Breaking new ground through

continuous innovation BASF residue

FCC catalyst technologies
Alexis Shackleford and Bilge Yilmaz BASF Catalysts

lthough Tight Oil has

captured the attention of
the world and changed the
Collection of Asphaltenes
landscape of North American
refining, resid type feeds continue
to play a key role in the global
Asphaltene
FCC market with around 66% of
the catalyst supplied on an annual
basis being specifically targeted
Multi-Ring Compound
for this segment. This is true
Small Chain Alkane

across all regions even in North
200 (Angstroms)
0
25
50
100
America where the Tight Oil boom
is occurring; the North American Figure 1 Relative size of molecules found in FCCU feeds
FCC catalyst market in 2014 is
42% resid on a volume basis. From an opera- found in higher levels in resid feedstocks includtional stand point resid feeds provide unique ing nickel (Ni), vanadium (V) and iron (Fe),
challenges to refiners as they contain higher catalyse a variety of unwanted secondary reacaromatic, conradson carbon residue (CCR), and tions in the FCCU. Resid catalysts are designed
metals content compared to VGO feeds. BASFs to have high tolerance to these metals and
reduce the impact of the unwanted side
research
and
development
reactions. BASF research and developefforts have been aligned with
Resid FCC
ment efforts have yielded a strong
these market needs and a
Catalysts
portfolio of resid FCC catalysts based on
progression of innovative FCC
DMS
innovative technology and manufacturing
catalyst products are in the

Flex-Tec
platforms.
developmental phase or have

Defender
This article will describe recent develbeen commercialised aimed

opment of BASFs resid catalysts, and

specifically at the resid market.
Endurance
introduce the latest in resid catalyst
FCC resid catalysts are engi Fortress
innovation: Boron Based Technology
neered to improve operation
Prox-SMZ
(BBT).
and meet these unique chal
Stamina
lenges. Due to large aromatic
A Flexible Portfolio of Products
compounds such as asphaltenes
DMS +
BASF currently offers a number of flexiin resid feeds, Figure 1, optiProx-SMZ
ble catalyst solutions for resid feed

Aegis
mised catalyst pore structure is
processing, Figure 2.
critical to convert the heavier
The product lines are based off BASF
material to more valuable prod- Figure 2 BASFs Resid FCC
award winning
Distributed Matrix
ucts.
Contaminant
metals Catalyst Portfolio

www.digitalrefining.com/article/1001082

May 2015 1

Figure 3a & b SEM picture of DMS platform on the left, and of Prox-SMZ platform on the right

Structure (DMS) platform and Proximal Stable

Matrix and Zeolite (Prox-SMZ) platform, both of
which have optimised porosity to allow the diffusion of heavy molecules into the catalyst for
maximum bottoms upgrading. The DMS platform has the highest zeolite content for
maximum conversion to gasoline and lighter
products such as propylene and butylenes. DMS
matrix is designed to provide enhanced diffusion
of feed molecules to pre-cracking sites which are
located on the external, exposed surface of
highly dispersed zeolite crystals. The feed
pre-cracks on the zeolite itself, rather than on
active amorphous matrix material resulting in
less coke and gas. This allows high bottoms
conversion with low coke, and higher yields of
gasoline and light olefins. The Prox-SMZ technology is designed for distillate maximisation.
The technology is built on two main features: the
presence of an ultra-stable and coke selective
matrix and the close proximity of an ultra low
sodium zeolite, which are created in one single
synthesis step. Unlike conventional low zeolite to
matrix surface area ratios (Z/M ratios), accentuated matrix cracking with poor coke and gas
selectivities does not occur.

Metals Tolerance
Traces of nickel and vanadium have detrimental
effects on performance. Nickel, and to a lesser
extent vanadium catalyse dehydrogenation reactions leading to coke and hydrogen production.
Vanadium is mobile under regenerator conditions and also leads to the destruction of zeolite.

2 PTQ Q3 2006

By examining equilibrium catalyst (Ecat) from

refineries with electron microscopy, it was
generally observed that while vanadium is
distributed homogenously through the particles,
nickel mainly deposits and accumulates on the
outer surface of the catalyst, as depicted in
Figure 4. Based on the understanding of how
metals deposit, BASF uses a specialty alumina in
the catalyst particle to trap the nickel. For vanadium, which is mobile and distributes evenly,
BASF uses a separate particle vanadium trap.

DMS Platform: Fortress

BASFs Fortress catalyst is based on the latest
FCC catalyst manufacturing innovation, MultiStage Reaction Catalyst (MSRC) platform
introduced in 2010 . The approach of the novel
MSRC platform is to combine two or more existing FCC catalyst functionalities within a single
catalyst particle.
In state of the art resid FCC catalysts like FlexTec, a specialty alumina is integrated in the
catalyst formulation to trap the nickel and form
nickel aluminate which is less deleterious for
dehydrogenation reactions in the FCC riser. Since
nickel mainly deposits and accumulates on the
outer surface of the catalyst, as depicted in figure
4, it would be advantageous to concentrate the
nickel trapping alumina at the outer layer to
make it more effective. With all current catalyst
technologies, the specialty alumina is uniformly
distributed through the catalyst microsphere.
This makes a large portion of it, located in the
interior of the particle, unavailable to react with

www.digitalrefining.com/article/1000133

the nickel and is essentially

wasted. By using the MSRC
concept, the spatial distribution of this specialty alumina
within the particle is adjusted
to maximise its efficacy in
nickel trapping and lead to
improved
catalyst
performance.
With the MSRC approach,
the inner stage of the catalyst
has the DMS structure to
allow enhanced diffusion of
heavy molecules, maximising
yields. The outer-stage is also
based on DMS technology,
but is enriched with specialty
alumina to trap the nickel
directly where it enters and Figure 4 Electron microprobe analysis. Line scan of an Ecat particle showing
deposits on the catalyst
as an even distribution of vanadium (blue) in the particle and nickel depositing

depicted in Figure 5. The mainly on the outer surface (red)
improved spatial distribution
of the trapping alumina
offers more efficient material
Alumina
utilisation
and
better
performance.
The first commercial trial
was a short contact time resid
Flex-Tec
Fortress (Resid MSRC)
unit located in the United
States. The unit operated in
deep partial burn and low Figure 5 Simplistic representation of alumina distribution in current resid
reactor severity, with primary catalyst Flex-Tec (left) versus novel MSRC resid catalyst technology (right)
constraints
of
wet
gas
compressor and air blower limit. With the cations, the novel resid distillate maximisation
improved metals tolerance of Fortress, the unit catalyst Stamina was introduced in 2009. With
could alleviate the wet gas compressor limit, and maximum distillate catalysts, the amount of
improve the coke selectivity to allow more oper- zeolite is moderated, and matrix increased to
ating
flexibility.
The
unit
successfully suppress over cracking to gasoline and lighter
transitioned from Flex-Tec to Fortress. The products while maintaining good bottoms
hydrogen selectivity improved by 12% at equiva- conversion. The advantage of Prox-SMZ catalyst

lent metals and coke selectivity
improved 17%. is a significantly better bottoms upgrading of
With the reduction in hydrogen and coke, lique- distillate to bottoms at constant coke versus
fied petroleum gas (LPG) plus gasoline increased competitive matrix material. BASFs unique
manufacturing process of in-situ forms the
0.7 wt%.
matrix and zeolite in a single step, bringing them
Prox-SMZ Platform: Stamina
in intimate contact with one another. While
BASFs Stamina catalyst is the second catalyst, other catalyst technologies can incorporate
and first resid catalyst based on the Prox-SMZ zeolite and matrix materials into the same cataplatform. Prox-SMZ was first introduced in 2008 lyst particle, they do not have the capability to
with HDXtra, a catalyst designed for distillate bring them together in such proximity. The
maximisation with VGO feed. In an effort to binder used in these processes creates a barrier
extend the Prox-SMZ family to resid feed appli- and will act as a separator between the matrix

www.digitalrefining.com/article/1000133

PTQ Q3 2006 3

and zeolite. It is this unique synergy between the

zeolite and matrix that leads to rapid transfer of
reactants and feed molecules from zeolitic acid
sites to matrix acid sites. BASF then combined
the matrix and zeolite with improved porosity to
handle heavier resid feeds and incorporate
metals passivation technologies to develop
Stamina. Testing shows Stamina exhibited a 6%
improvement in distillate selectivity at constant
conversion over Flex-Tec, while the coke yield
stayed constant. A bottoms reduction of 2% and
an increase in gasoline by ~1% was also
observed.
The first commercial trial of Stamina was at
Big West Oil in Salt Lake City. The refinery operates a UOP MSCC resid catalytic cracking unit.
The principal unit constraint was the LPG rate.
The refiners main objective was to maximise
feed throughput and improve bottoms conversion to distillate and gasoline. Stamina entered
the unit following the base catalyst Flex-Tec. The
unit data showed impressive results with the
delta coke decreasing 25%, and bottoms decreasing 45% compared to prior to the trial. As a
result of the improved stability of Stamina, the
conversion increased keeping the distillate yield
overall flat. Due to the lower bottoms yield, the
distillate selectivity improved from 65% to
~80%, while gasoline yield was 5% higher. The
refinery reported the FCCUs profitability
increased by more than +1.5 $/bbl.

Combining DMS & Prox-SMZ Platforms: Aegis

The development of BASFs catalyst Aegis was
accomplished by combining BASFs two technology platforms, DMS and Prox-SMZ. Aegis is a
flexible catalyst solution for maximising transportation fuels of distillate plus gasoline from
the FCCU.
One of the early commercial applications of
Aegis was at Tamoil S.A.Collombey refinery in
2011. The Collombey refinery operates a resid
FCCU processing 100% residue feedstock with
up to 7 wt% CCR and a high contaminant metal
level (Ecat Ni up to 6000 ppmw and V up to
6000 ppmw). At the time, adverse rare earth
(RE) market conditions lead to the refinery evaluating lower RE catalysts. A trial was conducted
using another suppliers low RE product at 2.6
wt% RE (vs. 3.3% RE prior), but was abandoned
due to poor performance (increased LPG yield
which was the main operating constraint). The

4 May 2015

refinery then changed to BASFs Aegis catalyst

with 2.8 wt% RE, 0.5 wt% lower RE than the
base catalyst. The plant LPG/gasoline selectivity
was improved. The dry gas and coke yields were
similar. An outstanding improvement in the
bottoms cracking was achieved with record
distillate yield and significantly reduced slurry
yield. Overall, Aegis improved the units profitability +1.2 $/bbl over the 2.6 wt% RE catalyst
and +0.4 $/bbl over the higher 3.3 wt% RE
catalyst.

Boron Based Technology

Continuing advancement for FCC resid catalyst
technology, BASF introduces a new fluid catalytic cracking catalyst technology. The new
technology is based on a novel chemistry for
metals passivation, where customisation and
flexibility to deal with contaminant metal passivation is crucial.
BASFs revolutionary new Boron Based
Technology (BBT) for resid applications is aimed
at minimising the negative impact of contaminant metals (especially nickel). The enhanced
nickel tolerance is achieved by loading a boron
compound on a special inorganic support that is
introduced into the catalyst. The boron is mobile
under regenerator conditions and will find and
passivate nickel, thus rendering the nickel inactive to catalyse the production of hydrogen and
coke. Combining this novel metals passivation
functionality with a pore architecture that minimises diffusional limitations of heavy feed
molecules, this new technology allows lowest
hydrogen and coke yields coupled with higher
make of valued gasoline and light olefin
products.
The BBT platform offers a variety of catalysts
to refiners that are tailored for the metals passivation needs of their resid-FCCUs. Advanced
cracking evaluation (ACE) results of a BBT
catalyst deactivated and loaded with 3000 ppm
Ni and 3000 ppm V are presented below in
comparison with BASFs heavy resid catalyst,
Flex-Tex, with identical metals loading levels. As
shown in the table below, BBT results in significantly lower hydrogen and coke yields of -27%
and -22% respectively. These findings demonstrate the enhanced metals tolerance and
improved catalytic performance of the BBT
compared to conventional metals passivation
technologies. There are multiple patents pending

www.digitalrefining.com/article/1001082

for this new technology. The first BBT manufacturing trial was successfully carried out in June
2014, with commercial trials to start in the latter
half of 2014.
BASF is committed to providing new and
innovative catalysts to refiners supporting
current and future market needs. With resid
feeds continuing to be an important feedstock to
FCCUs globally, BASF has a broad and flexible
catalyst portfolio that addresses the many challenges FCCUs processing resid feeds face. BASF
continues to push boundaries and introduces the
novel chemistry of boron in the BBT platform
for enhanced metals passivation. The new BBT
catalyst significantly lowers hydrogen and coke
yields to improve FCCUs profitability and
operation.

www.digitalrefining.com/article/1001082

ACE Results

Flex-Tec

BBT

Hydrogen
Coke

Base
Base

- 27%
- 22%

Figure 6 ACE results at 75 wt% conversion comparing

Flex-Tec with BBT after cyclic propylene steaming (CPS3) deactivation with 3000 ppm Ni, 3000 ppm V, showing
lower hydrogen and coke with BBT

Links
More articles from: BASF Corporation,
Catalysts Division
More articles from the following categories:
Catalysts & Additives
Fluid Catalytic Cracking

May 2015 3