Olefins by High Severity Operation and ZSM-5
Addition", Catalysis Today, 60, p. 111.
 Is your CAT purring?

Let us take a look at it.

Our in-depth FCC design knowledge and technical
service experience will deliver innovative, cost
effective solutions to maximize your FCC units
performance.
Our patented feed injection nozzles, direct-
coupled cyclones and riser technology can provide
superior yields and run lengths, as proven in many
units throughout the world.
Whether integrating this technology into an
existing FCC unit or building a grassroots unit, your
plant will deliver the best performance possible.
For more information on this and other Lummus
refining technologies, call us at 713-821-5381, fax us
at 713-821-3587, or email us at fcc@us.abb.com.

ABB Lummus Global

3010 Briarpark Drive
Houston, Texas 77042 USA

50
Make Propylene the FCC/SCC Way
by
Dalip Soni
ABB Lummus Global
The FCC unit, the most flexible and trusted work-
horse of the refining industry, has successfully met
the increasing challenge of producing high octane
motor fuels. It is now being challenged to meet the
demands of the petrochemical industry for more
propylene, or even ethylene.
The FCC unit is flexible in several ways. Its mode of
operation can be easily changed to maximize either
motor fuels, like gasoline and diesel, or petrochemi-
cals. This unit is also able to process a wide range of
feedstocks from naphtha boiling range materials to
portions of vacuum residue. Thus an FCC unit is an
ideal fit for a frequently fluctuating marketplace.
This paper discusses how a modern FCC unit, as
designed by ABB Lummus Global, can be used to pro-
duce more propylene. Lummuss FCC unit is shown
in Figure 31. It incorporates the hardware and the
design features needed to achieve the highest con-
version and selectivity to lighter products. This unit
is operated in Selected Component Cracking (SCC)
mode to maximize production of propylene. In the
SCC mode of operation, certain components of the
FCC product slate and/or cracked or straight run
products from other units are recycled back to the
same riser or fed to a second riser as shown in Figure
30. This mode of operation can provide very high
propylene yield with relatively low dry gas and coke
production. This design and operation of the FCC
unit is based on a thorough understanding of the
interactions between the FCC reaction paths, the
operating conditions, and catalyst formulation.
FCC Reaction Paths
In an FCC unit, the main catalytic cracking reactions
proceed via the formation of an olefin. Larger olefins
crack to form smaller olefins. However, olefins can
also react to form naphthenes or paraffins as shown
in Figure 31. These undesirable side reactions need
to be eliminated, or reduced substantially, to maxi-
mize the yield of propylene. Thus for high propylene
production, the reaction conditions, catalyst, and
51
 Figure 30
FCC Unit Modified for Selected Component Cracking (SCC)

Direct Coupled Cyclones

SCT Riser SCT Riser

Advanced Stripper
Internals

RCSP

MicroJet Injectors
Square Bend
Transfer Line

From Second RCSP

52
 Table X
FCC Unit Operated in SCC Mode:
Product Yields
Feed, VGO
Riser Outlet Temp.
C2 minus, wt.%
C3, wt.%
C3=, wt.%
C4s, wt.%
C5 to 221 C, wt.%
LCO, wt.%
HCO, wt.%
Coke, wt.%
design of the unit should maximize production of
larger olefins and then preferentially crack them
to smaller ones, while hindering the slower side
reactions.
FCC Unit Operation
The inherent flexibility of the FCC unit enables it to
be run in SCC operating mode wherein the hydro-
carbon molecules can be selectively cracked to shift
the product slate in favor of a higher yield of propy-
lene. The operating parameters that significantly
influence the yield of propylene and also the design
of the unit include temperature, residence time,
hydrocarbon partial pressure, and the catalyst type.
As with many chain reactions, initiation and termi-
nation are important steps. For initiation, quick feed
vaporization and contact with the active sites on the
catalyst are critical. These requirements led to the
design of the patented MicroJet feed injectors and
the feed injection zone of Lummuss FCC unit. High
temperature/high severity is required for initiation
and to crack the larger olefins to propylene. MicroJet
injectors enhance the ability of the unit to be operat-
ed at very high temperatures while minimizing the
detrimental effects of high temperature operation,
such as high dry gas and coke.
The reaction time, on the other hand, has to be con-
trolled to inhibit slower, undesirable hydrogen trans-
fer and other side reactions that reduce the produc-
tion of lighter olefins and produce higher amounts of
dry gas and coke. This requirement, along with the
need to operate the unit at high temperature, influ-
ences the design of the FCC riser reactor and the ter-
25.9 API
570 C
7.23
2.82
23. 84
20.40
25.46
9.57
3.21
7.50
mination device at the end of the riser. The products
made in the riser need to be quickly and efficiently
recovered at the end of the riser to maximize propy-
lene selectivity. This is accomplished in Lummuss
FCC unit by the use of a cyclone system (two stages)
that is directly connected to the riser. A unique fea-
ture of the system is that the primary cyclone oper-
ates at a lower pressure than that in the cyclone con-
tainment vessel. The recovery of hydrocarbons at the
end of the riser is almost complete, post riser resi-
dence time is minimized, and undesirable side reac-
tions are essentially terminated.
In the SCC mode of operation, the FCC unit is run at
a significantly lower hydrocarbon partial pressure.
At lower hydrocarbon partial pressure, larger olefins
selectively crack to smaller olefins to yield high
propylene production. Lower hydrocarbon partial
pressure is attained by operating the unit at lower
pressure and/or by using higher amounts of feed dis-
persion steam or additional steam injection in the
riser. Lummus has optimized the operating pressure
of the unit to yield the highest propylene selectivity.
The catalyst formulation is another critical factor in
high propylene production. In the SCC mode of oper-
ation, an optimized catalyst formulation converts
larger olefins to propylene and other light olefins.
This catalyst formulation consists of a high activity
base catalyst that maximizes the primary cracking
reactions and minimizes the undesirable bimolecular
reactions that destroy the olefins produced in the
first step of the cracking reactions. This base catalyst
is then mixed with a certain amount of catalyst from
the high activity, shape-selective ZSM5 family of
catalysts.
53
 Figure 31
Reaction Paths in FCC
To maximize propylene yield, undesirable olefin side reactions
to naphthenes or paraffins must be minimized.

4
Naphthenes

4Olefins
io n
l iza t
cyc
Paraffins hyd

4Paraffins
rog
en
tran
sfe
r

4
Paraffins
fer

4Olefins
ans
H-tr

4
Naphthenes

4Branched
iso

4
de me
hy riza
dra tion
ti on

4Aromatics + (H )
Olefins
Cycloolefins + (H2)
2

4 Unsubstituted
cracking
Aromatics + Olefin

4 Heavy Coke or
de Ring
hy
dra
ti on

Heterocyclic Aromatics

4
n Naphthenes
lizatio
cyc

4Smaller Olefins
cracking
Olefins

4Paraffins
hyd
rog
en t
ran
s fer

54
The FCC unit operated in SCC mode can attain very
high propylene yield as shown in Table X. Figure 32
shows the jump in propylene yield selectivity that is
achieved by following this approach. Propylene yield
of over 24 wt.% can be attained depending on the
feedstock characteristics.
Maximizing propylene production requires maximiz-
ing the production of gasoline-range larger olefins to
feed the reactions catalyzed by ZSM5. Therefore,
the FCC unit design and the operating conditions
must first give the highest conversion to gasoline-
range material. Advanced FCC reaction system hard-
ware, along with a high activity base cracking cata-
lyst, is essential to achieving a higher propylene
yield.
LUMMUS FCC Unit Design
The thrust of the Lummuss design philosophy for
the FCC unit is to reduce delta coke (i.e. coke added
to the catalyst as it passes through the reaction zone)
so that the regenerator temperature is relatively low
and the catalyst-to-oil (C/O) ratio is very high at the
high riser temperature required in the SCC mode of
operation. In addition, selected lighter components
are recycled to the same riser at an appropriate point
where the reaction severity is maximized and thor-
ough contact of this material with the catalyst is
achieved. In cases where a large amount of the light
material needs to be cracked or re-cracked, a sepa-
rate riser reactor can be employed as shown in
Figure 30.

Figure 32
FCC Unit Operated in SCC Mode Yields
Increased Propylene Selectivity

n
io
r at
e
e op
n
pyle
C3H6 Selectivity

o
pr
um
xim
Ma ne ope r
ation
yle
ed prop
Increas

60 65 70 75 80 85 90
Feed Conversion, wt.%

55
The unit design aspects that reduce the delta coke,
increase the catalytic conversion, and provide the
high degree of selectivity to lighter products are:
MicroJet Feed Injectors: The heart of the
injector is a specially designed tip that generates
several micro-jets of finely atomized feed. These
small jets combine to form a flat fan spray. The
design achieves uniform distribution of the feed
across the tip and in turn across the riser cross
section.
Short Contact Time Riser: The riser is precisely
designed for the optimum contact time and
velocity profile as calculated using advanced
kinetic and hydraulic models. The velocity in the
riser is calculated at various points along the
length of the riser to better ascertain
hydrodynamic conditions in the riser.
The optimized riser design is key to increased
catalytic conversion, reduced delta coke, and high
olefin selectivity.
Reaction Termination Device/Direct-Coupled
Cyclones: As discussed, the unique feature of this
proprietary system is that the primary cyclone is
at a lower pressure than that in the cyclone
containment vessel, resulting in a negligible
amount of vapors entrained with the separated
spent catalyst. This reduces delta coke
substantially and the yield and selectivity of light
olefins is increased.
Advanced Stripper Design: The small amounts of
product vapors entrained with the spent catalyst
and in the pores of the catalyst are removed in the
high efficiency stripper. The stripper internals con
sist of perforated plates or baffles positioned in
such a way as to utilize almost all the cross
sectional area of the stripper vessel for catalyst
flow, and at the same time maximize surface area
for mass transfer between the fluidized catalyst
phase and stripping steam. The lower catalyst
velocity (higher catalyst residence time), along
with thorough and uniform contact of the catalyst
and the stripping steam, provides very high
stripping efficiency. In addition, the advanced
design ensures that the stripping efficiency does
not drop with increases in catalyst mass flux.
The FCC process operated in SCC mode offers a flex-
ible, stepwise approach to the production of higher
quantities of propylene. Depending on the feedstock,
propylene yield of over 24 wt.% is achievable. The
FCC unit is a tried and trusted conversion/upgrading
process in the refining industry and can be easily tai-
lored to meet the demands of the petrochemical
industry.
56
 ZSM-5 FCC Additive Development
A Brief History
by
Girish K. Chitnis
ExxonMobil Research and Engineering Company
Fairfax, VA
and
Thomas F. Degnan
ExxonMobil Research and Engineering Company
Annandale, NJ

Introduction octane from non-traditional sources. Beginning in

Almost two decades passed between the initial dis-
covery of ZSM-5 in 1965 and its initial commercial
trial in a cracking unit in 1983. That initial com-
mercial trial in Neste Oys Naantali, Finland refinery
was the product of many years of painstaking testing
and analysis of ZSM-5 activity, selectivity, and sta-
bility in both laboratory and pilot scale catalytic
cracking units. ZSM-5 FCC additive development
within ExxonMobil is the subject of a separate
review (1).
Interestingly, the motivation for developing a ZSM-5
additive changed over the course of its development.
In the early 1980's, lead was eliminated from gaso-
line which prompted a search for a means to increase
the mid-1980's, a manifest need developed for "clean-
er gasoline", depleted of sulfur, olefins, and aromat-
ics. This, in turn, produced more favorable econom-
ics for light paraffin-olefin alkylation. Finally, in the
early 1990's, a robust market for polypropylene drove
an interest in producing more propylene from FCC
units.
Early Cracking Catalyst Evaluation
Landolt and Argauer first synthesized ZSM-5 in 1965
(2). Because it was only synthesized in very small
quantities (<5g), ZSM-5 remained a laboratory
curiosity. In 1967 it was first evaluated for process-
ing waxy gas oils and was soon determined to be a
very shape-selective material that preferentially

57
cracked normal or slightly branched paraffins. For
much of the late 1960s most of the ZSM-5 that was
synthesized was directed toward the development of
new dewaxing catalysts (3).
When ZSM-5 was first evaluated as a cracking cata-
lyst, its initial evaluation was quite unremarkable.
A blend of 10% REY and unsteamed 5% ZSM-5 eval-
uated in a fixed fluid bed gave the same octane
improvement as the REY alone. Separate experi-
ments aimed at evaluating the effect of processing
wide cut FCC gasoline over ZSM-5 also showed that
gasoline research octane was not affected. However,
additional experiments showed that the heavier frac-
tion of FCC gasoline (355K+) could be separately
upgraded over ZSM-5 and that octane did increase
when this was blended back into the lighter gasoline.
In the early 1970s efforts to evaluate ZSM-5 in
cracking applications began to gain momentum. By
then, several studies with small quantities of ZSM-5
showed that mildly steam deactivated ZSM-5 did, in
fact, improve gasoline octane. However, the mecha-
nism for octane improvement was not yet under-
stood. Prior to considering ZSM-5 for service in TCC
and FCC units, several key properties of the zeolite
had to be thoroughly studied. Principal among these
were steam stability, metals resistance, and selectiv-
ity maintenance.
ZSM-5 Zeolite Manufacture
Another major hurdle along the path to achieving
producing a ZSM-5 FCC additive was actually the
commercial manufacture of the ZSM-5 crystal. Prior
to ZSM-5, virtually all zeolites were manufactured by
low temperature, atmospheric pressure synthesis.
Higher-pressure syntheses using organic directing
agents were mainly the province of scientists work-
ing in academic and industrial laboratories.
"Templated zeolites" were first synthesized in 1960
by Barrer and Kerr (4), but the scale-up of these
materials remained a challenge. Thus, there were no
precedents to draw upon when ExxonMobil decided
to construct its own pilot scale zeolite synthesis and
catalyst plant in Beaumont, Texas in 1973. Over the
next five years, the demand for fixed bed ZSM-5 cat-
alysts transformed the plant from a pilot scale facili-
ty to small catalyst manufacturing plant. Still, the
capacity of the plant was not sufficient to supply the
needs of a process as large as FCC. The economies of
scale achieved through several plant expansions and
the experience gained in synthesizing ZSM-5 in larg-
er and larger volumes, decreased the manufacturing
costs to the point where cracking applications could
at least be considered.
Thermofor Catalytic Cracking ZSM-5 Catalyst
Commercialization
The Thermofor Catalytic Cracking (TCC) unit of the
Neste Oy refinery in Naantali, Finland was the set-
ting in 1983 for the first full scale commercial trial of
ZSM-5 in a catalytic cracking unit (5). The bead cat-
alyst contained both REY and ZSM-5. A TCC, rather
than an FCC, was used because of ExxonMobils
experience with TCC catalyst formulation and TCC
unit operation. The renewed emphasis on octane
prompted by the phase out of tetraethyl lead had
transformed the economics of ZSM-5 addition.
In the trial, gasoline RON and MON both showed
steady increases that paralleled the ZSM-5 addition
rate. Gasoline yield decreased. However, this was
offset by increases in propylene and butylene. The
ZSM-5/REY catalyst was added over the course of 92
days. The stability of the gasoline octane uplifts was
the most surprising result of this test. Based on lab-
oratory testing, it was anticipated that product
octane and yields would revert to pre-test levels soon
after the ZSM-5 addition stopped. However, the
three to five number RON and two number MON
shifts were sustained through nearly the entire trial,
even though gasoline yield returned to the original
values fairly quickly. It is now known that the long-
lived residual octane enhancement results from the
relatively stable isomerization activity of ZSM-5
compared with the shorter-lived cracking activity.
ZSM-5's olefin cracking activity is responsible for
gasoline yield loss. The TCC catalyst was commer-
cialized by ExxonMobil as Durabead 11 (6).
Development of the Additive Concept
One of the critical questions in the development of a
ZSM-5 catalyst was whether ZSM-5 could be incor-
porated into a separate additive or whether it was
most effective when incorporated in the same parti-
cle as the Y-zeolite. Testing showed that there was
no synergy between Y and ZSM-5 and therefore the
separate additive case was attractive. The main rea-
son for combining ZSM-5 and Y in the same particle
was to reduce the effect of dilution attributable to the
additional binder used in the additive. The separate
particle approach was attractive mainly because it
allowed much greater flexibility in ZSM-5 addition
and make-up rate.
ZSM-5 FCC Additive Development
The events leading up to the development of a ZSM-
5 FCC additive and subsequent milestones are
depicted in Figure 30. Davison Catalysts was instru-
mental in scaling up the manufacturing of a ZSM-5
58
 Figure 34
ZSM-5 Additive Development Timeline

ZSM-5 Lab & Pilot Scale First Commercial Ultra-high activity

Discovered Cracking Studies Cracking Trial (TCC) ZSM-5 Additive
of ZSM-5 at Neste Oy Introduced
Steam and Metals High ZSM-5
Tolerance Evaluated Additive Demonstrated

1965
{ 1975
ZSM-5 First
Commercially
Manufactured
1985

Selective ZSM-5
1995

Additive Commercial
2000

Demonstration
Initial Lab
Cracking
Studies First FCC Trial
of ZSM-5 Additive

only additive and was the first company to introduce
a commercial ZSM-5 additive for FCC in 1984.
Davison has been improving the technology ever
since.
Phosphorus Stabilization of ZSM-5
Several studies have demonstrated the benefits of
phosphorus on the stability and shape-selectivity of
ZSM-5 (7).
The benefit of adding phosphorus appears to be due
to its ability to retard aluminum from leaving the
zeolite framework. Phosphorus reduces the initial
acidity of the zeolite but, after severe steaming,
produces a zeolite that retains a larger fraction of
its acidity. MAS NMR analyses have shown that
the stabilization of cracking activity is entirely due
to the improved retention of framework aluminum
in ZSM-5.
Phosphorus has also been used as a marker for
the ZSM-5 additive that allows refiners to track the
amount of ZSM-5 in the catalyst FCC inventory.
Beginning in 1987, ZSM-5 additive manufacturers
began to add phosphorus to their formulations.
The effects were dramatic in improving the effec-
tiveness of ZSM-5 and reducing the amount of
additive required to achieve the desired effect on
octane and light olefin yield. The increased effec-
tiveness translated into reduced additive costs for
refiners and ultimately led to a much wider use of
the ZSM-5 additive.
Development of Selective ZSM-5 Additives
Many refiners make use of the additional propylene
and butylene for alkylate feed. The resulting alky-
late usually more than offsets the gasoline loss pro-
duced by ZSM-5. Nevertheless, a demand developed
in the late 1980s for an additive that produced
octane shifts similar to ZSM-5 but without the gaso-
line losses obtained with the conventional ZSM-5.
ExxonMobil began work on such an additive in 1986
and by 1988 had commercially demonstrated a
selective version that provided similar shifts in
RON and MON at roughly half the gasoline yield loss
(8). While some FCC operators still use this type of
additive, the current focus on propylene maximiza-
tion has driven most refiners to use high activity ver-
sions of ZSM-5.
Process Modeling ZSM-5 Yield Predictions
Extensive laboratory work on the chemistry of ZSM-
5 catalyzed cracking together with large riser pilot
scale and commercial evaluations allowed several
companies to construct process models (9). The mod-
els are capable of predicting yield shifts and octane
changes as a function of ZSM-5 loading, feed proper-
ties, riser operating conditions, riser configuration
and base cracking catalyst properties. It has been
updated over the past ten years to incorporate the
results of more recent work on FCC conventional and
selective additives (10,11). The model includes a
decay function for ZSM-5 coking along with kinetics

59
and associated rate constants for the primary reac-
tions. This model permits a tailoring of the ZSM-5
addition rate for particular applications.
Recent ZSM-5 Additive Developments
Additives with high levels of ZSM-5 have only
become commercially available in the last few years
(12). These new ZSM-5 additives produce high levels
of light olefins with minimal dilution of the base
cracking catalyst. Indeed, ExxonMobil conducted its
own trial of a high ZSM-5 additive at its Joliet refin-
ery. The results of that trial verified the value of
high levels of highly active ZSM-5 in the inventory
for the production of propylene and butylenes. More
recently, a new generation of ultra-high activity
ZSM-5 additives, Davisons OlefinsUltra, has been
reported to deliver high yields of propylene while
allowing the refiner to reduce fresh catalyst addi-
tions(13). If coupled with improved hardware modifi-
cations such as closed cyclones, improved atomizing
nozzles and second risers of lift zones for recracking
FCC naphtha, the impact of such new ZSM-5 addi-
tives on propylene and butylene makes can be mag-
nified even further.
Conclusions
Nearly two decades passed between the discovery of
ZSM-5 and its widespread acceptance as a fluid cat-
alytic cracking additive. The development of ZSM-5
technology for FCC was unique in the significant
number of challenges that the technology had to
address on the path to commercialization.
However, the significant incentives provided by the
need for additional gasoline octane in the early
1980s combined with more recent favorable econom-
ics for producing light olefins provided the momen-
tum to overcome all these hurdles.
References
[1] T. F. Degnan, G. K. Chitnis, and P. H. Schipper, "The History
of ZSM-5 FCC Additive Development at Mobil," Microporous and
Mesoporous Materials, Vol. 35-36, 245 (2000).
[2] R. J. Argauer and G. R. Landolt, U. S. Patent 3,702,886,
November 14, 1972.
[3] N. Y. Chen, W. E. Garwood, and F. G. Dwyer, Shape Selective
Catalysis in Industrial Applications, 2nd ed., Mercel Dekker, New
York, 1996.
[4] D. A. Breck, Zeolite Molecular Sieves, John Wiley Interscience,
New York, 1973.
[5] C. D. Anderson, F. G. Dwyer, G. Koch, and P. Niiranen,
Proceedings of the Ninth Iberoamerican Symposium on Catalysis,
Lisbon, Portugal, 1984.
[6] C. D. Anderson, L. L. Breckenridge, R. G. Bundens, F. G.
Dwyer, and J. A. Herbst, Natl. Pet. Refiners Assoc. Annual
Meeting, San Antonio, TX, March 29-31, 1987.
[7] W. W. Kaeding, J. Catal. 61 (1981) 240.
[8] R. P. L. Absil, R. J. Cimini, G. W. Kirker, D. A. Pappal, J. A.
Herbst, and D. J. Klocke, RPS Seminar on Advances in Fluid
Catalytic Cracking Technology, Houston, TX, November 12-14,
1991.
[9] P. H. Schipper, F. G. Dwyer, P. T. Sparrell, S. Mizrahi, J. A.
Herbst, S. P. Donnelly, and A. Huss, Jr. ACS Symp. Ser. 375, 1988,
p. 64.
[10] J. S. Buchanan, Appl. Catal. 74 (1991) 83.
[11] J. S. Buchanan, Appl Catal. A: Gen, 171 (1998) 57.
[12] P. K. Niccum, R. B. Miller, A. M. Claude, M. A. Silverman, N.
A. Bhore, K. Liu, G. K. Chitnis, and S. J. McCarthy, NPRA Annual
Meeting, San Francisco (1998).
[13] J. R. D. Nee, Catalagram 91 (2002)
60
 Davison 8500 Series
Polypropylene Catalysts
for Superior Resins
by
Kyle Lorton
Marketing Manager, Polypropylene Catalysts
Davison Catalysts
Davison Catalysts, the worlds leading supplier of
catalysts for polyolefin production, announces our
8500 Series polypropylene catalysts for producing
polypropylene resins with properties that are superi-
or to other impact copolymers (ICPs) and random
copolymers (RCPs) and, at minimum, competitive
with other homopolymers (HPs).
With a half-century of experience in polyolefin cata-
lyst assembly technology and our fundamental mate-
rial science position, Davison has expanded our cata-
lyst portfolio with the acquisition of Borealis ABs
spherical magnesium chloride (MgCl2) production
capacity. We now produce fourth-generation,
Borealis-developed, polypropylene catalysts that are
commercially proven in the SpheripolTM and
BorstarTM process technology platforms.
The Davison 8500 Series high performance Ziegler-
Natta catalysts have demonstrated commercial suc-
cess in producing HP, RCP, and ICP resins for
-Injection molding
-Film
-Fibers
-Blow Molding
-Thermoforming
These catalysts are cost effective in slurry, bulk and
bulk/gas phase processes and provide an outstanding
combination of high activity, polymer morphology,
and polymer properties. Our 8500 Series includes
catalysts with a particle size range of 35 to 75
microns in size.
Other notable performance achievements of our 8500
Series catalyst family include higher HP isotacticity
levels versus the isotacticity levels received from con-
ventional catalysts. Stiffness properties in both the
HPs and ICPs are extraordinary without sacrificing
ability to control stereospecificity. Both the RCPs
and ICPs have a high degree of comonomer random-
ness. Lastly, the desired isotacticity, melt flow rate
(MFR), molecular weight distribution, and
comonomer content are easily controllable through
the polymerization conditions.
Figure 35, laboratory data comparing XPO 8501 to
the same competitive PP catalyst, demonstrates the
higher activity of XPO-8501 compared to the same
competitive PP catalyst, at all ranges of Al/Si ratio.
Figure 36 demonstrates the TEAL/donor ratio versus
xylene solubles (XS) of XPO 8501. The lower XS val-
ues translate to superior crystallinity and strength of
the homopolymer resins.
61
 Figure 35
XPO 8501s Donor Response Activity

60

50
XPO 8501
Activity Kg/g

40

30

20
Competitive Catalyst A

10

0
0 10 20 30 40
Al/Si

Figure 36
XPO 8501 Delivers Superior Crystallinity
8
Donor Response XSRT
7

6
XS wt.%

5
Competitive
4 Catalyst A

2
XPO 8501
1

0
0 5 10 15 20 25 30 35 40

Teal/Donor Molar Ratio

Davisons 8500 Series polypropylene catalysts are Kyle Lorton

currently being commercially used and providing Marketing Manager,
operation enhancement in the Spheripol and Polypropylene Catalysts
Borstar processes. For more information on these Davison Catalysts
proven, superior catalysts or to find out how
Davisons extensive history of collaborative relation- W. R. Grace & Co.
ships can provide you with a total catalyst solution to 7500 Grace Drive
the meet the specific needs of your process technolo- Columbia, Maryland 21044 USA
gy segment, contact: (410) 531-4148
kyle.lorton@grace.com

62
Davisons 8500 Series
Commercially proven to deliver
superior polypropylene resins

Davison Catalysts is pleased to announce the

8500 Series of Ziegler-Natta polypropylene
catalysts for producing resins with superior
properties. In commercial operations, Davison
8500 Series catalysts have achieved excellent
results, yielding HP, RCP, and ICP resins for a
complete range of end uses, including injection
molding, film, fibers, blow molding, and
thermoforming.

These fourth-generation, Borealis-developed

catalysts have proven success in the
Spheripol and Borstar process technology
platforms. Davisons 8500 Series catalysts
are cost effective in slurry, bulk and bulk/gas
phase processes, providing an outstanding
combination of high activity, polymer
morphology, and polymer properties.

For more information on how the Davison

8500 Series of polypropylene catalysts can
improve your resins, contact:

Kyle Lorton
at (410) 531-4148;
e-mail kyle.lorton@grace.com.

catalysts@grace.com
Lin
k your refinery to the
propylene opportunity
As the demand for propylene outpaces the
supply from steam crackers, operators of FCC
units will have opportunities to further boost
revenues by making incremental propylene for
the petrochemicals market.
ZSM-5 based additives are the most cost
effective way to increase propylene production
in the FCCU. OlefinsUltra provides the highest
For more information on OlefinsUltra or any of Davisons FCC ZSM-5 additives, contact:
Jim Nee
Phone: +1 (410) 531-8212
Fax: +1 (410) 531-8248
e-mail: james.nee@grace.com
activity per pound of any commercially proven
ZSM-5 additive and is now being used in 17
FCC units around the world. In one commercial
application, a major European refiner obtained
more than 8 wt.% propylene, while cutting
ZSM-5 consumption by almost half. This en-
abled the refiner to reduce fresh catalyst con-
sumption by more than 10%.
Markus Lesemann
Phone: +1 (410) 531-4597
Fax: +1 (410) 531-8248
e-mail: markus.lesemann@grace.com
 2004 W.R. Grace & Co.-Conn.

Davison Catalysts Davison Catalysts Davison Catalysts Europe

W.R. Grace & Co.-Conn. Asia Pacific Grace GmbH & Co. K.G.
7500 Grace Drive W.R. Grace Pte. Ltd. In der Hollerhecke 1
Columbia, MD 21044 501 Orchard Road Postfach 1445
(410) 531-4000 #05-11/12 Wheelock Place D-67545 Worms, Germany
Singapore 238880 49 (6241) 40300
(65) 6737-5488
catalysts@grace.com
The information contained herein is based on our testing and experience and is offered for the user's consideration, investigation and verification. Since
operating and use conditions vary and since we do not control such conditions, we must DISCLAIM ANY WARRANTY, EXPRESSED OR IMPLIED, with
regard to results to be obtained from the use of this product. Test methods are available on request.