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Increased activity in FCC pretreat

Advances in metal chelation techniques deliver higher performance catalysts


for FCC pretreat
Charles Olsen and Brian Watkins Advanced Refining Technologies

he process of optimising a catalyst is no


easy task. A few of the keys to success are
designing the proper pore size distribution
into the catalyst, optimising the metals composition and maximising utilisation of the metals.
Extensive work has been completed to define the
optimum pore architecture of catalysts for
processing heavy feeds.
Figure 1 compares the relative activity of different catalyst preparations as a function of
increasing catalyst pore size. The pore size and
surface area of a catalyst are dependent variables, meaning that as the pore size increases, the
surface area decreases, and thus the number of
active sites decreases. On the left side of Figure
1, the catalysts have a high surface area, but the
pores are too small to allow large VGO molecules
access to the active sites. On the right side of the
figure, the pores are very large and allow easy
access, but the surface area (and thus the
number of active sites) is quite low. In both
cases, the activity is low. The optimum support
has a pore size distribution which minimises

diffusion constraints and maximises the number


of accessible active sites.
Another important parameter for catalyst
performance is the composition of active metals.
Figure 2 shows the relationship between the relative activity of a catalyst and the active metals
loading. As expected, activity increases with
increasing level of metals, but there is a limit.
The figure indicates that there is an optimum
metals loading beyond which adding more
metals actually hurts catalyst performance.
Catalyst activity decreases when excess metals
are added because they begin to block the pores.
Yet another critical aspect is the utilisation of
metals, or maximising the number of active
sites. Current generation catalysts typically rely
on the formation of Type II active sites during
catalyst activation. Type II sites are known to
provide significantly higher activity at the same
metals loading as catalysts containing Type I
active sites. An effective way to maximise the
concentration of Type II active sites is through
the use of chelate technology during the metals
120

115

Decreasing
pore size

Increasing
pore size

Optimum region for


best performance

Relative activity

120

100
90
80

115
100
90
80
70

Relative activity

130

60

70

50

60
Decreasing access to active sites

Increasing access to active sites

Figure 1 Optimised pore structure is key to performance

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Catalysis 2015 1

170

Relative activity

160
150
140
130
120
110
100
90

Metals surface coverage

Figure 2 Proper metals surface coverage is critical

Relative volume activity

130
125

586DX
AT575

120
115
110
105
100
95
90

HDS

HDN

Relative volume activity

Figure 3 586DX out-performs AT575 in FCC pretreat

190
180
170
160
150
140
130
120
110
100
90
80
70

HDS
HDN

AT775

AT792

AT795

486DX

Figure 4 486DX has superior performance in high pressure FCC pretreating

2 Catalysis 2015

impregnation step. ART has


been steadily improving the
application of chelates with its
DX technology.
The latest catalysts developed
via this optimisation process
are
Advanced
Refining
Technologies (ART) 586DX and
486DX catalysts which are new
catalysts designed for maximum performance in FCC
pretreat applications. 586DX is
a NiMo catalyst with significantly improved HDS and HDN
activity. In FCC pretreat applications, this catalyst can
provide
superior
nitrogen
removal as well as aromatic and
polynuclear aromatic (PNA)
saturation in order to provide
significant FCC feed upgrading
for increased FCC yields. Figure
3 compares the activity of
586DX and AT575. The figure
shows that 586DX has nearly
20% higher HDN activity and
15% higher HDS activity
compared to AT575. 586DX has
a large pore size distribution,
similar to AT575, which gives
the catalyst exceptional stability
on heavy feeds.
It benefits from the latest
advancement in DX technology.
It has lower loss on ignition
than conventional chelated
catalysts and requires no
special handling or start-up
procedures. In just a short time
since its commercialisation,
586DX has been installed in
four FCC pretreat units. The
performance has been excellent
with as much as 10F improvement in HDS activity over the
previous catalyst. 586DX has
already been selected for
another cycle in some of these
units.
Another recent advancement
to ARTs FCC pretreat catalyst
technology is 486DX. This is a

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Activity advantage, F

Relative volume activity

CoMo
catalyst
that
has
190
outstanding
HDS
activity
HDS
180
coupled with high HDN activity.
HDN
170
Figure 4 shows a comparison of
160
the activity of several genera150
tions of ART HDS catalysts for
140
FCC pretreat along with 486DX.
130
The results from side-by-side
120
testing clearly show that 486DX
110
exhibits a significant improve100
ment in performance over the
90
prior generation. There has
80
been continuous improvement
70
AT775
AT792
AT795
486DX
in activity with each generation
since the introduction of ApART
in 2004. Most recently, 486DX Figure 5 486DX performance in low pressure FCC pretreat
has been shown to have a 20%
HDS advantage as well as a 10%
25
improvement for HDN over
HDS
AT795.
HDN
20
In lower pressure applications, 486DX continues to
maintain its advantage over
15
previous generations, including
AT795 (see Figure 5). Figures 4
10
and 5 demonstrate the robustness of 486DX performance and
5
indicate that it is an effective
catalyst over a wide range of
conditions.
0
AT575 / AT795
586DX / 486DX
Both the hydrotreating catalyst system and the operating
strategy for the pretreater are Figure 6 Comparison of AT575/AT795 and 586DX/486DX ApART catalyst systems
critical to providing the highest
quality feed for the FCC. Driving the hydro- ics involved in FCC pretreating and, through its
treater to remove nitrogen and PNAs improves relationship with Grace Refining Technologies, a
FCC product value when targeting gasoline detailed understanding of the effects of hydroproduction, but this needs to be balanced against treating on FCC unit performance.
The appropriate choice of an FCC pretreat
the increased costs of higher hydrogen consumption and shorter cycle length that result from catalyst system must, in addition to other potenthis mode of operation. To address this need, tially important considerations such as feed
ART utilises the ApART catalyst system for FCC metals removal, represent an optimisation of
pretreatment. This technology is designed to sulphur removal capability as well as HDN and
provide increases in HDS conversion while at saturation activity. The flexibility of the ApART
the same time providing significant upgrading of system offers the potential to provide maximum
FCC feedstock quality and increasing yields. In HDS activity, and thus lowest FCC gasoline
essence, an ApART catalyst system is a staged sulphur content, while also providing a maxibed of high activity NiMo and CoMo catalysts mum in FCC unit conversion at constant coke
where the relative quantities of each catalyst can operation.
The addition of 586DX and 486DX to the
be optimised to meet each refiners goals and
constraints. ART has continued to develop a ApART system portfolio enhances the flexibility
better understanding of the reactions and kinet- and performance of these systems for FCC

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Catalysis 2015 3

pretreat. They expand the capability to significantly reduce required SOR temperatures for
both HDS and HDN. The optimised system of
586DX/486DX offers refiners an enhanced ability to generate lower sulphur FCC products as
well as still delivering the benefits of nitrogen
removal and polyaromatic saturation. Figure 6
shows a comparison of an AT575/AT795 system
with the new 586DX/486DX system. There is a
clear and significant improvement in both HDS
and HDN activity with the ApART system.
The additional HDS activity combined with
maximum nitrogen removal and aromatic saturation allows refiners to utilise 586DX as a
standalone catalyst for maximum upgrade in
refinery markets demanding increased yields.
Refiners can also choose to utilise 486DX as a
standalone catalyst in order to minimise hydrogen consumption while still achieving excellent
sulphur removal for meeting Tier III sulphur
regulations. Combining these two catalysts in an
ApART catalyst system is ideal for hydrotreaters
that need to operate with controlled or minimised hydrogen consumption yet still require low
sulphur while maintaining yield gains in their
FCC. These units are able to benefit from a lower
start of run temperature as well as being able to
gain some additional improvements that are not
often achieved in a system of 100% NiMo or
CoMo.

Conclusion
Advanced Refining Technologies (ART) first
introduced the catalyst system for FCC feed

4 Catalysis 2015

pretreating in 2002. The ApART technology was


designed to provide maximum HDS activity
while also providing significant upgrading of
FCC feeds. This technology has been applied in
over 70 units in commercial service since its
inception.
Extensive pilot testing and experience enable
the right catalyst system to be tailored for maximum refinery profit. 586DX and 486DX will
enable refiners to enhance their operation with
either increased cycle length or additional feedstock processing in order to maximise margin.
The ability of these catalysts to perform in different configurations provides a high level of
versatility and makes it a catalyst capable of
exceeding refiners needs in demanding FCC
pretreat applications.
Charles Olsen is Director, Distillate R&D and Technical Services
with Advanced Refining Technologies (ART).
Brian Watkins is Manager of ARTs Distillate Pilot Plants and
Technical Service, providing customer support and monitoring
globally.
Email: brian.watkins@grace.com

Links
More articles from: Grace Catalysts Technologies/ART
More articles from the following categories:
Catalysts & Additives
Fluid Catalytic Cracking

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