Catalagram

No. 115 | Fall 2014

®

A Catalysts Technologies Publication

GRACE®, CATALAGRAM®, ACHIEVE®, OlefinsUltra® GSR®, SuRCA®, SHAC®, HYAMPP®, MAGNAPORE®, POLYTRAK®, D-PriSM®, OlefinsMax®, CONSISTA®, and Super
DESOX® are trademarks, registered in the United States and/or other countries, of W. R. Grace & Co.-Conn.

DCR™ and Talent | Technology | Trust™ are trademarks of W. R. Grace & Co-Conn.

ApART®, DX®, ART®, ART & Design®, and ADVANCED REFINING TECHNOLOGIES® are trademarks, registered in the United States and/or other countries, by Advanced
Refining Technologies LLC.

UNIPOL® and UNIPOL UNIPPAC® are trademarks of The Dow Chemical Company or an affiliated company of Dow. W.R. Grace & Co.-Conn. and/or its affiliates are licensed
to use the UNIPOL® and UNIPOL UNIPPAC® trademarks in the area of polypropylene.

ACE™ is a trademark of Kayser Technology.

This trademark list has been compiled using available published information as of the publication date of this journal and may not accurately reflect current trademark
ownership or status. GRACE CATALYSTS TECHNOLOGIES is a business segment of W. R. Grace & Co.-Conn.

© Copyright 2014 W. R. Grace & Co.-Conn. All rights reserved.

The Leader
EDITORIAL

In Catalysts On June 30, 2014, Grace announced the appointment of

Albert F. Beninati Jr., as President of its market-leading
$1.1 billion Grace Catalysts Technologies segment.

Built on talent, technology, and trust, Grace® high-performance specialty chemicals

“I’m excited to challenge Grace’s global catalysts teams to
and materials improve the products and processes of our customer partners continue to put customer value at the center of the world’s
around the world. A Fortune 1000 company, Grace (NYSE: GRA) is a leading broadest, fully-integrated portfolio of complementary
global supplier of catalysts, engineered and packaging materials, specialty
construction chemicals, and building materials. Al Beninati, President catalysts technologies.”
Grace Catalysts Technologies
Grace Catalysts Technologies develops and manufactures catalysts and related
products/technologies used in energy and refining, polyolefins and plastics,
as well as petrochemical and other chemical manufacturing applications. Dear Friends,

After 24 years in the chemical industry and many commercial and business leadership roles, it’s truly a pleasure
to settle at Grace and assume leadership of an organization built on the greatness of its members. And it’s an
honor to lead a global business that develops and manufactures catalysts and related technologies for energy and
refining, polyolefins and plastics, and other applications. From FCC and hydroprocessing catalysts to polyolefin
catalysts, supports, and gas-phase polypropylene process technology, the Grace Catalyst Technologies portfolio is
broad and truly is built on talent, technology, and trust.
A Global Leader in Catalysts, Materials
and Construction Technologies In fact, longtime Catalagram® readers will notice that, for the first time in a decade we have incorporated news from
across our catalysts portfolio, including an article introducing our UNIPOL® Polypropylene Process Technology.
Catalysts Technologies
As I meet new people now, it’s tempting to introduce Grace in terms of its amazing history of catalysts technology
#1 in FCC catalysts breakthroughs and decades-long relationships with some of the best companies in the world. But it’s even more
intriguing to look ahead to the opportunities to help customers succeed in the new landscape driven by non-
#1 in resid hydroprocessing catalysts traditional crudes, rising demand for plastics, environmental imperatives, true global markets, and so much more.
What strikes me as so promising is that Grace’s model of close customer partnership, technology leadership, and
#1 in independent polyethylene catalysts flexible worldwide manufacturing is so well suited to the uncertainty and change driving our industry.
#2 in hydrocracking catalysts Of course, we’re very proud of our top positions in FCC catalysts, resid hydroprocessing catalysts, independent
polyethylene and independent polypropylene catalysts. Yet, I’m especially excited about what these leadership
#2 in polypropylene catalysts
positions mean for our customers. Working with a leader means you’re not left wondering if there is a better team to
Leading polypropylene process licensor solve the complex riddles of catalysts chemistry and refinery operations, or to reach across the portfolio to address
a variety of catalysts challenges. Working with the leader means you don’t have to worry that you’re not delivering
Materials Technologies the most reliable catalyst to your process. Working with the leader means partnering with an organization whose
commitments you can count on and who is focused on excellence. If there’s anything I’ve learned in this life, it’s that
#1 in specialty silica gel excellence is fun.

#1 in can sealants This fall the Grace Catalysts Technologies teams are pleased to be participating in the 2014 AFPM Q&A and
Technology Forum in Denver and the ERTC 19th Annual Meeting in Lisbon. Through customer visits and other
Construction Products industry events, I look forward to meeting the fascinating people who form the global community of Grace
customers and partners.
#1 in cement additives
#2 in concrete admixtures
Al Beninati
President, Grace Catalysts Technologies

2 Catalagram® No.115 | Fall 2014 3

NEWS
“We’re also pleased to further our
cooperation with Oman’s oil refining
industry as well as ties to the local
(left to right) André
Lanning, Grace Catalysts
Technologies(EMEA) community in Oman.”
General Manager; Abdullah
Al Farsi, Orpic ICV Team
Leader; and Raymond
Volker, Sohar University
Vice-Chancellor
Building on Orpic ICV Achievements
Orpic, Grace, and Sohar University to Create State-of-the-
Art Laboratory in Oman
Sohar, Sultanate of Oman— the nearby Orpic refinery. Grace
On September 3, at the Crowne will provide technical support in
Plaza Hotel Sohar, officials from the training of personnel and,
Orpic, W. R. Grace & Co. (NYSE: as the world’s leading supplier
GRA), and Sohar University signed of FCC catalysts, will assist in
a Memorandum of Understanding knowledge transfer to support Sohar
(MoU) marking the first phase in a University’s research programs.
three-party collaboration designed to
create and sustain a state-of-the-art The agreement is a result of
R&D facility at Sohar University at an discussions early in 2014 between
estimated cost of over USD 3 million. Orpic and Grace regarding ways
of creating In-Country Value
The R&D facility will be equipped (ICV) for Oman. Sohar University
with the latest catalyst testing was then approached and
technology, and will employ subsequently became an integral
highly skilled Omani scientists. part of the partnership. This initiative
The advanced catalyst testing underscores Grace’s commitment
techniques utilized in the laboratory to the petroleum refining industry
will result in a high-quality service in Oman and the Middle East and
with rapid response times for many represents the first step toward
of the technical requirements of long-term cooperation intended to
Catalagram® Editor-in-Chief: Contributors:
Rosann Schiller John Aikman, Grace
Issue 115 | Fall 2014
Maadh Al Badrin, Orpic
Managing Editor: Talal Al-Rawahi, Grace
Kendra Parlock Colin Baillie, Grace
Ann Benoit, Grace
Stefan Brandt, Grace
Ken Bryden, Grace
4 Catalagram® No.115 | Fall 2014
-André Lanning, Grace
spur more joint activities, technology
development, training, and
knowledge transfer to Oman.
Commenting at the ceremony,
Abdullah Al-Farsi, Orpic’s Head of
ICV, said, “This is a fine example
of creating In-Country Value, a key
policy in Oman and one which Orpic
wholeheartedly supports. Having
access to such a modern laboratory
will be of paramount significance to
Omani students, and it will be just 20
km away from Orpic’s Sohar Refinery,
reinforcing the support our refinery
teams need to safely and profitably
operate our business. The initiative
represents excellent technology and
knowledge transfer opportunities to
Omani scientists as well.”
Marta Calvo, BP Castellon
Ella Chen, Grace
Wu-Cheng Cheng, Grace
Nathan Ergonul, Grace
Christoph Fougret, Grace
Rafael Gonzalez, Grace
Stuart Kipnis, Grace
Jürgen Knöll, Grace
André Lanning, the General
Manager for Grace in the region,
said “We’re excited by this
collaboration, which will serve
the interests of all three partners.
Grace will be able to improve
service with a faster response
to its customers in the region
thanks to the close proximity of
the laboratory to key customers
including Orpic. We’re also
pleased to further our cooperation
with Oman’s oil refining industry
as well as ties to the local
community in Oman.”
“This cooperation will enhance
Sohar University’s research
and development capability by
providing access to world-class
expertise in the field of catalysis,
as well as bringing skilled jobs to
the country,” said Professor Ray
Volker from Sohar University. v
Angel Llanes, BP Castellon
Jeff Nicolich, Grace
Charles Olsen, ART
Ana Pietra, BP Castellon
Terry Roberie, Grace
Greg Rosinski, ART
Dilip Singh, Orpic
Udayshankar Singh, Grace
CONTENTS
EDITORIAL 28 ART RESPONSES
3 AL BENINATI 1.
2.
Improving ULSD product color
Cloud point improvements
A welcome from new Grace Catalysts
Technologies President Al Beninati 3. Pre-treatment options for Tier 3
4. Understanding silicon poisoning
5. Renewable diesel and biodiesel
NEWS
4 NEW LAB IN OMAN CUSTOMER PARTNERSHIP
Global leadership and customer partnership
working at the regional level 35 REDUCING SOx
EMISSIONS AT BP CASTELLON
TECHNOLOGY LEADERSHIP USING FCC ADDITIVES
6 ADVANCES IN PROPYLENE FCC additives offer an attractive alternative
to reduce SOx emissions
MAXIMIZATION
38 IMPROVING SAFETY,
FROM THE FCC UNIT
A new method to characterize ZSM-5 based RELIABILITY AND
PROFITABILITY AT THE ORPIC
materials is introduced
13 ADDRESSING SOHAR REFINERY
Grace‘s catalyst management solutions
POLYPROPYLENE DEMAND stand up to the challenge at the Sohar
Leading the way with UNIPOL®
RFCC unit
Polypropylene Process Technology
AFPM Q&A RESPONSES
Grace FCC and ART HPC experts address
market trends and answer questions
submitted to the 2014 AFPM Q&A and
Technology Forum held in Denver, Colorado:
16 GRACE FCC RESPONSES
1. FCC gasoline sulfur reduction strategies
2. Tight oil impacts of FCC operations
3. LCO maximization best practices
4. Reducing particulate emissions
5. Enhancing FCC butylene selectivity
Brian Watkins, ART
Mike Ziebarth, Grace
7500 Grace Drive | Columbia, MD 21044 | 410.531.4000
Please address your comments to:
Kendra.Parlock@grace.com © Copyright 2014 W. R. Grace & Co.–Conn
5
TECHNOLOGY LEADERSHIP
Advances in Propylene
Maximization from the
FCC Unit
Udayshankar Singh, Senior R&D Engineer
v (methanol to gasoline), and in petroleum upgrading (gasoline
Mike Ziebarth, Director Catalyst Research
Terry Roberie, Director Corporate Analytical
Wu-Cheng Cheng, Director Research & Development
Jürgen Knöll, Senior Analytical Chemist
Christoph Fougret, Manager Catalyst Evaluations
Stefan Brandt, Director Evaluations and Technical
Support
Jeff Nicolich, Senior Analytical Chemist
Abstract: Using UCV to Understand ZSM-5
Dealumination and Stabilization
ZSM-5 containing additives are widely used to increase
propylene and butylene yields, as well as gasoline
octane, in fluid catalytic cracking (FCC) units. The stability
of the ZSM-5 additives, both with respect to surface
area retention and resistance to dealumination, under
FCC operating conditions is key to maximizing their
effectiveness and selectivity. This paper discusses the use
of unit cell volume (UCV) to understand the fundamentals
of ZSM-5 dealumination and stabilization. The fundamental
understanding of ZSM-5 deactivation, obtained in
these studies, has lead to the development of improved
stabilization technologies, which have been incorporated
into new ZSM-5 additives with step-out activity and stability.
Pilot plant results for the performance of the new additives
are presented, along with case studies of how refiners
can benefit from applying this technology to increase
propylene yield from the FCC.
Introduction
Since its invention by Mobil Technologies in 19721, ZSM-5
has been used commercially in a wide variety of catalytic
applications. The regular three dimension structure and the
acidity of ZSM-5 can be utilized in various shape-selective
reactions and acid-catalyzed reactions. ZSM-5 has been
used for decades as a catalyst and catalyst support in
chemical reactions including petrochemicals (for the
isomerization of meta-xylene to para-xylene), synthetic fuels
6 Catalagram® No.115 | Fall 2014
octane enhancement and dewaxing of oil). In refineries,
ZSM-5 has been used to enhance the gasoline octane and to
boost the propylene yield in the FCC unit.
In 1986 Grace, in collaboration with Mobil, developed the
first ZSM-5 based catalyst for use in the FCC unit.1 Within
a few years, the refining industry embraced ZSM-5 based
catalysts for octane enhancement and maximizing light
olefins from the FCC. Light olefins are the basic building
blocks for the manufacture of a variety of petrochemical
products and fuels. Today, light olefins are used for the
production of gasoline, polymers, antifreezes, solvents,
synthetic rubbers, and many other products. FCC supplies
30% of the propylene consumed by the petrochemical
industry1,2 and is the second largest supplier of worldwide
propylene production after steam cracking. FCC provides low
cost propylene feedstock for the petrochemical industry, and
the flexibility of the FCC mitigates the risk of large swings in
propylene demand and price.
The demand for propylene is primarily driven by the rapid
increase in polypropylene usage. In recent years, the
global demand for propylene has expanded in line with the
economic growth of developing countries such as China and
India and in the Middle East. The demand for propylene is
projected to increase by 5% per year. 2 To keep up with the
demand, a significant increase in propylene production from
FCC units will be required. The use of ZSM-5 based additives
in FCC is expected to increase.
The ZSM-5 based additive, OlefinsUltra® HZ, is Grace’s
patented technology and is the market leading additive
to maximize propylene production in the FCC unit. The
composition provides a unique combination of stability,
selectivity, and outstanding attrition resistance. Grace is
committed to continue to provide step-out FCC technology
to the market. This paper describes our understanding of
factors which influence the hydrothermal stability of olefins
additives. The concept of using unit cell volume (UCV), is
introduced for the first time, in the characterization of fresh,
laboratory deactivated, and commercially deactivated
ZSM-5 based olefins additives. The paper also describes
TECHNOLOGY LEADERSHIP
Grace’s methodology for separating commercially deactivated
olefins additive from Ecat. Using the fundamental understanding
Table 1: Correlation of silica-to-alumina ratio
(SAR) in the ZSM-5 framework with UCV and the
gained from these studies, Grace introduces our new
olefins additive, OlefinsUltra® MZ, which provides a step-out
improvement in activity and stability over the current industry-
Brønsted acidity.
leading OlefinsUltra® HZ. ZSM-5
Samples
Brønsted Acid Site
[micromoles / g]
UCV,
[Å3]
Relationship of Propylene Activity with Unit Cell Volume
and Silica-to-Alumina Ratio SAR 27 1832 5393
Zeolites are crystalline aluminosilicates with a three- SAR 55 922 5382
dimensional pore structure. The relative amounts of silicon SAR 80 592 5372
and aluminum in a zeolite framework changes its structural
SAR 250 168 5354
size, acidity, and catalytic properties. The catalyst for
use in FCC units usually contains Y-zeolite, but may also SAR 400 133 5349
contain ZSM-5 to boost propylene. Therefore, the ZSM-5 SAR 1000 3 5343
based catalysts are referred to as additives in FCC. During
the cracking process, the catalyst is deactivated due to
the hydrothermal conditions in the regenerator leading to
dealumination of the zeolites, in which the aluminum sites
are removed from the framework. For Y-zeolite, which has
a cubic structure, the reduction in Si/Al ratio has been
correlated with its unit cell size (UCS).3 The UCS of Y-zeolite
is measured by powder x-ray diffraction where the peak
position of a certain reflection is measured accurately, from
which the UCS can be calculated with a precision of 0.01 Å.
To correct for any displacement errors silicon powder with
known reflection positions is added to the sample as an
internal standard.4 However for ZSM-5, which crystallizes
in an orthorhombic system, where the three dimensions
of a unit cell a, b, and c are not equal, the length of all
three edges are necessary to describe the unit cell (Figure
1). Alternatively, the product of all three can be used to
calculate the unit cell volume. As the orthorhombic lattice
system produces a much more complex diffraction pattern, Figure 1: Unit cell size versus unit cell volume.
the UCV cannot be measured accurately enough by just
measuring the peak positions for some reflections. In this
case, the use of Rietveld refinement which evaluates the
whole diffraction pattern, is required. This method uses a
least squares minimization technique to refine a theoretical
powder pattern until a best match with the observed one
is achieved.5,6 The theoretical pattern contains all the
information about the sample from which the UCV of the
ZSM-5 can be calculated.
In this paper, we have made use of UCV to characterize the
fresh, laboratory deactivated, and commercially deactivated
ZSM-5 in the samples of olefins additives. The effect of
phosphorous on the UCV of fresh and deactivated ZSM-5
was compared. The fundamental understanding learned
on the stabilization of ZSM-5 in these studies was used to
7
TECHNOLOGY LEADERSHIP TECHNOLOGY LEADERSHIP

design and develop Grace’s new highly active and 0.045 improves the ZSM-5 stability by limiting dealumination 4500
5374
stable olefins additive, OlefinsUltra® MZ. of the zeolite.

Total acidity / µmol NH3 m-2, %

0.040 4000
5372
0.035

Unit cell volume / Å3

Table 1 shows the aluminum content in the ZSM-5 Use of UCV to Characterize Commercially 3500 Float Fraction/ EQ03-32A

framework, as reported by the silica-to-alumina ratio (SAR) 0.030 EQ03-32A calcined

5370 Deactivated Olefins Additives 3000 Y- Zeolite Sink Fraction/EQ03-32A
and the UCV for the as-synthesized ZSM-5 samples. The 0.025 The concept of UCV was extended to characterize
Brønsted acidity, as measured by isopropyl amine titration7 5368 2500

Counts, a.u.
0.020 the commercially deactivated ZSM-5 based ZSM-5
is superimposed. The data shows a nice correlation 0.015 olefins additives towards stability and propylene 2000
between the SAR, acidity and the UCV. The UCV and 5366
0.010 activity. Samples of Ecat with two different ZSM-5 1500
the acidity decrease with the increase in the SAR ratio 5364 additives, from the same refinery, were collected.
providing a nice calibration curve for the analysis of 0.005 1000
The ZSM-5 additives were isolated from the FCC
deactivated samples. 0 5362 base catalyst by a sink-float density separation
0 20 40 60 80 100 120 500
technique as described by Boock et. al. 8 The density
To understand the correlation better, a fresh sample of Steam Concentration, % separation is performed by adding the catalyst 0
4 14 24 34 44 54 64 74
OlefinsUltra® was deactivated in the laboratory at 1500 Total acidity Unit Cell Volume sample to a mixture of tetrabromoethane (TBE) and
°F for 24 h at atmospheric pressure and varying steam 2 θ, degrees
tetrachloroethane (TCE), which have density values
concentration of 0 to 100%. The relationship between of 2.96 g/cm3 and 1.58 g/cm3, respectively. The Float Fraction/ EQ03-32A EQ03-32A calcined Sink Fraction/EQ03-32A
Figure 2: Relationship between unit cell volume and the total acidity, as
total acid sites, as determined by ammonia temperature determined by NH3 TPD. The OlefinsUltra® sample was deactivated at skeletal density of the olefins additive is lower than
programmed desorption (TPD), and the UCV is shown in 1500°F for 24 h at various concentration of steam. that of the FCC base catalyst. The density of solvent Figure 4: XRD pattern for float fraction (Olefins additive) and sink fraction
Figure 2. The data show that as the steam concentration is adjusted by controlling the ratio of TBE to TCE. (FCC Base catalyst) separated from Ecat by density separation method.
increases the dealumination from the framework increases, Separation of the catalyst components occurs, as
which leads to a decrease in the UCV of the ZSM-5 crystal. shown in Figure 4, when the density of the TBE/TCE
The data also show that UCV correlates very well with the mixture is in between the skeletal density values of
total acidity. The sample steamed at 1500 °F for 24 h in Propylene,wt%
Propylene, wt%
Propylene, wt% Surface Area,Surface Area,
m2/g Area,
Surface m2m
/g /g
2
the olefins additive and the base catalyst. Table 2: Physical and chemical properties of olefins additives
100% steam shows UCV of 5363 Å3, which is comparable 10.8 10.8
10.8
10.8
220
220 220
220 separated from Ecat by density separation method.
to the UCV, 5362 Å3, of a standard ZSM-5 produced with 9.6 9.6
9.6
9.6 The sink and float fractions isolated after density
a SAR of ~80, shown in Table 1. This shows there is a 8.4 8.4
8.4
8.4 200
200 200
200 separation were characterized by XRD for sample
significant loss in framework alumina, which causes the 7.2 7.2
7.2
7.2 Propylene, wt%
180
180 180 Surface Area, m /g
180
2
purity and UCV, by N2 sorption measurement
loss of acidity of ZSM-5 crystal. 6.0 6.0
6.0
6.0 10.8
220 for BET surface area, and by ICP for chemical Properties Competitor OlefinsUltra® HZ
9.6 160
160 160
160
0 6 12 0 0186 6241212 18182424
200 analysis. The XRD pattern of Ecat, Figure 4, shows
The UCV measurements were used to compare 0 6 12000 186668.4
18 24
18
18 12
24
2412
12
24
7.2 180
that it is a blend of base FCC catalyst and olefins Ni, ppm 1731 2523
OlefinsUltra® HZ, with Grace’s proprietary stabilization 6.0 additive. The diffraction peaks due to Y-zeolite and
160 V, ppm 3150 3190
process, versus an unstabilized ZSM-5 additive. Both Unit Cell Volume,
Unit Å30Volume,
Unit Cell
Cell Volume, ÅÅ3 18
3
0 6 12 18 24 ZSM-5 are apparent for Ecat. The float fraction,
additives contained equal amounts of ZSM-5. The additives 6 12 24 SA, m /g 2
145 149
5380 5380
5380
5380 which is comprised mainly of olefins additive,
were deactivated using a standard steaming protocol of5370 5370
5370
5370 shows the diffraction pattern of ZSM-5. The peaks UCV, Å3 5354 5361
1500 °F in 100% steam for various times between 0 h and 5360 5360 Unit Cell Volume, Å3
5360
5360 due to Y-zeolite are negligible, indicating a clean
24 h. The deactivated samples were characterized by BET 5350 5350 5380
5350
5350 5370 separation of the additive from the Ecat. The sink
surface area, unit cell volume, and by propylene activity 5340
as 5340
5340
5340 5360 fraction shows peaks only due to the Y-zeolite. The
determined by ACE™ testing. For ACE testing, the olefins 5350 physical and chemical properties of OlefinsUltra®
0 6 1200 1865340 6 241212 18
12 18 24
18 24
24
additives were blended at 5wt% with an Ecat and tested at HZ versus competitor olefins additives, separated
simulated FCC conditions. Figure 3 shows the propylene Steam Time, h
Steam Time, h
0 6Steam
12 Time,
18 24h from the Ecat by density separation method, are
yield, UCV, and surface area trends for the additives Steam Time, h shown in Table 2. The chemical analysis shows
OlefinsUltraOlefinsUltra
®
HZ
OlefinsUltra
®
HZ UnstabilizedUnstabilized
®HZ
Unstabilized
formulated with stabilized and unstabilized ZSM-5. that the contamination of metals such as nickel,
The non-stabilized ZSM-5 additive loses its propylene OlefinsUltra HZ
®
Unstabilized
and vanadium on both additives are similar. These
activity rapidly, whereas the OlefinsUltra HZ retains
®
metals accelerate the deactivation of catalysts under
significant propylene activity after deactivation. After a 24 Figure 3: Relationship of propylene yield in ACE testing with UCV and hydrothermal conditions in the FCC unit. The similar
h deactivation, the surface area for both samples is similar surface area. Olefins additives were steamed at 1500°F for varying contaminant metals indicate that both additives were
but the OlefinsUltra® HZ shows much higher UCV to go lengths of time, and then blended at 5% level with base FCC catalyst. subjected to comparable deactivation conditions in
along with the higher propylene activity. The data suggests the commercial unit. The data show the surface areas
Grace’s proprietary stabilization technology significantly for these samples are identical but the measured

8 Catalagram® No.115 | Fall 2014 9

TECHNOLOGY LEADERSHIP TECHNOLOGY LEADERSHIP

UCV of 5361 Å3 and 5353 Å3 for OlefinsUltra® HZ and the density and attrition properties to that of OlefinsUltra® HZ. Table 3: ACE interpolated yields at constant conversion Table 4: Physical and chemical properties of OlefinsUltra® MZ
competitor additive, respectively, are considerably different. of 75wt%. Olefins additives were blended at 5wt% with compared to that of OlefinsUltra® HZ
The OlefinsUltra® HZ maintains higher UCV under the Most laboratory deactivation protocols are designed to the base FCC catalyst and were tested in ACE at constant
commercial hydrothermal conditions of the FCC unit. This simulate the field deactivation of base FCC catalysts, and conditions.
demonstrates that the OlefinsUltra® HZ, which is formulated may not properly simulate the field deactivation of olefins Sample: OlefinsUltra® HZ OlefinsUltra® MZ
by our proprietary stabilization technology, is more stable additives. It is important that we compare the properties and
towards dealumination under commercial deactivation performance of olefins additives using a deactivation protocol 5wt% 5wt% ABD, g/cm3: 0.72 0.75
ACE Yields Base
conditions. which will mimic the deactivation of commercial units. To Competitor OlefinsUltra® HZ DI, -: 4 4
identify the appropriate deactivation conditions, a sample of APS, microns: 75 85
The activity of olefins additives for propylene yield was OlefinsUltra® was steamed at 1500°F in 100% steam for 5 h, Cat-to-Oil Ratio 5.8 6.2 6.3
Surface Area, m /g: 2
156 184
determined by testing in an ACE unit. For ACE testing, the 10 h, and 25 h. The properties and propylene activity of the Hydrogen, wt% 0.1 0.1 0.1
commercially deactivated olefins additives, which were steamed samples were compared against a commercially UCV, Å 5363
3
5360
Ethylene, wt% 0.6 0.8 0.9
isolated from the Ecat, were blended back into a steamed deactivated sample of OlefinsUltra®, which was separated Deactivation: 4 h at 1500°F in 100% Steam
deactivated FCC base catalyst at 5wt% level. Performance from Ecat by density separation. The deactivated samples, Total Dry Gas, wt% 1.7 1.9 2.0
Surface Area, m2/g: 181 210
for propylene activity in ACE was compared at constant from the laboratory and commercial unit, were blended with Total C3's wt% 6.3 9.3 10.7
conditions. The ACE data, at a constant conversion of 75wt%, an Ecat at constant additive level and then tested in the ACE UCV, Å3 5360 5360
Propylene, wt% 5.5 8.2 9.5
are shown in Table 3. The high activity of OlefinsUltra® HZ is unit. The results show that the performance of laboratory Deactivation: 8 h at 1500°F in 100% Steam
Delta Propylene 2.7 4.0
revealed by higher propylene yield when compared to the deactivated sample overlaps with the commercially
Surface Area, m2/g: 172 214
competition’s olefins additive, shown in Figure 5. The increase deactivated sample after 20 h of hydrothermal steaming, Total C4's, wt% 12.5 14.8 15.4
in propylene yield is accompanied by a decrease in gasoline shown in Figure 6. Therefore, to match the performance of a UCV, Å 3
5360 5360
Total C4='s, wt% 7.2 8.4 9.0
yield which is due to cracking of gasoline range olefins commercially deactivated sample the olefins additive in the Deactivation: 24 h at 1500°F in 100% Steam
C5+ Gasoline, wt% 51.4 46.5 44.2
(Table 3). The data show that the OlefinsUltra® HZ delivers laboratory has to be steamed for a minimum of 20 h in 100% Surface Area, m2/g: 161 205
40% more incremental propylene compared against the steam at 1500°F. These conditions are severe, but necessary LCO, wt% 19.4 19.2 19.2
UCV, Å 3
5360 5360
competitor’s high ZSM-5 olefins additive. The higher activity for the development of additives in the laboratory to simulate Bottoms, wt% 5.6 5.8 5.8
of OlefinsUltra® HZ is a result of its superior hydrothermal the conditions the additives will face in commercial units. Coke, wt% 3.0 2.8 2.6
stability and resistance to dealumination, as indicated by the
UCV measurement. These results are consistent with the The properties and performance of OlefinsUltra® MZ were
higher activity and stability observed in the field and support compared against OlefinsUltra® HZ after 4 h, 8 h, and 24
the market-leadership position of OlefinsUltra® HZ. h of hydrothermal deactivation in 100% steam at 1500 °F. 8 Propylene yield for
11 Propylene yield
Conversion == 70wt%
70wt% ® for
The data are summarized in Table 4, which shows that the Conversion OlefinsUltra ®
OlefinsUltra®
OlefinsUltra , float
OlefinsUltra®, float
7 fraction, separated
fraction, separated
Grace’s Newest High-Performance Additive OlefinsUltra® MZ maintains its high surface area and UCV 10 from Ecat
from Ecat
OlefinsUltra® MZ after deactivation. Both samples show an initial increase in 9 6

Propylene yield, wt.%

surface area after deactivation, likely due to the unblocking

To keep up with growing propylene demand refineries
around the world use significant amounts of olefins additive
to boost propylene production from the FCC units. The high
usage of olefins additives in the FCC unit may lead to a loss
in conversion, due to the dilution of the base catalyst. To
minimize dilution effects max-propylene units require a highly
Propylene, wt%
of pores of the ZSM-5 crystals and the matrix during
steaming. The additives were evaluated for propylene
activity in ACE at standard FCC conditions, after blending
with an Ecat at 5wt% and 25wt%. The high blending ratio
was used to evaluate its application for the max-propylene
5
8
7 4
6 3
5 2
Ecat

active and propylene selective additive. The activity of olefins
additive can be enhanced either by adding more ZSM-5 to
the formulation or by improving the stability of the ZSM-5.
Exploiting our understanding of ZSM-5 stabilization, Grace
has designed a new olefins additive, OlefinsUltra® MZ, which
provides a step-out improvement in stability and propylene
activity over the industry leading OlefinsUltra® HZ.
OlefinsUltra® MZ combines the features of high ZSM-5
input with our proprietary stabilization technology without
any compromise on attrition resistance. Table 4 shows
OlefinsUltra® MZ has higher surface area, but has similar bulk
units. The ACE data for 5wt% olefins additive, at constant
conversion, is shown in Table 5. The data reveal that 4 1
the OlefinsUltra® MZ, after severe deactivation, makes 3 0
higher propylene compared to the OlefinsUltra® HZ. A 67 69 71 73 75 77 79 0 5 10 15 20 25
corresponding decrease in gasoline is observed, which
Conversion (wt%) Time on Steam, h
is due to the cracking of gasoline range olefins to light
olefins. The OlefinsUltra® MZ shows a 20% increase in Base Competitor OlefinsUltra HZ
®
delta propylene yield over the current best technology
in the market, OlefinsUltra® HZ, as shown in Figure 7. Figure 5: Propylene yield for commercially deactivated olefins additives Figure 6: Propylene activity of laboratory deactivated OlefinsUltra®
The ACE data for the higher blend level, shows a similar isolated by density separation method. The separated additives were compared against commercially deactivated OlefinsUltra® isolated by
blended back at 5wt% with base catalyst for ACE testing. density separation method. The laboratory sample was deactivated at
propylene yield advantage for OlefinsUltra® MZ (Figure
1500°F in 100% steam for various times. Additives were blended at 2.5
7). The data demonstrate that the OlefinsUltra® MZ, with
wt% level and tested in ACE at constant conditions.

10 Catalagram® No.115 | Fall 2014 11

TECHNOLOGY LEADERSHIP TECHNOLOGY LEADERSHIP

Grace proprietary stabilization technology,

delivers improved propylene yields and is
Table 5: ACE interpolated yields at constant conversion of 76wt%.
Olefins additives were blended at 5wt% with the base FCC catalyst and Addressing Polypropylene
the clear choice for max-propylene units.

Conclusion: A Valid Technique

were tested in ACE at constant conditions.
Demand with Efficient Solutions
In this paper we have shown the
significance of unit cell volume for
Catalyst OlefinsUltra® HZ OlefinsUltra® MZ v Ella Chen (Grace)
the characterization of ZSM-5 in the Polypropylene a colorfast, heat- and corrosion-resistant A State-of-the-Art Process
additive formulation. We have shown Cat-to-Oil Ratio 6.8 7.0 plastic, has experienced steady growth in use since The UNIPOL® PP process technology, which includes
that the technique is valid for fresh, Hydrogen, wt% 0.06 0.06 its discovery in 1954. From food packaging to medical the UNIPOL UNIPPAC® process control software, is a
laboratory deactivated, and commercially equipment to automotive parts and more, it has become recognized leader in the industry. Globally there are 51
Total C1's & C2's, wt% 1.8 1.9
deactivated ZSM-5 additives, where other a preferred material for a variety of applications due UNIPOL® PP process licensees with 16 plants in the design
catalyst properties such as surface area Ethylene, wt% 0.8 1.0 to its high versatility. Its low density, recyclability, and and construction phase. In China there are seven plants
can be misleading. The fundamental Total C3's, wt% 10.2 11.0 higher heat distortion temperatures compared to other successfully making polypropylene with eight startups over
understanding of the deactivation of Propylene, wt% 9.1 9.8 plastics, along with processing ease in conventional the next three years; four scheduled for 2015, one for 2016,
ZSM-5 gained in these studies has systems, have made polypropylene the plastic of choice and three for 2017. The successful UNIPOL® start-ups
Total C4’s, wt% 15.7 16.2 among manufacturers and consumers. include the first ever Chinese polypropylene plant using
lead to the development of improved
stabilization technologies, which have been Isobutane, wt% 5.3 5.6
incorporated into our new ZSM-5 additive. Isobutene, wt% 3.1 3.3 “The UNIPOL® brand and the capabilities it represents are highly respected
The introduction of OlefinsUltra® MZ raises
the bar on olefins additive performance,
Total C4=’s, wt%
Gasoline, wt%
9.5
45.3
9.7
43.8
in the marketplace. Grace is committed to strengthening that position with its
providing step-out catalyst stability and
propylene activity, for the next generation RON 94.5 94.7 capabilities and full portfolio of products and services to our customers and the
max-propylene catalytic solution. v MON
LCO, wt%
82.0
17.2
82.2
17.3
broader global marketplace.”
Bottoms, wt% 6.8 6.7
Reference: Coke, wt% 3.0 3.0 Polypropylene Market Growth coal-based propylene as the feedstock. That success has
1. R.K. Miller, P.K. Niccum, M.A. Silverman, N.A. Bhore, The steady growth the polypropylene market has seen is proven UNIPOL® PP process technology as the natural fit for
G.K. Chitinis, S.J. McCarthy, K. Liu, NPRA Annual expected to continue with Chemical Market Resources the emerging coal-to-polyolefin industry, particularly for the
Meeting, 1998. 14 reporting global capacity growth of 6% annually through coal-rich Chinese market.
2. R. Hamada, M. Watabe, 18th Annual Saudi-Japan 2017. Ninety percent of announced polypropylene
Symposium on Catalysts in Petroleum Refining and 12 capacity will be concentrated in Asia, Middle East, and The UNIPOL® PP process technology is simple to build,
Petrochemicals, 2008. Eastern Europe, with China encompassing nearly 40% operate and maintain. It offers manufacturers a one-
3. D.W. Breck, E. M. Flaningen, Synthesis and Properties 10 of new supply. China, which is becoming less reliant stop shop for polypropylene with the ability to streamline
Propylene Yield, Wt%

of Union Carbide Zeolites L, X and Y, Molecular Sieves,
Soc. Chem. Ind.: London, 1968, p. 47.
4. ASTM Method D3942-08, Standard Test Method for
Determination of the Unit Cell Dimension of a Faujasite-
Type Zeolite, ASTM International, West Conshohocken,
PA, 2008.
 . M. Rietveld, Acta Crystallographica, Vol. 22(1),
5. H
151, 1967.
6. H. M. Rietveld, Journal of Applied Crystallography,
Vol. 2, 65, 1969.
7. O
 . Kresnawahjuesa, R.J. Gorte, D. Oliveira, L.Y. Lau,
Catalysis Letter Vol. 82, No. 3-4, 2002.
8. L .T. Boock, J. Deady, T.F. Lim, G. Yaluris, Elsevier
Science – Catalyst Deactivation 1997, editors C.H.
Bartholomew and G.A. Fuentes, Page 367.
on imported raw materials, is experiencing a growth
8 rate closer to 11% per year, making it a high growth
market for such material. For China the increase in locally
6 manufactured polypropylene will cut down on import costs
and provide easy access to polypropylene resins.
4
Grace is helping to address the growth in demand through
2
expansion of its capabilities and catalyst portfolio. Last
year Grace completed the acquisition of the polypropylene
0
0 wt% 5 wt% 25 wt% licensing and catalysts business of The Dow Chemical
Company (DOW). The acquisition includes UNIPOL®
Olefins Additive in Ecat blend
polypropylene process technology and makes Grace the
Ecat OlefinsUltra® HZ OlefinsUltra® MZ second largest polypropylene licensor in the world based
on installed capacity, advancing Grace’s leadership in the
Figure 7: Propylene activity of OlefinsUltra® MZ compared to that of OlefinsUltra® broader polyolefin sector.
HZ. Additives were blended at 5wt% and 25wt% with hydrothermally deactivated base
catalyst for ACE testing at constant conditions
the process. UNIPOL® PP process technology is an all
gas-phase technology based on a fluidized bed reactor
system. With single line capacities up to 650 KTA it is
the largest amongst all the polypropylene manufacturing
technologies. UNIPOL® PP process technology provides
the highest operating on-stream time in the industry
while also providing the ability to produce high-quality
polypropylene. Many licensees have achieved the benefits
of operating significantly above their nameplate capacities
with UNIPOL® technology. The core UNIPOL® PP process
facility (purification, reaction, purging, vent recovery,
additive addition, and pelleting) has the smallest footprint
in the industry. Additionally, it is the least complex of all
polypropylene process technologies requiring the fewest
number of reactors and major pieces of rotating equipment.

12 Catalagram® No.115 | Fall 2014 13

TECHNOLOGY LEADERSHIP

Catalyst Technology Innovation
Grace is the only polypropylene licensor to make
and sell both proprietary catalysts and donors that
are designed specifically for gas phase processes.
UNIPOL® PP process licensees benefit from Grace’s
sustained investment in R&D resulting in access to a
continuous innovation pipeline that puts them ahead of
the competition. With growing market demand in China,
along with growing demand for higher performance
grade polypropylene, Chinese customers have the
necessary tools to address current consumer demand
without the use of expansive imported resins. UNIPOL®
PP process technology, combined with CONSISTA® or
SHAC® catalyst systems, can produce differentiated,
high-quality, market-leading products and has the
flexibility to produce high quality basic resins.
The CONSISTA® and SHAC® catalysts and donor
systems allow one production of a wide variety of high
value products in a simple, easy to operate process.
Particularly, CONSISTA® polypropylene catalyst is
a 6th generation, non-phthalate based technology
that offers the ability to produce higher performance
resins with broader applicability at a competitive cost
position. This catalyst technology offers excellent
product performance via resins that are cleaner. It
allows the fabricators to produce lighter and clearer
articles at a faster speed allowing for potential light
weighting without loss of stiffness, increased cycle time
efficiencies, enhanced environmental advantages, and
change to the basic process. This drop-in technology
development allows producers to keep their process
and product technology up to date without requiring
any changes to the process. UNIPOL® PP process
technology customers receive best-in-class technology
transfer for smooth design, construction, and startup
and the fastest time from startup to production of prime
grade polypropylene products. v
Simplicity
is a key characteristic of UNIPOL®
Polypropylene Technology:
• Fewer moving parts and less equipment
overall compared to competing systems
• Smallest Inside Battery Limits (ISBL)
footprint in the industry
• Easy access to key plant equipment for
simplified maintenance
The result of our simple, common sense
design approach is that the licensee will
enjoy low capital costs and the low operat-
ing costs compared to competing systems.
Simple and Reliable

p p p p p p
preferred optics.
Broadest Product Range
CONSISTA® catalyst with CONSISTA® donors provides
the benefits of excellent reactor operability and
Low Investment Cost
on-stream time. This is a “drop-in” technology with Low Operating Cost
advanced product benefits that can be used broadly
in commodity grade production. The UNIPOL® PP Easy to Operate
process technology tailored SHAC® catalysts systems, Outstanding Profit Potential
6th generation non-phthalate CONSISTA® catalysts and
advanced donor systems all enhance Grace’s polyolefin
catalysts portfolio. These products complement Grace’s
polypropylene catalysts families of POLYTRAK®, and
HYAMPP® and its polyethylene catalyst systems such
as Cr-based catalysts (MAGNAPORE®), Ziegler-Natta
catalysts, and Single Site Catalysts.

Grace’s investment in R&D offers UNIPOL® PP process

UNIPOL
technology customers access to continuous innovations
®
in catalyst and donor technology and, as a result,
access to product improvements without requiring any

Polypropylene
14 Catalagram® No.115 | Fall 2014 Technology
AFPM Q&A RESPONSES - GRACE FCC AFPM Q&A RESPONSES - GRACE FCC

Question: What FCC gasoline sulfur reduction technologies are being used Grace’s GSR® clean fuels
solutions create economic
Japanese refiners faced similar
challenges that US refiners
approximately 40% reduction in
gasoline sulfur.
to control sulfur during cat feed hydrotreater or gasoline product hydrotreater advantages around: face today in meeting Tier 3.
Since 2005, these refiners have Grace GSR® technologies: D-PriSM®
outages? Will these products be a viable option for Tier 3 gasoline sulfur specs? • Feedstock blending
• Asset optimization to: successfully utilized Grace GSR® and GSR® 5 FCC additives and
m Preserve octane
products to maintain compliance, SuRCA® FCC catalysts, are the
v Stuart Kipnis (Grace) m Maximize throughput
observing 35%-40% reduction in result of almost two decades
Extend pre-treatment
m 
the gasoline sulfur / feed sulfur of innovation. Grace GSR®
Refiners have created operating flexibility while maintaining sulfur savings during the hydrotreater and/or post-treatment ratios allowing them to meet the technologies have been used in
flexibility during hydrotreater compliance and profitability. outage. The results were so hydrotreater life 10 ppm gasoline specifications.2 more than 100 FCC applications
outages by utilizing Grace’s clean encouraging that the customer • Gasoline stream blending worldwide delivering 20%-40%
fuels GSR® additive technology. One such example of a refiner that elected to continue using GSR® options An example of a Japanese refiner sulfur reduction in FCC naphtha in
used Grace GSR® 5 sulfur reduction technology, switching to a SuRCA® • Generation of gasoline sulfur meeting 10 ppm gasoline sulfur both full and partial burn operations.
Proper management of FCC feed additive during a feed hydrotreater catalyst and operating with post- ABT credits to defer capital spec without increasing gasoline The GSR® additive technologies
hydrotreater outages becomes outage is shown in Figure 1. The outage feed sulfur 10-15% higher investment post-treater severity can be seen in are used at a 10%-25% loading
increasingly important as more and refiner was able to process higher than the typical operation. This Figure 2. In this case, as much as in inventory, whereas the catalytic
more refiners rely on hydrotreating than typical feed sulfur and maintain change to their operation grew Tier 3 regulations require the 35% gasoline sulfur reduction was solutions are a customized 100%
to meet their per gallon gasoline gasoline pool sulfur compliance. annual profits by approximately reduction of average gasoline achieved with SuRCA® catalyst. drop-in replacement for your base
sulfur limits. Running at higher Use of GSR® 5 began two months $8 million.1 pool sulfur level to ≤10 ppm catalyst. GSR® products can
severity increases the frequency of prior to the 45-day feed hydrotreater with an 80 ppm cap by January Another example [Figure 3] be used for short or long term
turnarounds. Conventional methods outage. During that time, feed sulfur Continued operation during a 2017, compared to the current shows a Japanese refiner that applications; the longest continuous
of ensuring that the gasoline pool increased by as much as 35%. hydrotreater outage is just one limit of ≤ 30ppm with an 80 ppm was able to maintain compliance application is now 12 years.
stays below the sulfur limit during The three periods represented are way that refiners can benefit from cap. Grace has substantial with the 10 ppm gasoline sulfur
the hydrotreater turnaround are typical operation (Base Period), application of Grace’s patented experience in similarly demanding spec while maintaining flexibility Grace’s multiple product offerings
purchasing low sulfur feed or GSR® 5 before and during the GSR® technologies. In-unit environments like Japan. to either blend high sulfur coker allow for a truly custom GSR® clean
reducing FCC throughput. Either outage where gasoline sulfur reduction of FCC gasoline sulfur gasoline into the gasoline pool fuels solution for your refinery’s Tier
approach can significantly reduce reduction ranged from 20-25%, and creates a variety of opportunities In the mid 2000’s, Japan committed or extend the VGO hydrotreater 3 compliance plan. Ask your Grace
refinery profitability. An alternative finally GSR® 5 following the outage. and options for refiners to drive to lower gasoline sulfur levels. As catalyst life. Again, SuRCA® representative which product is best
is to use one of Grace’s gasoline profitability while meeting new Tier 3 early adopters of more stringent catalyst technology was used for your operation. v
sulfur reducing technologies during The customer estimated that use gasoline requirements. gasoline quality regulations, and the refiner observed
the outage to provide operational of GSR® 5 netted $1.7 million of
500
2.1%
3.0%

Gasoline Sulfur / Feed Sulfur (%)

Reference:
Gasoline Sulfur / Feed Sulfur (ppm/wt.%)

Gasoline Sulfur / Feed Sulfur (%)

2.8%
450 1.9% 1. L. Blanchard, C. Borchert, M. Pu, NPRA
2.6%
2.1%
Annual Meeting, AM-07-06, 2007
400 2.4%
1.9%
2. L . Blanchard, T. Oishi, B. Teo, J. Haley,
2.2%
"SuRCA® Catalyst Reduces Gasoline Sulfur at
350 1.7% 2.0% Three Japanese Refineries", Catalagram® 98,
1.5% 1.8% 2005
300
1.6%
1.3%
250 1.4%
1.1% 1.2%
200 0.9% 1.0%
310 315 320 325 330 335 330 332 334 336 338 340 342 344 346 348 350 410 415 420 425 430 435 440 445 450 455 460
D86 T95 (˚F) D86 Gasoline T90 (˚F)
SIMDIST Gasoline T99 (˚F)
Base Period GSR® 5 Outage GSR® 5 Post Outage SuRCA® Base
(Days 1-71) (Days 116-375) (Days 116-375) SuRCA® Base

Figure 1: GSR® 5 delivered 25% gasoline sulfur reduction during a Figure 2: A Japanese refiner realized 35% gasoline sulfur reduction w/ Figure 3: SuRCA® catalyst reduced gasoline sulfur by 40% at constant gasoline cut point
feed HT outage. SuRCA® catalyst.

16 Catalagram® No.115 | Fall 2014 17

AFPM Q&A RESPONSES - GRACE FCC

ACHIEVE ®
THE ADVANTAGE
Question: The increase in light tight oil as a percentage of North
American crude slate has resulted in lower FCC feed production, and Grace developed the ACHIEVE® FCC
consequently a reduced FCC feed rate at several refineries. To address these catalyst technology specifically
issues, what strategies have been implemented operationally and catalytically? for the challenges
Are refiners looking at sending new streams to the FCC or increasing the
of opportunity feeds
proportion of existing streams such as resid? If so, what steps do refiners
ACHIEVE® 400 catalyst, the first member of this
take to evaluate these potential new feedstocks and what steps do refineries family, is in commercial use and designed to
take to minimize uncertainty and reduce risk? Increase production of butylenes

v Kenneth Bryden (Grace)
The increase in the quantity of
tight oil as a percentage of the
North American crude slate has
resulted in numerous changes at
refiners. Tight oils, like other light
sweet crudes, have a much higher
ratio of 650°F- to 650°F+ material
when compared to conventional
crudes. Bakken tight oil has a
nearly 2:1 ratio, while typical
crudes such as Arabian Light,
have ratios near 1:1. A refinery
running high percentages of tight
oil could become overloaded with
light cuts, including reformer feed
and isomerization feed, while at
the same time short on feed for the
fluid catalytic cracking unit (FCCU)
and the coker. Some refiners
have balanced the use of larger
amounts of tight oil with increased
use of heavier crudes such
as Canadian syncrude. Other
refiners have charged a portion of
whole tight oil to the FCC to keep
the FCC full.
As refiners consider new
feedstocks, testing is a valuable
tool to reduce risk. Testing
provides understanding of feed
properties and potential yield
changes. Below are examples
of potential tests to use when
evaluating a new feedstock.
Testing of feed metals levels is
especially important since tight oil
derived feeds often contain varying
levels of conventional contaminants
such as sodium, nickel and
vanadium and unconventional
contaminants such as iron and
calcium. Understanding the
expected metals levels of a new
feed allows refiners to work with
their catalyst vendor to choose
catalyst options that mitigate
the challenges of these metals.
Grace’s newest catalyst family,
ACHIEVE® catalyst, is designed
to address the unique challenges
associated with tight oils.
ACHIEVE® catalyst formulations are
flexible, enabling Grace to design
a custom solution for refiners
proactively increasing the amount
of tight oil in their crude diet.1
p p p p
Increase gasoline octane
Feed properties such as API, Decrease slurry production
concarbon and hydrocarbon
types can provide insight into the
Increase LCO yield
expected crackability of a feed,
but may not tell the whole story. A Let Grace technical experts show you how
fuller understanding of how a feed to attain these advantages.
will crack in a unit can be obtained
through testing. Either bench-scale grace.com
testing (ACE or MAT) or pilot-scale
testing (such as Grace’s DCR™
circulating pilot plant) can be done.
MAT and ACE testing have the
advantages that they are easy to
set up and require small amounts
of material.2 However, these
units cannot provide the detailed
product analysis or feedback
on extended operation that pilot
scale units can. Larger scale
test equipment such as a pilot
unit can provide sufficient liquid
product for distillation and detailed
analysis (such as API gravity and
aniline point of LCO produced,
viscosity of bottoms, octane engine
testing of gasoline, etc.) and can
provide information on continuous
operation. Additionally, compared
to bench scale units, the DCR™
(continued on page 20)

18 Catalagram® No.115 | Fall 2014 19

AFPM Q&A RESPONSES - GRACE FCC
(Tight Oil continued)
pilot plant has the advantage
that it mimics all the processes
present in commercial operation
and it can operate at the same
hydrocarbon partial pressure as
a full-scale commercial unit.
Grace’s technical service and
R&D teams help refiners assess
potential challenges from
feedstock shifts before they
occur via feed characterization,
feed component modeling,
and pilot plant studies.
Understanding feed impacts
earlier provides an opportunity
to optimize the operating
parameters and catalyst
management strategies,
enabling a more stable and
profitable operation. v
Reference:
1. “Processing Tight Oils in FCC: Issues,
Opportunities and Flexible Catalytic
Solutions”, AM-14-16, 2014 AFPM
Annual Meeting, Orlando, FL.
2. “ Predicting FCC Unit Performance with
Catalyst Testing,” PTQ Catalysis, 2013
20 Catalagram® No.115 | Fall 2014
Question: What are the best practices in
the industry for profitable LCO maximization?
Please elaborate on (a) FCC catalyst/additive
technologies, (b) cetane maximization, (c) process
design and operations strategies and (d) any
impact on naphtha octane and how to mitigate it.
v Ann Benoit (Grace)
Maximizing light cycle oil (LCO)
is largely a slurry management
process. To increase LCO,
refiners can simply change
operating conditions and
lower catalyst activity to
shift operations into a lower
conversion regime. The negative
impact of shifting to a lower
conversion regime is that this
shift will typically decrease
volume swell and also increase
bottoms, unfavorably impacting
profitability. The true challenge
is to maximize LCO without
producing incremental bottoms
while maintaining volume
expansion.
In general, refiners tend to focus
on the following strategies to
maximize LCO yield:1
1. Distillation changes (reduce
gasoline end point and
increase LCO endpoint)
2. Feedstock
• Removal of diesel range
material from the FCC
feedstock
3. Recycle Streams
• Heavy cycle oil (HCO) or
bottoms
4. Operating Conditions
• Lower reactor temperature
• Higher feed temperature
• Lower equilibrium catalyst
activity
5. Catalyst Optimization
• Increased bottoms
conversion
• Lower zeolite-to-matrix
surface area
• Maintenance of C3+ liquid
yield and gasoline octane
A quick, simple and effective
way to increase LCO is to make
distillation adjustments such as
lower gasoline endpoint and/or
increased LCO endpoint. Flash
point specification and main
fractionators salting often will
determine how low a refiner
can reduce the LCO initial
boiling point (reduce gasoline
end point).1 Maximum main
fractionator bottoms temperature,
slurry exchanger fouling and
diesel hydrotreating constraints
will often determine how much
the LCO endpoint can be
increased.
Regarding feedstock, it is
recommended that diesel range
material be removed from the
FCC feedstock. This material is
typically higher quality diesel for
the overall refinery diesel pool.
Recycle streams can be
employed to fully maximize LCO
at reduced conversion. The
quality of the recycle stream can
make a difference in the products
being produced. The effects
of different recycle streams are
discussed in detail in the AFPM
paper “Strategies for Maximizing
FCC Light Cycle Oil” (Hunt, et
al, AM-09-71). The 650°F –
750°F recycle stream produced
the most LCO and gasoline
at the lowest coke for a given
conversion.1 However, this stream
is not produced in sufficient
quantities to fully maximize LCO.
The 650+°F and 750+°F streams
have high Conradson carbon
levels (consistent with higher
quantities of tetra-aromatics and
heavier compounds) which limit
the yield of LCO when these
streams are recycled to the FCC.1
The 650°F to 800°F or 650°F to
850°F recycle streams produced
the highest LCO when recycled
against a coke burn and bottoms
constraint.1
Adjustments to operating conditions
such as reactor temperature,
preheat, and/or catalyst activity
to lower conversion and increase
LCO can be made, but this may
come with a price. By reducing
conversion through operating
conditions, LCO yield and potentially
cetane will increase2, but so will
slurry. The primary challenge in the
FCC unit is to increase LCO, while
AFPM Q&A RESPONSES - GRACE FCC
minimizing incremental slurry
yield and maintaining volume
There are several avenues that
can be taken to increase LCO
swell. Gasoline octane may yield on the FCC, but overall
also be a concern due to lower refinery economics will dictate
reactor temperature and lower which move or combination
conversion. This is why a catalyst
reformulation strategy is needed
of moves proves the most
beneficial to the refinery. Catalyst
to address the incremental slurry, reformulation strategy should
lower volume swell, and lower always be considered in LCO
gasoline octane when operating maximization cases since this can
conditions are adjusted to address the incremental slurry
maximize LCO. and lower volume swell in a lower
conversion regime. v
Application of the correct catalyst
technology is critical for high
LCO yield and minimal bottoms
and coke yield. Keep in mind
that a balanced approach is
required to achieve maximum Reference:
1. Hunt, D.A., et al, “Strategies for Maximizing
bottoms upgrading to LCO and
LCO” NPRA Annual Meeting, AM-09-71, 2009.
other valuable products. An
2. Ritter et. al., “Light Cycle Oil From the FCC
LCO maximization catalyst is
Unit,” NPRA Annual Meeting, AM-88-57,1988.
typically an improved bottoms
cracking catalyst with a lower 3. Bryden, K.; Federspiel, M.; Habib, E.T.; Schiller,
R., “Processing Tight Oils in FCC: Issues,
zeolite-to-matrix ratio. Grace Opportunities and Flexible Catalytic Solutions,”
typically considers our MIDAS® AM-14-16, AFPM Annual Meeting, 2014.
technology in LCO maximization
applications due to premium high
matrix bottoms cracking ability.
Due to the economic penalty
with lower volume swell, ZSM-5
additives such as OlefinsMax®
or OlefinsUltra® should be
considered to maintain or improve
volume swell and/or gasoline
octane while operating at a lower
conversion. If butylene has a
greater value than propylene,
a reformulation to the Grace’s
ACHIEVE® 400 FCC catalyst
could be optimal.3 ACHIEVE® 400
catalyst features a moderate Z/M
ratio and dual-zeolite functionality,
delivering increased gasoline
octane and butylene yield at
minimum bottoms.
21
 AFPM Q&A RESPONSES - GRACE FCC
MIDAS GOLD ®
The Gold Standard for Resid Upgrading
MIDAS® FCC catalysts are Grace’s high
matrix catalysts with proven success for Question: What are the characteristics of FCC catalyst to minimize
deep conversion of resid. MIDAS® Gold, particulate emissions at the stack?
the latest member of the family, is a high
activity formulation that delivers v John Aikman (Grace)
Superior coke-selective bottoms While there are several operational diameter which can reliably density, per Equation 1 below.

p
upgrading and mechanical factors that can be collected by a cyclone This means that cyclones can
influence a unit’s particulate and is used to model cyclone retain smaller particle sizes as the
Stable activity against metals

p
emissions, the question asks performance. Particles below this particle density increases. This is
contamination specifically about the FCC catalyst; size will be lost by the cyclone. due to the centrifugal force acting
Formulation flexibility for a customized as such, the following discussion on a heavier particle. However,

p
yield profile
We offer several distinct MIDAS® formulas,
suitable for a broad range of feed and
operating objectives. Let Grace technical
experts show you the best fit for your operation.
grace.com
will address characteristics of fresh
catalyst only.
There are four basic
characteristics of FCC catalyst
that can have direct effects on
particulate emissions. These
same characteristics will also
affect particulate losses to the
fractionator and slurry product.
The first characteristic is simply
the amount of fines content
coming into the unit with the fresh
catalyst due to the manufacturing
process. Figure 1 is an example
of a typical fresh catalyst particle
size distribution, with a theoretical
depiction of a cyclone’s ability
to retain fresh catalyst particles.
DpTH is the smallest particle
A review of the Grace Ecat
database showed that none of
the FCCU’s in North America can
retain any 0-20 µ range particles.
In addition, they only retain
an average of approximately
4.0 wt.% in the 0-40 µ range.
Fresh catalyst typically ranges
anywhere from 9% to 16%
of 0-40 µ depending on the
supplier and manufacturing
process. Some units require
higher amounts of 0-40 µ range
particles to help with circulation.
The next characteristic of fresh
catalyst that must be considered
is the particle density. The DpTH
mentioned above will decrease
with increased catalyst particle
particle density is not the same
as apparent bulk density (ABD).
Industry typically measures and
reports ABD as part of the routine
Ecat analysis, but this should not
be mistaken for particle density
for cyclone efficiency purposes.
Since Al2O3 is denser than SiO2,
catalysts with higher alumina
content will have higher catalyst
particle density.
The third characteristic is the
inherent attrition resistance of
the fresh catalyst. Industry
measures the attrition resistance
via a variety of tests, with the
primary goal of providing a
relative indication of catalyst
attrition resistance. Grace utilizes

𝟗𝟗𝝁𝝁𝑮𝑮 𝑳𝑳𝑾𝑾  
𝑫𝑫𝑷𝑷𝑻𝑻𝑻𝑻 =
𝝅𝝅𝑵𝑵𝑺𝑺   𝑽𝑽𝒊𝒊   𝝆𝝆𝑷𝑷 − 𝝆𝝆𝑮𝑮

𝝁𝝁𝑮𝑮  , 𝝆𝝆𝑮𝑮 , 𝑽𝑽𝒊𝒊 = Gas viscosity, density and velocity

D PTh
𝑳𝑳𝑾𝑾 , 𝑵𝑵𝑺𝑺 = Width, number of spirals
Predominantly
Lost 𝝆𝝆𝑷𝑷 = Particle density

MIDAS ® GOLD
The Gold Standard for Resid Upgrading
Figure 1: Theoretical depiction of a cyclone’s ability to retain particles Equation 1: Cyclone performance theory calculation
Grace FCC Catalyst

22 Catalagram® No.115 | Fall 2014 23

 

 
AFPM Q&A RESPONSES - GRACE FCC
the DI test or Davison Index. On
the DI scale, a lower number is
less likely to cause attrition and
generate microfines. It is usually
not valid to compare attrition
resistance results obtained
from different laboratories.
Additionally, it is important to
note that the energy applied to
a catalyst sample during attrition
testing is much more severe than
commercial conditions.
As discussed above, the majority
of the microfines created in
the FCCU will leave the unit
through either the reactor or
regenerator cyclones, with the
latter potentially contributing to
increased particulate emissions
at the stack.
The attrition resistance of the
catalyst is a function of the
manufacturing process and the
binder material utilized during
the manufacturing process.
Figure 2 is an example of how a
refiner improved the FCCU stack
opacity with catalyst formulation.
The reduction was achieved
changing to a Grace supplied
60
55
50
Stack Opacity, %
45
40
35
30
25
20
15
10
-3 months -1 months
Figure 2: Commercial application of lower DI fresh catalyst
24 Catalagram® No.115 | Fall 2014
catalyst with lower DI and lower
0-40 µ content in the fresh catalyst.
The final characteristic of fresh
catalyst that affects particulate
emissions is its morphology.
Morphology can be defined
as the study of the form and
structure of a particle and its
specific structural features.
A catalyst particle that has a
smoother exterior surface is less
likely to generate microfines in an
FCCU. Even catalysts with a low
fresh DI measurement can cause
increased particulate emissions
if there are surface irregularities
resulting from the manufacturing
process. In order to demonstrate
this visually, Figure 3 presents
SEM’s (scanning electron
microscopy) of “bad” and “good”
fresh catalyst morphology for a
side by side comparison.
In conclusion, there are
several characteristics of fresh
catalyst that can be controlled
to reduce particle losses
and thereby reduce flue gas
emissions. Specifically, to lower
emissions the fresh FCC catalyst
Change to Grace Catalyst
“Bad Morphology”
+1 months +3 months +5 months
Date
Figure 3: SEM’s of fresh catalyst (magnified X250)
should possess the following
characteristics: a particle size
distribution with an optimal
range of 0-40 µ particles, higher
catalyst particle density, lower
DI, and superior morphology.
Grace’s alumina-sol technology
provides superior binding to the
catalyst particle leading to best-
in-industry attrition resistance.
The versatility and performance
of alumina-sol catalysts coupled
with Grace’s manufacturing
capability, have resulted in wide-
market acceptance and as a
result, Grace is the preferred
FCC technology for loss sensitive
units around the world. v
“Good Morphology”
Question: What factors influence butylene selectivity in the FCC LPG?
What is the relative role of feedstocks, catalysts, additives, and operating
conditions?
v Kenneth Bryden (Grace)
Fundamentals:
A number of factors influence
butylene selectivity in the FCC
LPG stream. Figure 1 summarizes
the fundamentals of butylene
selectivity and maximization. The
cracking pathways involved can
be thought of as four stages. In
Figure 1, the desired pathways for
maximizing butylenes are in green
and the undesired pathways are
in red. The first stage is cracking
of the feed to naphtha range
olefins. These cracking reactions
can occur on zeolite or matrix. In
the second stage, these naphtha
olefins can react to naphtha
paraffins by hydrogen transfer (an
undesired pathway), or crack to
C3 and C4 olefins. The cracking
of gasoline range olefins to C3
and C4 olefins is much faster
on ZSM-5 zeolite than Y-zeolite.
Catalyst factors that influence
Figure 1: Butylene maximization and
selectivity fundamentals
the selectivity of butylene versus
propylene will be discussed later
in this answer. The C3 and C4
olefins that are produced in Stage
3 can further react by hydrogen
transfer to form propane,
iso-butane and butane, which
are undesired when maximizing
butylene. These reactions occur
much faster on zeolite than on
matrix. Based on this fundamental
reaction scheme, butylenes can
be maximized by decreasing the
hydrogen transfer activity and
by minimizing the cracking of
naphtha olefins to propylene. The
effects of individual factors on
butylene selectivity are discussed
in detail below.
Feedstock Effects
The chemical nature of the starting
feedstock will affect the products
that can be produced from it. As
Stage 1 Stage 2
VGO/Resid Hydrogen
Cracking Transfer
(Zeolite or Matrix)
Naphtha
Feed
Olefins
Naphtha
Paraffins
Maximize C4= by decreasing hydrogen transfer activity
(Stage 2/4) and minimizing cracking to C3= (Stage 3)
AFPM Q&A RESPONSES - GRACE FCC
a feed becomes more paraffinic,
butylene production increases. As
a feed becomes more aromatic,
the olefinicity of the LPG stream
will drop.1 As a feedstock
becomes more naphthenic, LPG
olefin production drops. This is
because naphthenes are good
hydrogen donors and react with
gasoline range olefins to make
aromatics and gasoline range
paraffins.2 Since gasoline range
olefins are the precursors to LPG
olefins, this depletes the pool of
available material to make LPG
olefins and reduces LPG olefinicity.
Operating Condition Effects
Typically total C4 production
depends on conversion,
regardless if the conversion is
achieved by reactor temperature
or catalyst-to-oil ratio.3 However,
the ratio of isobutane to butylene
Stage 3 Stage 4
Olefin Cracking Hydrogen Transfer
(ZSM-5 >> Y-Zeolite) Zeolite >> Matrix
25
AFPM Q&A RESPONSES - GRACE FCC
is strongly influenced by reactor
temperature. Since hydrogen
transfer has higher activation
energy than cracking, the rate
of cracking increases faster
with temperature than the rate
of hydrogen transfer.4 Thus, as
reactor temperature increases, the
ratio of iC4/C4= is lowered. As a
rule of thumb, the ratio of iC4/C4=
drops by 0.025 per 10°F increase
in reactor temperature.3
Changing reactor pressure will
also affect the olefinicity of the
C4 stream. Since hydrogen
transfer is a bi-molecular reaction,
decreasing reactor pressure
lowers hydrogen transfer and
increases the olefinicity of the
LPG stream. Data quantifying
the effect of reactor pressure on
butylene selectivity can be found
in Reference 5.
Increased carbon on regenerated
catalyst (CRC) reduces the rate
of hydrogen transfer reactions
and results in a more olefinic LPG
Reactant
C8=
C7=
2 C3=
C6=
C2= + C4=
Figure 2: Selectivity from cracking gasoline range olefins over ZSM-5 additive and ACHIEVE® 400 Catalyst
26 Catalagram® No.115 | Fall 2014
stream. Also, increased CRC will
usually lower overall conversion.
Catalyst Effects
Base catalyst affects butylene
selectivity through both the rate
of hydrogen transfer and through
the amount of naphtha range
olefins produced. Since increased
hydrogen transfer reduces LPG
olefinicity, butylene olefinicity
drops as the amount of rare earth
on zeolite increases, as measured
by unit cell size (UCS). Higher
matrix activity increases C4
olefinicity. Lowering the zeolite/
matrix ratio of the base catalyst
increases gasoline range olefins
and thus the amount of butylene
produced from these precursors.
ZSM-5 based additives have a
significant effect on the olefinicity
of the LPG stream. ZSM-5 cracks
the C6+ gasoline range olefins to
propylene and butylene.4 Adding
more ZSM-5 additive will deplete
the gasoline range olefins and
produce both more propylene
Relative
Selectivity Reactivity
2 C4= 44%
C3= + C5= 100
56%
C3= + C4= 95%
C2= + C5= 2% 12
83%
1.5
16%
and butylene. The increased
propylene yield with ZSM-5
additives is not always desirable.
A better solution is to boost zeolite
isomerization activity within the
catalyst to selectively increase
the yield of FCC butylene.
Grace’s ACHIEVE® 400 catalyst is
formulated with multiple zeolites
with tailored acidity, to deliver
an optimum level of butylenes to
keep the alkylation unit full and
maintain refinery pool octane.
With traditional ZSM-5 technology,
cracking of gasoline olefins
continues past C7 into the C6
and generates a disproportionate
amount of propylene relative to
butylenes as shown in Figure 2.
The newly developed dual-zeolite
technology in ACHIEVE® 400
catalyst works synergistically with
Grace’s high diffusivity matrix,
to selectively enhance olefinicity,
preferentially cracking gasoline
olefins at C7 and above into
butylene. The result is a higher
ratio of C4 to C3 olefin yield than
separate light olefins additives.
C4=/C3= ACHIEVE 400
®
ZSM-5 Additive
1.57
1.0
0.1
Figure 3 illustrates the butylene
selectivity improvement of
ACHIEVE® 400 catalyst compared
to a system using conventional
ZSM-5 based additive6. In
addition to increasing butylene
selectivity, ACHIEVE® 400 catalyst
has been shown to increase the
octane of FCC naphtha.
In summary, butylene selectivity
is influenced by a number of
complex factors in the FCC.
Proper choice of catalysts and
additives based on operating
objectives and unit constraints
is critical in maximizing butylene
selectivity. Grace’s technical
service team has the experience
and resources to help refiners
evaluate feed, operating condition
and catalyst shifts to maximize
butylene selectivity. v
1.4
1.2
=
4
C4= C1.01
?
0.8
0.6
0.6
Base MIDAS® + OlefinsMax®
Figure 3: Butylene selectivity improvement of ACHIEVE® 400 catalyst compared to a system
using conventional ZSM-5 based additive.
AFPM Q&A RESPONSES - GRACE FCC
Reference:
1. H
 arding, R. H.; Zhao, X.; Qian, K.;
Rajagopalan, K.; Cheng, W.-C., “Fluid
Catalytic Cracking Selectivities of Gas Oil
Boiling Point and Hydrocarbon Fractions,”
Industrial & Engineering Chemistry
Research 1996, 35, 2561.
2. Z hao, X.; Harding, R. H., “ZSM-5 Additive
in Fluid Catalytic Cracking. 2. Effect of
Hydrogen Transfer Characteristics of the
Base Cracking Catalysts and Feedstocks,”
Industrial & Engineering Chemistry
Research 1999, 38, 3854.
3. Grace Guide to Fluid Catalytic Cracking,
Chapter 6, FCC Operation.
4. Z hao, X.; Roberie, T. G., “ZSM-5 Additive
in Fluid Catalytic Cracking. 1. Effect of
Additive Level and Temperature on Light
Olefins and Gasoline Olefins,” Industrial
& Engineering Chemistry Research 1999,
38, 3847.
5. H
 u, R.; Cheng, W.-C.; Weatherbee, G.; Ma,
H.; Roberie, T., “Effect of Hydrocarbon
Partial Pressure on Propylene Production
in the FCC,” AM-08-51, NPRA Annual
Meeting, 2008.
6. B
 ryden, K.; Federspiel, M.; Habib, E.T.;
Schiller, R., “Processing Tight Oils in FCC:
Issues, Opportunities and Flexible Catalytic
Solutions,” AM-14-16, AFPM Annual
Meeting, 2014.
1.0
0.8 1 1.2 1.4
? C3=
® ®
ACHIEVE® 400
®
27
AFPM Q&A RESPONSES - ART
AFPM QUESTIONS 2014
v Charles Olsen (Director, Distillate R&D and Technical Service, ART)
Brian Watkins (Manager, Hydrotreating Pilot Plant & Technical Service, ART)
Greg Rosinski (Senior Technical Service Engineer, ART)
Question: What solutions are available to refiners for extending cycle
length in distillate hydrotreating units limited by product color?
The color of distillate products is
affected by the reaction conditions
in the hydrotreater, especially
temperature and hydrogen partial
pressure. As (outlet) temperature
increases and/or hydrogen partial
pressure decreases, the product
color degrades. It is also generally
accepted that the species
responsible for color formation in
distillates are polynuclear aromatic
(PNA) molecules, some of which
cause color issues even at low
concentrations. Certain nitrogen
(and other polar) compounds also
have been implicated as problems
for distillate product color and
product instability. These species
can polymerize to form condensed
aromatic structures, which tend to
be green to yellow/brown and can
also form sediment via oxidation
and free radical reactions.
PNAs are readily saturated to
one- and two-ringed aromatics
under typical diesel hydrotreating
28 Catalagram® No.115 | Fall 2014
conditions at start of run (SOR),
but as the temperature of the
reactor increases towards EOR,
an equilibrium constraint may
be reached whereby the reverse
dehydrogenation reaction
becomes more favorable. At some
combination of low hydrogen
partial pressure and high
temperature, the dehydrogenation
reaction predominates and
PNAs begin to form, resulting
in a degradation of the color of
the diesel product. Other work
(Takatuka et.al., NPRA AM-
91-39) showed that the color
bodies responsible for diesel
product color degradation were
concentrated in the higher boiling
points in the diesel (>480°F).
This suggests that color can be
improved by adjusting the diesel
endpoint. To learn more about
color degradation in ULSD see
Catalagram® No.105.
Quenching the Bottom Bed of
the Hydrotreater
One approach to extend the cycle
life of a hydrotreater is to increase
quench to the bottom bed of the
hydrotreater. This reduces the
outlet temperature and helps
to increase the outlet hydrogen
partial pressure relative to lower
amounts of quench. Both actions
create a better environment for
PNA saturation.
This requires that the upper beds
of the hydrotreater operate at
higher temperatures in order
to maintain the required HDS
conversion. This also means that
the furnace must have sufficient
capacity to achieve the higher
inlet temperatures. Operating in
this manner offers the potential to
add an additional 10-20°F to the
cycle length depending on the
unit capabilities (furnace limits
and quench capacity).
Adjusting the Feed to
the Unit
Another approach, which
may be implemented with
the one just discussed,
involves adjusting the feed
to the unit. FCC LCO has a
significant impact on diesel
product color due to the high
amounts of PNAs present.
Reducing (or eliminating) the
amount of LCO in the feed
will help suppress product
color degradation as the unit
approaches EOR. Data also
show that the color bodies
that cause problems for ULSD
tend to be concentrated at
the higher boiling points of
the distillation on the feed/
product. Since data indicates
that the color bodies that
cause problems for ULSD
tend to be concentrated at
the higher boiling points
of the distillation of the
feed/product,reducing the
endpoint of the LCO reduces
the concentration of these
species, which will help
maintain acceptable product
color as the unit moves toward
EOR. Less ideal solutions
would be to find another unit
to process problematic feeds
or to reduce the LHSV, which
will lower the WABT and shift
the equilibrium to be more
favorable for PNA saturation. v
Question: What is a minimum cloud point
improvement that makes economical sense
to apply catalytic dewaxing vs. traditional
(i.e. additives and kero blending) Cold Flow
improvement methods?
The target market for these
products requires much more
than several degrees decrease in
cloud point below the value of the
feed, which is generally beyond
that observed by hydrotreating
alone. The utility of catalytic
dewaxing needs to be weighed
against the costs/benefits of other
cold flow improvement methods.
The ability to improve the cold
flow properties of the diesel in
the hydrotreater using a dewaxing
technology can have significant
economic advantages that
other options do not provide
especially if a high degree of
cold flow improvement is desired.
Understanding the cold flow
requirements is necessary to
create an individually tailored
process and avoid the pitfalls
associated with inappropriate
quantities of hydrodewaxing(HDW)
catalyst, such as yield losses and
not having the flexibility to meet
market demands.
Understanding the Trade-offs
as Dewax Catalyst is Changed
The typical process of dewaxing
utilizes a ZSM-5 type catalyst.
The structure of ZSM-5 is
such that only straight chained
hydrocarbon molecules (normal
paraffins or n-paraffins) fit
AFPM Q&A RESPONSES - ART
inside the cage structure and
are cracked into smaller, lighter
molecules. These molecules
have significantly lower cloud
and pour point characteristics.
One of the keys to successfully
combining a dewaxing catalyst
with an hydrodesulfurization(HDS)
catalyst system is an
understanding of the tradeoffs
between dewaxing activity and
HDS activity as the amount of
dewax catalyst is changed.
Similar to a hydrocracking
reactor, as the temperatures are
increased over the bed of HDW
catalyst, the ability to convert the
n-paraffins increases. The extent
of cloud point reduction at a given
temperature depends on the
LHSV over the dewax bed as well
as the hydrogen partial pressure
of the unit. Once the temperature
is high enough to begin
dewaxing, the kinetic response for
converting the n-paraffins is linear
for both catalyst systems.
The HDW function is to break the
n-paraffins into smaller molecules
in order create less waxy molecules
in the finished diesel product.
This chain breaking reaction has
the potential disadvantage that it
can convert diesel boiling range
material into naphtha and lighter
materials. These materials, if the
29
AFPM Q&A RESPONSES - ART
refinery is able to tolerate and
utilize them, could be quite
valuable. If a significant volume
of diesel is converted to lighter
products, the downstream
equipment might not be
capable of handling excess
light materials.
ART’s pilot tests show that
there is a complex interaction
between dewaxing and
hydrotreating in ULSD
applications. There is a
balance between dewaxing
activity and HDS activity which
needs to be understood when
designing a catalyst system.
Furthermore, the liquid yield
needs to be considered at
both SOR and EOR as this
is highly dependent on the
amount of dewax catalyst in
the system. ART technical
services staff work with
refiners to provide the right
catalyst system tailored for
maximum refinery profit. v
30 Catalagram® No.115 | Fall 2014
Question: How are refiners planning to
meet Tier 3 gasoline specifications? Please share
strategies for post-treat and pre-treat options,
feedstock selection and catalyst technologies.
Tier 3 gasoline regulations require
that all gasoline contain ≤10
wppm sulfur. This is a decrease
from the current Tier 2 regulations
of ≤30 wppm sulfur. This change
in product sulfur can have a
dramatic impact on refiners that
have a significant portion of their
gasoline pool generated from
the FCC. In order to meet this
regulation, there are only two
methodologies to reduce the
gasoline sulfur pool. Both involve
some level of hydrotreating, either
before or after the FCC unit. The
process of hydrotreating after
the FCC unit can have a dramatic
effect on gasoline octane levels
due to the additional olefin
saturation that occurs when
reducing the product sulfur sulfur.
Hydrotreating Before or After
the FCC Unit
For those refiners that utilize a
hydrotreater in front of their FCC
unit, changes to that operation
need to be considered in order
to meet the desired product
targets. To address these needs,
ART utilizes the ApART® catalyst
system for FCC pretreatment.
This technology is designed to
provide significant increases in
HDS conversion while significantly
upgrading FCC feedstock
quality and increasing yields. In
essence, an ApART® catalyst
AFPM Q&A RESPONSES - ART
correlation between FCC feed
sulfur and the corresponding
nitrogen and PNAs improves FCC
product value when targeting
FCC gasoline sulfur. In this case, gasoline production. But this
the sulfur content in the FCC needs to be balanced against
gasoline is roughly 100 times less the costs of higher hydrogen
than the sulfur in the feed to the consumption and shorter cycle
FCC. Increasing the severity of length that result from this mode
the pretreater operation to reduce of operation. Use of tailored
system is a staged bed of high
product sulfur will tend to move ApART® catalyst systems with
activity NiMo and CoMo catalysts
the catalyst towards more of a 486DX® and 586DX® can optimize
where the relative quantities of
PNA mode of operation. This the FCC in order to produce high
each catalyst can be optimized
mode, while beneficial to the quality feeds to the FCC as well
to meet individual refiner’s goals
FCC in many ways, can impact as lower sulfur products resulting
and constraints. ART continues
the cycle length due to increased in less impact on downstream
to develop a better understanding
temperatures. hydrotreating. A result is
of the reactions and kinetics
less impact on downstream
involved in FCC pretreating,
Both the hydrotreating catalyst hydrotreating. This tailoring can
and through its relationship with
system and the operating strategy also be beneficial if the lower
Grace, a detailed understanding
for the pretreater are critical to sulfur and higher gravity FCC
of the effects of hydrotreating on
providing the highest quality products can be blended directly
FCC unit performance.
feed for the FCC. Optimizing without hydrotreating, minimizing
the hydrotreater to remove potential octane loss. v
It is clear that FCC pretreating
plays an important role in
reducing the sulfur content Figure 1: Relationship between FCC
of FCC products. ART has 10,000 Gasoline Sulfur and FCC Feed Sulfur
completed many studies
analyzing the effects of
hydrotreating on FCC
FCC Gasoline Sulfur, ppm
performance and the quality of 1,000
the FCC products. The data
demonstrate that reducing the
sulfur in FCC gasoline and LCO
simply requires a reduction in 100
the sulfur of the FCC feed by
increasing the severity of the
pretreater. Figure 1 shows the
relationship between FCC feed 10
sulfur and the resulting sulfur of
the FCC gasoline.
This data is generated using a
variety of FCC feeds that had 1
been hydrotreated over several 10 100 1,000 10,000 100,000
types of catalysts and catalyst
systems. There is a positive FCC Feed Sulfur, ppm
31
AFPM Q&A RESPONSES - ART AFPM Q&A RESPONSES - ART

Question: Silicon uptake on hydrotreating catalysts is an increasing coker cycle. This means that
the silicon in the naphtha stream Question: Explain the differences with
problem. What operating conditions favor maximum silicon pickup by the will vary with the timing of the renewable diesel and biodiesel. Can renewable
coker cycle. In order to get a
catalyst? Are there differences between silicon from coker antifoams and representative amount of silicon feedstocks be co-processed with traditional diesels
in the coker naphtha stream, a
other sources? Does the presence of other contaminants such as nickel and composite should be made of
in an existing ULSD unit and how does this
vanadium affect the silicon pick-up by the catalyst? What best practices are hourly samples mixed together impact RIN’s?
for the time of the cycle. For
used for monitoring silicon pick-up by the catalyst? example, for an eight-hour Fuels that are produced when Managing n-Paraffins and
cycle, eight samples would vegetable oils or animal fats are Contaminants
Silicon is probably the most also are sometimes used in Another important aspect of silicon be mixed and the composite processed in traditional refining One consequence of co-
widespread catalyst poison barge unloading. poisoning is that silicon pick up sample analyzed for silicon. To processes are considered co- processing is an increase in
encountered in hydrotreater feeds. depends on catalyst temperature. measure the silicon, an ICP-MS processed renewable diesel. n-paraffins in the diesel. This can
The main source of silicon is from In the hydrotreater, the silica Commercial data clearly shows (Inductively Coupled Plasma Some common sources of be of significant value for ULSD
delayed coker operations that use a fragments from the antifoam agent that the operating temperature of Mass Spectrometry) instrument renewable feeds are those as they typically have cetane
polydimethylsiloxane-based anti- undergo a condensation reaction the application must be considered can be used. This instrument/ produced for food-grade oils numbers ranging from 95 to 110,
foam agent to suppress foaming with the alumina surface of the when discussing silicon pickup method can measure very low such as soybean, rapeseed, which can provide a significant
in the coker drums. The siloxane catalyst forming a strong chemical capacity and when designing (ppb) metal concentrations. and other vegetable oils. The boost for those refiners processing
polymer breaks down in the coking bond. Once the silicon is bound effective guard catalyst systems. traditional process for introducing feeds with lower cetane (i.e.
process to primarily methylsiloxane to the alumina surface, it cannot The maximum capacity of the Alternatively, the refinery could these sources into the diesel pool FCC LCO’s). The typical diesel
trimers. These species are volatile be removed by regeneration or catalyst needs to be considered measure the amount of anti- is to use the transesterification hydrotreater has only a small affect
at coker temperatures with boiling other means. It is a more moderate as well as the capacity at the foam used by the coker over the reaction for breaking the glycerol on cetane with cetane upgrade of
points ranging from 270-475°F poison compared to contaminants temperatures of the specific unit course of a month. Assuming from the fatty acid chains. Diesel about 2-4 numbers.
(132-246°C). As a result, these like sodium or arsenic, but it in order to accurately predict the that 70-80% of the silicon ends produced via transesterification
compounds tend to concentrate nonetheless results in activity loss point at which silicon will break up in the naphtha fraction, the is called biodiesel and earns the Another concern is that these
in the overhead products, and as on the order of 5-10°F (3-6°C) for through into the next bed of refiner then could estimate the Biomass-Based Diesel Renewable renewable feed sources can
a general rule of thumb, 70-80% each 1.0 wt% Si deposited on the catalyst or downstream unit. amount of silicon going into the Identification Number (RIN) include various contaminants.
of the silicon injected to the coker hydrotreating catalyst. naphtha hydrotreater. While this under the EPA's RFS2 program. An analysis of several different
ends up in the coker naphtha Accurately measuring silicon in would be less accurate than the Co-processed renewable diesel biofeed sources has indicated
fraction and the balance is in the A variety of analytical techniques naphtha streams can be done, preceding method, it would also qualifies for the Advanced the presence of contaminants
distillate fraction. More recently, have been applied to silicon but effort to get a representative be less costly. v Biofuel RIN. such as sodium, calcium and
refineries that do not have cokers poisoned catalysts, and this sample of the naphtha is required.
phosphorus. Since these
have experienced silicon poisoning confirms that the silicon is The silicon in the coker naphtha ART has completed extensive pilot renewable feeds are derived
of hydrotreating catalysts. These associated with the alumina depends on the type and amount plant studies demonstrating that from a biological source, they
refineries have begun processing support as opposed to the active of antifoam chemical at the delayed these types of feeds can be co- also contain a high concentration
synthetic or other opportunity metal sulfides of the catalyst. coker unit. Delayed cokers have processed with traditional diesels of oxygen. The oxygen content
crudes and the process of making Furthermore, the silicon is cycles ranging anywhere between in an existing ULSD unit. To ensure ranges from 10 to 15%, and is
synthetic crude often involves dispersed throughout the 8 – 24 hours. The coker unit is the finished blend quality, refiners entirely dependent on the length
a coking step. In addition, it available alumina surface as continually producing a coker who use the co-processing method and degree of saturation of the
is becoming more common opposed to poisoning only the naphtha stream during these have precise knowledge of the bio- fatty acid chains. This quantity
to use silicon additives in the exterior of the catalyst pellet. As cycles, which is typically being based fuels that are incorporated of oxygen is important, as under
drilling process, and for pipeline a consequence, the available sent from the fractionator straight into the diesel pool. normal hydrotreating conditions
companies to use them for both alumina surface area of a catalyst into the naphtha hydrotreater feed
flow enhancing performance and has a significant impact on silicon drum. The antifoam chemical is
foaming issues. Silicon additives capacity of a catalyst. not usually added for the entire

32 Catalagram® No.115 | Fall 2014 33

AFPM Q&A RESPONSES - ART CUSTOMER PARTNERSHIP

the oxygen will react with

the hydrogen to form water.
This water, if generated in a
significant enough quantity,
may cause problems such
as weakening the catalyst
support or redistribution of
Reducing SOx Emissions at BP
the active metals and loss of
surface area. At the expected Castellon Using FCC Additives
blending ratios of 10%, the
oxygen content is around 1 v Ana Piera, Marta Calvo, Angel Llanes (BP Castellon)
to 1.5 wt%, and even if all of Colin Baillie, Rafael Gonzalez (Grace)
the oxygen is converted, this
is unlikely to generate enough Explore the technical factors behind BP's decision to
water to be a significant use additives, rather than more costly alternatives.
problem.

An increase in hydrogen
consumption to saturate C=C
bonds is expected due to the
addition of unsaturated chains
from the bio component. The
co-processing of renewable
components may yield
improvements in the diesel
cetane due to the increase in
n-paraffin content in the diesel
product. These n-paraffins,
however, raise concerns about
the biofeed-based diesel cloud
point. Normal paraffins have
a significantly higher cloud
point than other hydrocarbons
of similar carbon number.
Since hydrotreating converts
the fatty acid chains into
long chain n-paraffins, it is
expected that the cloud point
of the hydrotreated product
will significantly increase
compared to the product when
processing just an
SR-base feed. v

34 Catalagram® No.115 | Fall 2014 35

CUSTOMER PARTNERSHIP
Additives Offer an Attractive Alternative to
Reduce SOx Emissions
Refiners often choose specialized additives
to achieve SOx reduction because it is an
extremely effective and flexible way to reduce
SOx emissions from the FCCU.
The other, more costly options for reducing SOx
emissions include flue gas scrubbing (FGS),
the use of lower sulfur-containing feedstocks,
and hydrosulfurization (HDS). FGS requires a
significant capital investment and the operating
costs are high. In addition, discarding the
spent treating compounds such as lime, caustic
soda, or other compounds can be problematic.
Choosing to process lower sulfur feeds can be
expensive and may not even be a viable option.
HDS provides improved yields as well as lower
SOx emissions, but also requires the highest
capital investment.
Operating Variables that Affect SOx
Emissions
Feedstock sulfur is the source of SOx in the
FCC unit. To a certain extent SOx emissions
correlate to feed sulfur levels with typically two
to 10 percent of the feedstock sulfur ending
up in the coke, which when burned off in the
regenerator creates SOx. The actual amount
of sulfur going to coke is largely affected by
the sulfur feedstock molecules. For example,
SOx reduction (%)
hydrotreating severity plays a large role.
Although hydrotreated feedstocks typically
have lower sulfur content, a higher amount of
the sulfur can end up in coke, with as much as
30 percent observed for severely hydrotreated
feeds. In addition, aromatic or thiophenic feed
sulfur is more likely to go to coke compared
to mercaptans. As a result, there is often a
stronger correlation between SOx emissions
with aromatic or thiophenic feed sulfur than
overall feed sulfur content. There is also often a
better correlation of SOx emissions with slurry
sulfur content than feed sulfur content. Although
sulfur content in the slurry itself is not a cause
of SOx emissions, the conditions leading to
increased sulfur content in the slurry are similar
to those leading to increased sulfur content in
coke, and thus SOx emissions.
36 Catalagram® No.115 | Fall 2014
CUSTOMER PARTNERSHIP
100
Stripper operation also plays a of combustion promoters can assist at ca. 6% of the catalyst addition
significant role in SOx formation the performance of SOx additives by rate decreased SOx levels to below
90 with lower efficiency resulting in helping to catalyze the reaction of the secondary target, achieving SOx
higher SOx emissions. For example, SO2 to SO3. reduction levels of close to 70%
Normalized SOx Emissions
80
heavy entrained hydrocarbons tend (Figure 2).
70 to be high in sulfur content, and if With the various factors that influence
60 not effectively removed from the SOx emissions, evidence shows that All Grace’s additives including Super
catalyst in the stripper, will result in before beginning a SOx reduction DESOX® can be pre-blended with the
50
higher levels of sulfur entering the additive trial it is necessary to FCC catalyst, or added separately
40 regenerator. establish a baseline for uncontrolled through the use of a Grace additive
30 SOx emissions. This will allow the system. Grace offers a variety of
There are additional variables that subsequent comparison of SOx catalyst and additive addition system
20
affect the performance of SOx levels obtained with and without models to enable accurate control
10 additives. Units with a high catalyst SOx reduction additives at constant of the circulating inventory activity.
circulation rate generally observe conditions. Optimum performance is achieved
0
0 20 40 60 80 100 120 140 higher pick-up factors when using by providing smaller, more frequent
Days
SOx reduction additives. This Grace Super DESOX® Trial at BP catalyst or additive doses, thus
is attributed to more available Castellon for SOx Reduction avoiding large slug additions.
% SOx Reduction Achieved % SOx Reduction Achieved Periods Using
with Super DESOX® without Super DESOX® Super DESOX®
catalytic sites for SOx capture. The BP Castellon refinery in Spain
The performance of SOx additives has a nameplate crude capacity of BP Castellon Reduced
are negatively affected by higher 110,000 bpd. The FCC unit is an SOx Emissions with Grace
Figure 1: Normalized Flue Gas SO2 Emission Levels With and Without Grace
regenerator temperatures. The Exxon Flexicracker model operating Environmental Additives
Super DESOX® Additive
oxidation of SO2 to SO3 is a in full burn with a capacity of 30,000 Based on the company’s commitment
critical reaction pathway in the SOx bpd . The FCCU typically processes to reduce emissions as well as
reduction mechanism since the a VGO feedstock with slurry increasingly stringent emissions
emissions control additive reacts recycle, and sometimes processes standards, the BP Castellon refinery
100 20.0
with SO3 not SO2. Although a higher additional Atmospheric Residue is reducing SOx emissions using
90
17.5 temperature increases the oxidation feedstock. As emissions standards FCC environmental additives from
80
of SO2 to SO3, the resulting sulfates tighten, the refinery seeks to reduce Grace. In a recent trial, Super
15.0 are less stable in the regenerator. In environmental emissions from the DESOX® achieved SOx reductions of
70 contrast, high reactor temperatures
FCC unit and from the refinery as a approximately 70%.
12.5 favor the required reduction of
60 whole.
sulfates to H2S in the reactor, thus
%CAR
50 10.0 These results affirm the performance
decreasing SOx levels. Accordingly, in the fourth quarter of Super DESOX®, with its patented
40
7.5 of 2013, the refinery began a trial magnesium-alumina spinel structure,
30 One of the key variables is the of Super DESOX®, a SOx reduction as the leading SOx reduction
5.0 influence of oxygen concentration additive from Grace. Prior to the additive, successfully used by over
20
and distribution in the regenerator. trial, FCC feed sulfur levels at BP 100 refiners worldwide. v
2.5
10 Because the oxidation of SO2 to Castellon were typically between 0.6-
0
SO3 is a key step for SOx removal, 1.7 wt.%, regenerator temperatures
0.0
0 20 40 60 80 100 120 140 an increase in excess oxygen or were typically around 720 °C, with
Days improved distribution enhances flue gas excess oxygen content
% SOx Reduction Achieved Super DESOX® Addition Periods Using Super additive performance. Not only does about 0.9 to 1.1%.
with Super DESOX® Rate (% of CAR) DESOX® improved stripper efficiency result
in a decreased amount of sulfur- The primary objective of the trial
Figure 2: Flue Gas SO2 Reduction Achieved Versus Additive Addition Rate containing hydrocarbons entering the was to decrease typical flue gas
regenerator, but it also helps to fully SOx levels by approximately 40%
hydrolyze the sulfide intermediate with a further secondary target of
to H2S, thus increasing additive just over 50% reduction (Figure 1).
performance. Finally, the presence The introduction of Super DESOX®
37
CUSTOMER PARTNERSHIP CUSTOMER PARTNERSHIP

Improving Safety, Table 1: RFCC Catalyst History at the Orpic Sohar Refinery company that completed advanced process
modeling simulating the commercial unit

Reliability and Profitability Period Description performance of the screened catalysts.

The outcome clearly demonstrated that the
1 2006-2009 RFCCU startup using competitor catalyst
optimized Grace catalyst was the most suitable
at the Orpic Sohar Refinery 2
3
2009-2011
2011-2013
Switch to Grace catalyst
Move to low rare-earth Grace catalyst
catalyst for the challenging operation at the
Sohar RFCC unit. As a result, Grace’s supply
contract was extended.
v Maadh Al Badri and Dilip Singh (Orpic) 4 2013- Application of optimized Grace catalyst
Nathan Ergonul, Talal Al-Rawahi, Colin Baillie (Grace) Table 4 shows the FCC unit yields obtained
from the optimized Grace catalyst compared
The FCC catalyst is one of the key factors in the B and Grace. This illustrates that feedstock properties to the previous catalyst. Bottoms conversion
profitability of Orpic’s resid FCC unit at Sohar, which deteriorated, with specific gravity, sulfur, ConCarbon, Table 2: FCC Unit Data Comparing Competitor B and Grace was increased by over 1.5 wt.%, resulting in
places a high level of responsibility on the supplier for nickel, and vanadium increasing considerably under Technology a substantial increase in conversion by nearly
both the product technology and technical service. This comparable operating conditions. The table also shows 2 wt.%. Due to a lower quantity of ZSM-5 in
article describes the many steps Grace has taken to help that, despite the poorer feed quality, unit performance Feed Properties Competitor B Grace the Ecat, as well as the improved gasoline
improve safety, reliability, and profitability at the Orpic significantly improved after switching from Competitor B Specific Gravity base +0.003 selectivity, naphtha yield was increased by
Sohar refinery. to Grace. Additionally, conversion increased by more than Sulfur Content wt.% base +22% nearly 2 wt.% at the expense of LPG yield.
1 wt.%, translating to a significant increase in propylene The optimized Grace catalyst led to a drop in
Concarbon wt.% base +9%
Orpic Background yield, which is a key unit objective. Bottoms yield was delta coke, which enabled greater operational
The first oil was discovered in Oman in 1963 at the Naith reduced by nearly 1 wt.%. Nickel Content ppm base +23% flexibility to process heavier feeds. As shown in
Field. Oman’s first refinery was commissioned nearly Vanadium Content ppm base +23% Table 4, the optimized catalyst allowed feed rate
20 years later in 1982 at Mina Al Fahal with a capacity In 2011, Chinese export quotas hit the FCC industry to be increased by 10%.
Operating Conditions
of 50,000 barrels per day. A series of investments in with skyrocketing prices of rare-earth metals, a critical
the early 2000s yielded the first production of unleaded component of FCC catalysts. The key index for FCC Feed Temperature °C base +14 °C Improving Reliability and Safety
gasoline followed by ultra low sulfur diesel. In 2006, catalysts is the cost of 99% lanthanum oxide FOB from ROT °C base -3 °C In the original system design at the Sohar
Orpic opened a new refinery in Sohar with a capacity China, which increased dramatically from $2,300/MT refinery, four hoppers were used for the storage
Cat-to-Oil Ratio g/g 9.6 8.5
of 116,000 barrels per day, and commissioned a new in January 2007 to more than $100,000/MT in August of fresh FCC catalyst, Ecat and ZSM-5 additive.
polypropylene plant. Oman’s first aromatics plant opened 2011, according to the Asian Metals Index. In response, SCAR kg/t FF base +4% In 2010, an additional system from Grace
in Sohar in 2010. Grace led the development of alternative technologies Ecat Properties was installed to allow multiple components to
and was the only supplier to commercialize low and zero be dosed, enabling the refinery to operate at
Nickel ppm base +17%
The resid FCC unit is a core process of the refining rare-earth FCC catalysts. In the case of Orpic, Grace maximum flexibility and reliability (Figure 1).
complex at Orpic Sohar. It is a 75 KBD UOP design, which developed a low rare-earth version of the previous Vanadium ppm base +13% This customized device now allows the refinery
processes untreated atmospheric residue from Oman catalyst being used at the resid FCC unit at Sohar. Product Yields to handle up to four components from different
crude as feedstock. The Mina Al Fahal and Sohar refineries hoppers and/or flowbins, and achieve total
Conversion wt.% base +1.1 wt.%
are integrated to optimize “molecule management.” Feedstock properties deteriorated during this trial. As dosage rates of up to 30 MT/day. In total, two
shown in Table 3, feed API, feed nickel, feed vanadium Dry Gas wt.% base -0.1 wt.% of these devices were installed and operate
Improving Profitability and feed ConCarbon all increased. Despite the decline Propylene wt.% base +1.0 wt.% on a stand-by basis, which allows operators
As shown in Table 1, there have been four distinct periods in feedstock quality, the low rare-earth technology to maintain an uninterrupted dosage of fresh
LPG wt.% base +0.3 wt.%
of catalyst technology that have been applied at the maintained the excellent performance seen in the unit. catalyst into the FCC unit. An extra flow bin also
Table 3 shows how the key FCC unit yields improved with Total Naphtha wt.% base -0.3 wt.% was included to allow separate injections of
Orpic Sohar resid FCC unit.
the low rare-earth FCC catalyst from Grace. Conversion LCO wt.% base -0.3 wt.% Grace additives.
Orpic started up the RFCC unit at Sohar using an FCC was maintained (even slightly increased) without a coke Slurry wt.% base -0.8 wt.%
catalyst from Competitor B. The RFCC unit at Sohar penalty and without increasing the catalyst addition rate. The catalyst and additive injection system was
Coke wt.% base -0.8 wt.% supplied by Grace’s partner, Pneumix, which
processes an extremely challenging feedstock. After a
period of underperformance, a Grace resid catalyst was In 2013, Orpic carried out a rigorous catalyst selection has installed over 130 loaders worldwide.
introduced in 2009, based on independent third-party process using pilot plant testing in an independent third- Grace’s partner for 25 years, Pneumix provides
laboratory testing. Table 2 shows average feedstock party laboratory to evaluate the impact of using catalysts innovative, state-of-the-art solutions for catalyst
properties, operating conditions, Ecat properties and from the main suppliers on FCCU profitability. Results and additive bulk handling to FCC units globally.
product yields for periods using catalysts from Competitor from these tests were used by a second independent

38 Catalagram® No.115 | Fall 2014 39

CUSTOMER PARTNERSHIP

In the conventional operation at Sohar, Table 3: FCC Unit Data Comparing Competitor B and Grace
approximately 20-30 super sacks (1000 kg each) Technology
of fresh catalyst were unloaded every day into
the storage hopper. The handling of such a large Feed Properties Prior Grace Low
volume of material previously had been costly, Grace Rare-Earth
intensively time consuming, and environmentally API base +0.11
unfriendly. There also were safety concerns
associated with the forklift truck movements in the Nickel Content ppm base +5%
area. In addition, during the unloading operation, Vanadium Content ppm base +6%
dust generation created catalyst loss, as well as ConCarbon wt.% base +0.12
safety issues that constrained maintenance activities.
Ecat Properties
One effective way to avoid the handling of super Rare Earth wt.% 3.0 2.4
sacks is to deliver larger volumes of catalyst and Operating Conditions
additives overseas in more suitable containers. A Catalyst Addition Rate MT/day base base
trailer tipper was supplied to allow the refinery to
move to a safer and logistically cleaner container Product Yields
system (Figure 2). This solution was successfully Conversion wt.% base +0.8 wt.%
installed on site without requiring engineering and Hydrogen wt.% base -0.1 wt.%
construction. The frame is adjustable to variable
C1-C2’s wt.% base +1.0 wt.%
trailer heights, accommodating maximum 40 ft.-
trailers without the front car. During the unloading LPG wt.% base +0.3 wt.%
TALENT that spans the globe TECHNOLOGY leadership in FCC TRUST built over time
operation, the trailer is locked with chains and a Total Naptha wt.% base -0.3 wt.%
safety bar is placed over the container. The catalyst LCO wt.% base -0.3 wt.% • Over 100 FCC experts stationed • Industry’s broadest portfolio • #1 global FCC supplier for over
is then transported into the storage hopper by the worldwide supported by global R&D team 70 years
Slurry wt.% base -0.8 wt.%
Power Pipe system (Figure 2). This easy-to-use
device is operated by vacuum, noticeably reducing Coke wt.% base -0.8 wt.% • Customized technical support • Flexible manufacturing enables • Application expertise to
unloading times. including unit optimization, and rapid commercialization of maximize refiner profitability
onsite troubleshooting innovations while minimizing risk
In addition, Grace has built a dedicated silo Table 4: FCC Unit Data Highlighting the Effect of Moving to
storage and logistics management facility at the Optimized Grace Technology
Orpic’s Sohar refinery to guarantee the timely
and secure delivery of product (Figure 3). This Operating Conditions Prior Optimized
facility was opened in 2013, and is operated by Grace Grace Catalyst
local Omani employees. The silo hub plant was Feed Rate BPD base +10%
designed to accommodate a large volume of
ROT °C base base
catalyst, enabling security of supply. Storing this
material at the plant avoids overloading the Orpic Feed Temperature °C base base
warehouse, which saves considerable costs. Cat-to-Oil Ratio base +0.44
Regen Bed Temp °C base -15 °C
Grace also provides Orpic with valuable Ecat
reworking solutions. The Sohar resid FCC unit Product Yields
processes feedstock high in Conradson carbon Conversion wt.% base +1.8 wt.%
and contaminant metals, which initially posed LPG Olefins wt.% base -1.0 wt.%
the refinery with Ecat disposal challenges. Grace
Total Naphtha wt.% base +1.8 wt.%
subsequently explored various options, and found
a solution that complied with local environmental LCO wt.% base -0.4 wt.%
regulations, and granted Orpic a governmental Slurry wt.% base -1.6 wt.%
export license for spent catalyst. A Grace partner Coke wt.% base base
recycles the Ecat from Orpic at their facilities in

(continued on page 42)

40 Catalagram® No.115 | Fall 2014 grace.com 41

 CUSTOMER PARTNERSHIP

(Orpic Solar Refinery Continued)

Germany, while operating under Grace‘s REACH
registration umbrella. This rework utilizes two
different patented processes within the steel
production and building industries.

A Partnership to Maximize Profitability

Throughout its partnership with Orpic, Grace has
worked constantly to enable the Sohar RFCC unit
to maximize profitability through the introduction
of state-of-the-art catalyst technologies. This has
allowed the refinery to reach its targets despite
processing an extremely challenging feedstock.
Grace has also provided Orpic with unique catalyst Figure 1: Multiple addition device provided by Grace
management solutions that have resulted in an
improvement of unit safety and reliability. v

Global leader in
hydroprocessing
catalysts offering
the complete
range of catalysts
Figure 2: Trailer tripper system to avoid the use of super sacks and services

Figure 3: Catalyst silo plant at Sohar

Advanced Refining Technologies
7500 Grace Drive, Columbia, MD 21044 USA
+1.410.531.4000
42 Catalagram® No.115 | Fall 2014 artcatalysts.com 43