Enhancing bottoms cracking and
process flexibility
Catalyst designed with advanced zeolite stabilisation technology provides
selective conversion of heavy FCC feed molecules
Yee-Young Cher, Rosann Schiller and Jeff Koebel Grace Catalysts Technologies
R
efiners require FCC catalyst technology that
delivers the right selectivity at the right
time. In a world where fuel demand is
satisfied through a careful balance of free trade,
weather events or refinery upsets could trigger
price volatility in product markets. The ability to
respond quickly to capture short-term market
opportunities is critical. Amid declining gasoline
demand in mature regions, refiners need to
enhance distillate production. Grace’s premium
bottoms cracking family, the Midas catalyst
series, can be used to enhance FCC process flexi-
bility and capture incremental profit as
opportunity arises. These catalysts crack deep
into the bottom of the barrel, enhancing total
distillate and liquid yield, and have been demon-
strated in over 120 refineries that vary broadly
in feed composition and operating modes. The
flexibility that the catalysts provide, used neat or
as a component in a Genesis catalyst system, can
enhance the yield value by $0.40-1.00/bbl of
FCC feed.1
Midas is a moderate zeolite to matrix ratio
FCC catalyst that has been successfully applied
in half of North America’s FCC unit capacity as
well as refineries in other parts of the world. Its
success is driven by the fact that it effectively
cracks all feed types: heavy resids, severely
hydrotreated light feeds, and shale oil-derived
feed streams, via the three-step bottoms crack-
ing mechanism discovered by Zhao.2 The
catalyst design minimises the thermal and cata-
lytic factors that result in coke formation. The
result is deep bottoms conversion, regardless of
the starting feedstock.
Resid streams present the greatest challenge in
terms of deep bottoms conversion. The dynamic
www.digitalrefining.com/article/1001015
molecular dimensions of paraffins and aromatic
species vary, based on carbon number and
molecular configuration. Paraffins species pres-
ent in the 700-1000°F boiling point fraction of
FCC feed are typically in the nC14 to nC34 range
for normal paraffins. The dynamic molecular
size of these compounds is 12-20 angstroms (Å).
The heavy resid fraction also contains an abun-
dance of aromatic molecules (C14 to C60) in the
700-1000°F boiling range. The range of molecu-
lar size for aromatics is 12-25 Å. Even aromatic
carbon molecules up to 60 carbon number are
still less than 30Å in molecular size.
Porphyrins are organic, cyclic macromolecules
that consist of a ring of nine or more atoms.
Porphyrins are aromatic species often present in
resid fractions and characterised by a central
gap that can bond to a metal atom, such as
nickel, vanadium, or iron. If a porphyrin is
complexed with vanadium, it is termed a vanadyl
porphyrin. The size of these metallic complexes
also varies with carbon number, but is in the
same dimensional range as typical resid hydro-
carbons: 10-30Å.2
The relatively large molecules at the bottom of
the barrel that need to be converted must first
be cracked by the catalysts’ matrix acidity. With
molecular sizes of 10-30 Å, the hydrocarbons are
too large to fit into the zeolite pores, which are
typically below 7.5 Å. It is important that the
catalyst have the proper pore size distribution to
enable large feed molecules to enter, crack into
lighter products, and diffuse out before being
over-cracked to coke and gas. For free diffusion
of resid molecules (>1000°F) to occur, the cata-
lyst pore diameter needs to be 10-20x the size of
the molecule, or 100-600 Å.2 The desired pore
PTQ Q4 2014 1
 desorption must be used to
Mesoporosity comparison
capture zeolite porosity. Grace’s
in-house manufacturing and
Catalyst Hg-PV, cc/g
quality monitoring of the
Micropores Mesopores Macropores
Total 36-100Å 100-600Å 600+Å specialty alumina used in Midas
Midas 0.389 0.092 0.206 0.091 provides control over the result-
Midas 0.412 0.107 0.232 0.071 ing porosity. It is generally
Cat 1 0.386 0.116 0.102 0.168
accepted that micropores (<100
Cat 2 0.413 0.092 0.089 0.232
Å diameter), though effective for
cracking, lead to poor coke and
Table 1 Higher mesoporosity of Midas promotes bottoms conversion gas selectivity as a result of poor
diffusivity and over-cracking.
Some competitive benchmarks
Micropores result Midas has the highest mesopores with high surface area and
in poor gas and plus best gas and coke-selective
coke selectivity bottoms cracking activity are also high in matrix
0.45 microporosity, resulting in wet
Pore volume of commercial Ecats

0.40 gas compressor limitations that

Midas
suppress feed rate and ulti-
0.35 Competitor A
mately profitability. In contrast,
Competitor B
0.30 Midas catalyst has the lowest
0.25 amount of small pores and the
highest amount of large meso-
0.20
pores. Optimal porosity
0.15 guarantees gas selectivity and
0.10
coke-selective bottoms conver-
sion. High pore volume also
0.05
serves to enhance the fluidisa-
0 tion characteristics. Several
10 100 1000 10000 units have observed substantial
Pore diameter, Å improvement in the Ecat fluidi-
sation factor following a
Figure 1 Pore volume comparison of commercial Ecats reformulation to Midas or
Genesis.1
volume should be in the large mesopore region The proprietary matrix in Midas can withstand
100-600 Å. The benefit of mesoporosity for the most severe applications, particularly those
bottoms cracking is well understood.5 However, challenged by high levels of contaminant iron
not all the measured pore volume is created and calcium. High alumina content in FCC cata-
equal. Catalysts with similar total pore volume lyst is known to reduce the degradation of the
measurements can vary widely in pore size catalyst surface due to iron and/or calcium
distribution. Midas is designed to have high poisoning.4 Optimum distribution of mesoporos-
mesoporosity in the 100-600 Å range, typically ity also plays a role in maintaining performance,
twice as high as competitive offerings (see Table because diffusion to the active sites remains
1). Optimal porosity is required for effective unhindered despite the high contaminant
kinetic conversion of bottoms. Midas catalysts metals. Midas has been successful in maintain-
crack deeper into the bottoms. ing bottoms conversion in units with some of the
Commercial examples of Midas’s high mesopo- highest levels of contaminant iron on Ecat in the
rosity, as measured by Hg porosimetry of Ecat, industry.
are shown in Figure 1. Note that Hg intrusion A good bottoms cracking catalyst requires high
measures the porosity greater than 36 Å, there- matrix surface area (MSA). However the activity
fore the result specifies the porosity associated of a high matrix catalyst needs to be balanced
with the catalyst matrix only; N2 adsorption or with an appropriate level of zeolite without
compromising attrition characteristics.

2 PTQ Q4 2014 www.digitalrefining.com/article/1001015

Additionally, an appropriate
rare earth exchange level on the 8
Competitor (Base Fe+Ca)
zeolite is critical to ensure opti- 6 Midas (+25% Fe+Ca)

Relative bottoms, wrt%

mal coke selectivity. An
4 Midas (+60% Fe+Ca)
optimum exists in the relation-
ship between zeolite unit cell 2
size (UCS) and coke selectivity.5
0
Too often, high matrix catalysts
also have a high UCS, meaning −2
they are over-exchanged with −4
rare earth. Low zeolite input
formulations with high rare −6
earth exchange (albeit low total −8
rare earth on catalyst) will −3 −2 −1 0 1 2 3
retain a higher percentage of the Relative coke, wt%
fresh zeolite surface area in a 3
severe regenerator, but the Competitor (Base Fe+Ca)
penalty for this over-exchanged 2 Midas (+25% Fe+Ca)
zeolite is poor coke selectivity. Midas (+60% Fe+Ca)
Relative coke, wt%

The rare earth exchange in 1

Midas catalysts is optimised to
result in a formulation that lies 0
in the so-called ‘sweet’ spot or
between 24.28-24.32 Å for Ecat −1
UCS to deliver the best coke
selectivity. The right distribu- −2
tion of mesoporosity coupled
−3
with optimal activity and UCS −1.0
gives the catalyst the coke selec-
tivity edge in commercial
cracking. Figure 2 Despite higher contaminant metals, Midas improved bottoms
cracking and coke selectivity at Refinery C
Commercial experience
Midas’s design features have led to high perfor-
mance in many commercial examples. The first
example comes from Refinery A that has an FCC
unit processing a mix of VGO and light resid.
The feed is moderately high in metals with good
cracking characteristics. The base catalyst was a
competitive high MSA catalyst with high rare
earth exchange. The unit suffered from a dry gas
constraint, especially in the summer. When the
refiner switched to Midas, a 5-10% drop in total
dry gas yield at equivalent riser temperature and
metals loadings was observed; this allowed the
refiner to maintain maximum feed rate through-
out summer. The better coke selectivity also
manifested itself in lower bottoms yield by 15%.
At Refinery B, the FCC unit was processing
light resid using a high matrix, high UCS cata-
lyst. While rare earth levels on the zeolite were
high, the catalyst itself had low total rare earth
−0.5 0 0.5 1.0
Relative kinetic conversion
because zeolite input was very low. In spite of
the high rare earth exchange and resulting UCS,
the unit was constrained on total wet gas and
bottoms yield. There wasn’t enough zeolite pres-
ent to complete the second stage of the bottoms
cracking mechanism.2 Zeolite is critical to reduce
the size of the hydrocarbon via dealkylation.
Insufficient zeolites cause coke precursors to
condense on the catalyst surface and become
coke before they can be converted into transpor-
tation fuels. Poor coke selectivity translates into
subpar bottoms conversion.
Introduction of Midas provided a reduction in
bottoms make on the order of 8-10% for
Refinery B. Higher zeolite and optimal UCS
improved coke selectivity, and the refinery
increased not only the fresh feed rate but also
the amount of resid in the feedstock by almost
10%. Higher zeolite also increased the circulat-

www.digitalrefining.com/article/1001015 PTQ Q4 2014 3

 benefits realised at Refinery C
‘A’ = Competitor A are shown in Figure 2.
3 0.6 150 Refinery D routinely processes

Dry gas shift SCFB

Feed CCR shift
2 0.3 100 heavy resid in the FCC unit.
Feed API shift

1 0 50 Similar to the other examples,

the objectives were to reduce dry
0 −0.3 0
gas and improve the yields of
−1 −0.6 −50
liquid fuels (gasoline and distil-
−2 −0.9 −100 late), without compromising feed
‘A’ Midas ‘A’ Midas ‘A’ Midas
rate. A switch to Midas catalyst
6 5.0 3.0
met the objectives despite deteri-
LPG yield shift, %

Slurry shift, vol%

LCO shift, vol%

4 2.5 2.0 orating feed quality coming to

Gasoline +

2 0 1.0 the FCC. Over time, the feed-

−0 −2,5 0 stock became heavier, contained
more concarbon, and had higher
−2 −5.0 −1.0
metals loadings. Lower dense
−4 −7.5 −2.0 bed temperatures minimise ther-
‘A’ Midas ‘A’ Midas ‘A’ Midas
mal cracking, reducing dry gas
Figure 3 At Refinery D, Midas increased gasoline and distillate yield and yield. Slurry yield was held
reduced dry gas at a similar feed rate constant (see Figure 3).
The primary operating objec-
ing activity, enabling a 5% reduction in catalyst tive of the FCC unit at refinery E is to maximise
additions on a lb/bbl basis. Incremental resid at LCO yield. Reformulating to a high matrix cata-
lower catalyst additions caused Ecat metals to lyst from the starting low matrix catalyst
increase by 1000 ppm, which drove a corre- presented a challenge for this refinery. A whole-
sponding increase in dry gas. However, the sale change in the catalyst formulation was
balanced zeolite and matrix surface areas of the deemed to be risky. Grace introduced Midas to
catalyst meant that more feed was converted the FCC unit in a step-wise fashion. Initially,
into gasoline and distillate, rather than LPG and Midas was blended with the refiner’s base high
coke. zeolite catalyst (also a Grace catalyst) in a 50/50
At Refinery C, the FCC unit processes resid ratio. The FCC unit realised a reduction in slurry
feedstock high in iron (Fe) and calcium (Ca). yield of 12% (see Figure 4). Refinery E later
Over time, the unit suffered from classic symp- increased the amount of Midas to 100% of the
toms of iron poisoning.4 As iron nodules built on fresh catalyst requirement. Again, a step-change
the surface, Ecat activity, unit conversion and improvement in slurry was observed, and the
bottoms cracking all began to suffer. A switch to incremental conversion was maintained as distil-
Midas provided higher activity and improved late as desired. Higher distillate yield (+15%)
coke selectivity, delivering deeper bottoms was observed over a wide range of conversion
conversion. Eventually the feed became heavier levels with Midas over the original base catalyst.
and more contaminated. The catalyst never lost
its selectivity edge over the competitive high Maximum matrix surface area
MSA base formulation, even after increases of Midas Gold is the latest innovation in this cata-
25-60% in Ecat Fe and Ca. The high mesoporos- lyst family, and is designed to provide maximum
ity is particularly effective in preventing a loss in matrix surface area allowing refiners to further
cracking activity often seen during periods of upgrade the bottom of the barrel while minimis-
high metals loadings. Fe and Ca can form eutec- ing coke. These catalysts feature Grace’s Low
tics that serve to essentially melt over the Coke Matrix (LCM) technology, which renders
catalyst surface, blocking pores and suppressing nickel inactive for dehydrogenation reactions.
conversion. The high mesoporosity of Midas The coke selectivity advantage of Midas Gold
ensures that high diffusivity is maintained. It is delivers a 15% reduction in bottoms yield over
the preferred catalyst technology for FCC units prior formulations. Multiple commercial applica-
processing high Fe feedstocks. The selectivity tions are under way.

4 PTQ Q4 2014 www.digitalrefining.com/article/1001015

Conclusion
Midas is Grace’s premium high 7.5
matrix bottoms cracking catalyst
family. It is designed to possess
5.0
the key characteristics necessary

Relative LCO yield, vol%

for selective conversion of heavy
FCC feed molecules. These char- 2.5
acteristics are controlled during
proprietary manufacturing 0
processes of specialty aluminas,
zeolites and ultimately the
−2.5
whole catalyst itself. The net
result is:
−5.0 Base
• Maximum matrix mesoporos-
Base + 50% Midas
ity to minimise coke and gas
100% Midas
formation and maximise −7.5
bottoms upgrading −15 −10 −5 0 5 10
• Ideal pore size diameters to Relative conversion, vol%
preserve free diffusion in and
7.5
out of the catalyst, even in the
face of metals contamination
• Optimised rare earth exchange 5.0
Relative slurry yield, vol%

to deliver best-in-industry coke

selectivity 2.5
• Balanced zeolite-to-matrix
activity to maximise product
0
value from the FCC.
Midas contains the highest
mesoporosity in the desired −2.5
range of 100-600 Å and the
most optimal UCS in the −5.0 Base
market, providing a clear selec- Base + 50% Midas
tivity advantage over 100% Midas
−7.5
competitive catalysts. Several −15 −10 −5 0 5 10
distinct grades are available, Relative conversion, vol%
suitable for a wide range of feed
and operating objectives. The
catalyst’s in-unit fluidisation Figure 4 Refiner E observed higher distillate yield over a range of conversion levels
properties are a solution for
FCCs with fluidisation or circulation difficulties. blower constraint
Applied neat or in a Genesis catalyst system, • Ability to process high Fe and Ca feedstocks,
Midas provides the option of running difficult or such as Bakken and Eagle Ford
opportunity feedstocks to the FCC without • Incremental fuels yield, for instance LCO, or
suffering from poor coke and gas selectivity. gasoline and distillate maximisation
Finally, the catalyst provides the flexibility to • Relief against a wet gas compressor constraint
fine-tune the yield of the individual product when cracking resid
streams to exploit short- or long-term economic • Capability to process opportunity crudes
opportunities. • Improved catalyst fluidisation characteristics
In summary, the catalyst should be considered • Flexibility to capture the value of opportunity
by any refiner seeking: crudes
• Deeper bottoms cracking • Ability to shift between gasoline and distillate
• Enhanced bottoms conversion against an air modes of operation

www.digitalrefining.com/article/1001015 PTQ Q4 2014 5

 • Rapid catalytic response to capture short-term
economic opportunities.
References
1 Schiller R K, Grace Davison’s GENESIS catalyst systems provide
refiners with flexibility to capture economic opportunities,
Catalagram 107, 2010.
2 Zhao X, et al, FCC bottoms cracking mechanisms and
implications for catalyst design for resid applications, NPRA
2002, AM-02-53.
3 Mitchell Jr. M M, et al, Fluid catalytic cracking: science and
technology, Magee J S, Mitchell M M Jr. (Eds.), Studies in Surface
Science and Catalysis, Vol 76, Elsevier, Amsterdam, 1993, 293.
4 Yaluris G, et al, The effects of iron poisoning on FCC catalysts,
NPRA 2000, AM-01-59.
5 Cheng W C, et al, Fluid catalytic cracking, Ertl G, et al (Eds.),
Handbook of Heterogeneos Catalysis, 2nd Edition, Wiley-VCH,
2008, 2763.
6 PTQ Q4 2014
Yee-Young Cher is Regional Technical Service and Business
Manager for Grace Catalysts Technologies, based in Singapore.
Rosann Schiller is Marketing Director for Grace Catalysts
Technologies, based in Columbia, MD, USA. She holds an MSE
in chemical engineering.
Jeff Koebel is National Technical Sales Manager for Grace
Catalysts Technologies, working with customers in the eastern
US.
Links
More articles from: Grace Catalysts Technologies/ART
More articles from the following categories:
Catalysts & Additives
Heavy/Sour Crudes
www.digitalrefining.com/article/1001015