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shaped charges
Catalyst size and shape are critical contributors to hydroprocessing
reactor performance
A
chieving increases in pressure on refiners to maximise
hydrocracker capac- Trilobe (TL) shape hydrocracking unit throughput up
ity of 20-35% without to hydraulic limitations which in
any capital investment sounds many cases is a limit set by reac-
impossible; however, novel tor pressure drop. Limitations in
changes in catalyst design reactor pressure drop can be mit-
have enabled just that for igated by many means, but ulti-
two North American refiners. mately catalyst selection is the most
Conventional HC catalyst shape
Hydrocracking units have rap- Used in all HC catalysts critical factor in hydrocracker opti-
idly become one of the high- offered after 1994 misation. Criterion developed the
est profile units in the modern Gradient Advanced Trilobe eXtra (ATX) cat-
refinery with increasing pres- Low High alyst shape to allow hydrocracking
sure to maximise charge rates units to reduce pressure drop and
up to a multitude of con- Advanced Trilobe eXtra (ATX) shape improve activity simultaneously.
straints including reactor sys- There are several significant advan-
tem pressure drop. This article tages of the ATX shape (see Figure
provides two examples of 1), but it is first important to reflect
hydrocracking units process- on how catalyst shape affects reac-
ing significantly higher rates tor performance to understand fully
as a direct result of Criterion’s the benefits of this revolutionary
Proprietary technology offered
new hydrocracking catalyst for majority of HC catalyst product.
shape. Lower CBD
Approx 10% lower fill cost
Criterion and its custom- Catalyst shape and size
Better liquid yield;
ers have seen that a fine bal- shorter diffusion path All hydroprocessing reactor sys-
ance of activity and pressure Reduced over-cracking tems operate with a few stand-
Larger void fraction
drop has long since created ard objectives that apply from the
Higher particulate uptake
a challenge when consider- Delayed onset of rapid ∆P build smallest of naphtha hydrotreating
ing the maximisation of per- Lower SOR ∆P applications to the largest of hydro-
formance for hydroprocessing 15 to 20% lower commercial cracking operations. While this
performance demonstarted vs.
and hydrocracking units. It is conventional TL list may seem rudimentary, every
especially a critical balance for hydroprocessing unit must provide
high profile units in hydroc- Figure 1 ATX catalyst shape advantages the desired catalytic activity, pro-
racking service that receive tection from feed poisons and the
large margins for product upgrades and also have filtration of feed contaminants (though not gen-
high incentives for incremental processing capac- erally a desired function for catalytic solutions). A
ity. Recent margins have placed a great deal of properly designed catalyst system should employ a
wide variety of shaped and sized particles to sup- form of cylindrical shapes of varying diame-
port this set of target objectives for each specific ters, but in the early 1970s American Cyanamid
hydroprocessing unit large or small. Company pioneered the production of shaped
catalysts with the introduction of trilobe (TL)
Grading catalysts catalysts for residual oil and gasoil hydrodesul-
For several decades, the industry has capital- phurisation.2 To this day, a large majority of the
ised on the advantages offered from graded hydroprocessing market’s catalysts are still man-
bed solutions to enable improved performance ufactured in this same shape, and the transition
with respect to increasing system pressure in the past to the use of shaped catalyst parti-
drop throughout the catalyst cycle life. This has cles is one of extreme importance because of the
employed the use of a multitude of materials impact it has had on overall reactor performance.
that have varying void fractions and structures Currently, the two most common main bed cat-
with a common objective to provide the opti- alyst shapes offered by hydroprocessing catalyst
mum available bed void space and transition lay- manufacturers are TL and quadlobe (QL) extru-
ers to remove contaminants from the feed stream dates of varying particle diameters (see Figure
over an extended portion of the catalyst bed. 3). The particle length of commercial catalysts
The application of grading materials and layers offered is variable to some degree within toler-
is common to hydroprocessing units as pressure ances set by each manufacturer, but ultimately
drop across the leading bed remains a challenge is determined by properties of the substrate mix-
for many units in the industry. This deep bed fil- ture, operating conditions, and particle diameter
tration phenomenon has led to the development as the weight of the extruded mixture drives the
of several extruded shapes with varying degrees length by breakage of the extrudate simply as a
of catalytic activity including, but not limited to, function of gravitational force. While both cata-
hollow cylinders, macroporous lobed particles, lyst shapes are common in industry, each offers a
and specialty shaped extrudates (see Figure 2). distinct set of advantages and disadvantages.
In many cases, these materials developed as top Multi-lobed catalyst shapes offer significant
bed grading are not suitable for a large volume of advantages in general over historical conventional
the reactor due to low inherent activity. In addi- shapes and have higher particle surface area (Sp)
tion, many refiners are beginning to capitalise on to particle volume (Vp) ratios when compared to
new technologies with regard to reactor internals a standard cylinder of equal particle length (Lp)
to further improve the filtration of feed contami- and particle diameter (Dp). This increase in sur-
nants and extend catalyst life cycles.1 face area results in greater activity as a result of
reactions that occur on the catalyst particle sur-
Main bed catalysts face, and those that occur within the pore struc-
Historically, main bed catalysts used in hydro- ture of the catalyst pellets. Since many of the
processing reactors were manufactured in the reactions that occur in the hydroprocessing reac-
Shape dp, Lp, Sp, Vp, Sp/Vp, dpe, Brunner, dpe, Ancheyta, εB, dhp, ηB Relative ΔP/LB
mm mm mm2 mm3 mm mm mm Dense mm (ΔPi/ΔPTL)
SPH, 2.5 mm 2.5 - 19.63 8.18 2.40 2.50 2.50 0.36 2.50 0.27 1.25
CYL, 2.5 mm 2.5 5.0 49.09 24.54 2.00 3.61 3.95 0.34 3.00 0.23 1.15
TL, 2.5 mm 2.5 5.0 56.93 17.20 3.31 3.20 4.26 0.41 2.41 0.49 1.00
QL, 2.5 mm 2.5 5.0 55.17 17.76 3.11 3.24 4.19 0.42 1.93 0.55 1.20
ATX, 2.5 mm 2.5 5.0 - - - - - 0.50 2.02 0.55 0.80
Table 1
tions in two phase trickle bed systems without overall catalyst system load since the increase in
correlated modifying constants. These modifiers pressure drop can result in hydraulic limitations,
are functionally dependent on the physical char- reducing hydroprocessing unit capacity. QLs can
acteristics of the particle shape and can be deter- be loaded at higher void fractions via sock load-
mined by experimental methods. Ultimately, the ing methods or applied in larger particle diame-
resulting modified diameter value is applied as ters to overcome the increases in system pressure
the effective particle hydraulic diameter (dph) drop, but these methods reduce the effectiveness
for the comparisons in this work and the devel- advantages offered from the shape difference by
opment of novel catalyst shapes of the future by reducing the overall catalyst mass loaded in the
Criterion. Table 1 illustrates a variety of catalyst fixed volume. The QL shape is also often used to
particle shapes, their physical characteristics and boost the activity of lower performance catalyst
calculated properties. Figure 5 provides insight formulations to achieve close to similar activ-
into the effect of particle shape on system pres- ity of high activity TL catalysts. Thus, when tar-
sure drop for each of the particles listed in Table geting development of an all new revolutionary
1 with the common TL particle set as the stand- catalyst shape, Criterion chose to modify the con-
ard for comparison. ventional TL shape and release to the market the
It is clear from this comparison of the various ATX shape.
particle shapes in Table 1 and Figure 5 that the
modern catalyst particle shapes deliver higher ATX-shaped catalysts
effectiveness at lower packing densities, leading Criterion has been producing catalysts for hydro-
to overall greater system performance with less cracking applications in the ATX shape for
catalyst mass in a fixed volume such as a com- several years and the commercial results are
mercial reactor. However, when
comparing TL and QL parti- 130
cles, there is a distinct advan-
tage to the use of TL-shaped 120
main bed catalyst particles due 110
to the reduction in system pres-
∆PI/∆PTL, %
)
m
m
.5
.5
.5
.5
.5
(2
(2
(2
(2
H
YL
TL
AT
SP
trilobe shape
reactor operation has shown
extremely stable performance.
This stable performance from
Current cycle
the cracking reactors is attrib- wih ATX shape
uted to excellent operations
and the highest activity pre-
treat catalyst system available
which provides the cleanest
possible feed to the cracking Time on stream, days
reactor.
Figure 9 highlights the expert
control of the hydrocracking Figure 8 MPC Garyville hydrocracking reactor WABT
Yield
vacuum gas oil (SRVGO) and
synthetic gasoil (GO). Figure 13
depicts a plot of the normalised
pressure drop from the hydro-
cracker at Shell Scotford where
the previous cycle applied
Criterion’s previous genera- Time on stream, days
tion TL hydrocracking catalysts
and a recent cycle operated Figure 12 MPC Garyville light ends yields
with ATX catalysts. The reduc-
tion in pressure drop enabled
a project to debottleneck the Standard trilobe cycle
Normalised pressure drop
Conclusion
Two of the most critical fac-
tors affecting hydroprocessing/
hydrocracking reactor cata-
lyst performance are simply
shape and size. For generations,
Criterion has led with innovation
0 100 200 300 400 500 600 700 800 in the use of specialised shaped
Time on stream, days particles for maximum catalytic
performance. The application
Figure 15 Shell Scotford hydrocracking reactor WABT and operation of hydroprocess-
ing units with these products has
resulted in both profitability and
sustainability gains for refiners.
Criterion’s ATX-shaped line of
Overall conversion, wt%
References
1 Visser T, Maas E, How state-of-the-art
Figure 16 Shell Scotford overall HCU conversion reactor internals helped debottleneck a
Total hydrocracker, Impact, issue 3, 2013.
is maintained throughout the cycle, permitting 2 Carruthers J D, DiCamillo D J, Pilot plant
increases in feed rate for the unit. testing of hydrotreating catalysts influence of catalyst condition,
Figures 15 and 16, in combination, demonstrate bed loading and dilution, Applied Catalysis 43, Elsevier Science
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shape on the performance of a trickle fixed-bed recycle reactor for
remained very close to the same as the previous
Fischer-Tropsch synthesis, Industrial and Engineering Chemistry
cycle, with a slight advantage offered from the
Research, Feb 2015.
ATX catalyst system. This is the result of a higher
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catalyst effectiveness factor which inherently Capital Expenditure, CEP Magazine, Jan 2004.
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