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Hydroprocessing rate increase using

shaped charges
Catalyst size and shape are critical contributors to hydroprocessing
reactor performance

Adrienne Van Kooperen Criterion Catalysts & Technologies/Zeolyst International


James Esteban Criterion Catalysts & Technologies
Brandon Murphy Marathon Petroleum Company

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

www.digitalrefining.com/article/1001491 April 2018 1


Medallion Inert, high void, flow improvement
Trilobe
16 mm Crush strength: >8 lb/mm
Loaded density: 50 lb/ft3
MacroRing dp
Macro porous, high void, low activity
8 mm Crush strength: >8 lb/mm
Loaded density: 45 lb/ft3 Lp

Ring High void, good activity Quadlobe


6.4, 4.8, 3.2 mm Crush strength: >1.2 lb/mm
Loaded density: 35 lb/ft3

FilterLobe Large diameter, extra long trilobe dp


5.6, 3.2, 2.5 mm Crush strength: >3.0 lb/mm
Loaded density: 26lb/ft3
Lp

Figure 3 Typical TL and QL catalyst


Figure 2 Common graded bed particle shapes shapes

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-

2 April 2018 www.digitalrefining.com/article/1001491


tor are governed by mass trans-
fer, the advent of shaped particles 0.9
has provided increased access for ATX
0.8 QL

Effectiveness factor (η)


reactants to contact active sites
0.7 T
in the pore structure closer to
Cylinder
the centre of the pellet by reduc- 0.6 Sphere
ing diffusion distance limitations.
Inherently, this also provides 0.5
greater selectivity when consid- 0.4
ering reactions that continue to
0.3
propagate, such as the formation
of light ends from over-crack- 0.2
ing. Furthermore, an increase in 0.1
the number of lobes is associated 1 2 3 4 5
with increasing the overall cat- Effective particle diameter (dpe), mm
alyst effectiveness factor, which
implies a catalyst with more lobes Figure 4 Catalyst effectiveness factor as a function of effective particle
is capable of providing higher diameter
activity per volume, assum-
ing that the catalyst is manufactured in the same of the shape, which influences diffusivity to the
manner as its comparison. Figure 4 illustrates this inner surfaces of the catalyst pellet, plays a key
concept as a function of catalyst pellet effective role in overall system activity. This implies that
diameter (dpe) as defined in Equation 3 for a typ- shapes with a higher Sp/Vp ratio will inherently
ical hydrodesulphurisation operation.3,4 The effec- provide a higher effectiveness factor which is syn-
tiveness factor (η) and Thiele modulus (Φ) for the onymous with activity given the same catalyst
catalyst pellets are determined from the relation- mass. This does not, however, imply that com-
ships in Equations 1 and 2:5 parative samples of the same total volume of two
differing catalyst shapes will result in differing
𝑡𝑡𝑡𝑡𝑡𝑡ℎ(𝛷𝛷)
𝜂𝜂
= (1) activity performance, because the overall loaded
𝛷𝛷 density also plays a key role in the available activ-
!!"
𝑘𝑘! 𝐶𝐶! 𝑛𝑛!" + 1
ity that can be loaded in a fixed volume such as a
𝛷𝛷
= 𝐿𝐿!" (2) reactor.
2𝐷𝐷 𝐶𝐶
! ! When considering TL versus QL catalyst
shapes, both exhibit similar effectiveness factors
! 6𝑉𝑉

𝑑𝑑!" =
! (3) on the basis of common effective particle diam-
𝜋𝜋 eter, and commercial experience demonstrates
that both load with similar bed void fractions
ke = Activation energy (εB). QL catalysts do provide higher effectiveness
CA = Concentration of species A factors than TL catalysts of the same actual phys-
nro = Reaction order ical diameter which in many cases can permit
Lpe = Effective diffusion length lower activity catalysts to provide similar perfor-
De = Effective diffusivity mance to higher activity TL catalysts at the cost
Φ = Thiele modulus of increased bed pressure drop. This disadvan-
Vp = Particle volume tage generally limits the layer size of QL materi-
als in reactor loading design, especially for units
Since the catalyst effectiveness factor is a func- limited by pressure drop. However, when com-
tion of the Thiele modulus, there are only a few pared to traditional shapes, lobe-shaped particles
key variables which differ between the various load with a higher bed void fraction.
catalyst particle shapes. This includes the effec- When considering the value of shaped par-
tive diffusion length and the effective diffusiv- ticles in reactor applications, it is important to
ity, since individual reaction rates are constant observe the relative crush strength of the cata-
for similar catalyst activities. Thus, the geometry lyst particles as it relates to operating pressure

www.digitalrefining.com/article/1001491 April 2018 3


drop across the catalyst bed. This can be per- extruded shape load at similar void fractions
ceived as an area of exposure for particles with and densities for commercial sized vessels since
shapes that inherently have weaknesses, and packing efficiency is determined by the parti-
lobed particles certainly have a central weakness cle shape rather than particle diameter when
when compared to cylinders and spheres since considering a bed of particles of equal diame-
the lobes can be broken away from the centre ter.7 In addition, there is very little influence on
of the pellet under high stresses. In general, the bed void from wall effects in commercial scale
crush strength and any other typical bulk prop- reactors because of the large ratio between the
erty of the catalyst is also a function of the Sp/ diameter of the vessel and the diameter of the
Vp ratio.4 The resulting changes in bulk proper- particles.8
ties have led the industry to target TL and QL However, larger particle diameter extrudates
shapes, as these shapes result in acceptable bulk of a similar shape do result in lower catalyst bed
properties for optimum performance. pressure drop at the same operating conditions
Another key factor in the value of shaped par- (i.e. equal mass flow rate of vapour and liquid).
ticles is a reduction in reactor pressure drop at This is due to the effect of liquid hold-up and
constant operating conditions and particle diam- relative velocity in the bed voids.9 Larger par-
eters from beneficial changes in reactor bed void ticles, while having similar bed voids, create a
(εB). This is when comparing lobe-shaped parti- less tortuous path for materials flowing across
cles to conventional particles. More specifically, the catalyst bed and ultimately it is the frictional
individual lobe- shaped particles also exhibit dif- losses due to the impact of particle contact which
fering performance with regard to pressure drop results in a pressure gradient across the packed
across the catalyst bed. Pressure drop in packed bed. Thus, less particle contact results in lower
beds is commonly modelled by the Ergun equa- pressure drop given the same overall packed bed
tion which is applicable for single phase flow, but void space. In addition to particle size, particle
to model two phase flow through packed beds shape also has a significant impact on pressure
there are modified versions of the Ergun equa- drop. Note that pressure drop is inversely pro-
tion. Using the modified Reynolds number, the portional to the effective hydraulic diameter of
Ergun equation can be simplified as shown in the particle which is a direct function of the phys-
Equation 4:6 ical characteristics of the particle shape. In order
to model the comparative pressure drop perfor-
𝛥𝛥𝛥𝛥 150 𝑣𝑣 ! mance of differing particles in a packed bed, it
= + 1.75 ∗ 𝜌𝜌 ∗
𝐿𝐿! 𝑛𝑛𝑛𝑛𝑛𝑛 𝑑𝑑!! ∗
1 − 𝜀𝜀! (4) is common practice to relate the actual diameter
𝜀𝜀!! of the particles to an effective particle diameter.
Work from Brunner et al asserts that the effective
dph = Particle hydraulic diameter diameter of a catalyst particle can be modelled
εB = Catalyst bed void fraction by a sphere which exhibits the same physical vol-
LB = Catalyst bed length ume as the catalyst particle,3 while work from
Ancheyta et al asserts that the effective diameter
This equation illustrates that pressure drop of a catalyst particle can be modelled by a sphere
across the reactor bed is inversely proportional to which exhibits the same physical surface as the
both catalyst bed void fraction (εB) and the effec- catalyst particle.5 Since lobed particles provide
tive particle hydraulic diameter (dph). higher Sp/Vp ratios than spheres, these particles
Void fraction itself is a function of loading result in effective diameters that are a fraction
method (dense versus sock) and particle shape. of their actual diameter regardless of the calcu-
Since the maximum system activity is achieved lation method mentioned above. It is common
when a bed is dense loaded, it is common to practice in industry to model the effective diam-
apply one of many commercial techniques to eter of particles in a packed bed by either afore-
improve the arrangement of catalyst particles mentioned method for use in modelling pressure
during the loading process. In general, the dense drop with the Ergun equation to achieve a rela-
loading process can result in a load that achieves tionship for normalised particle characteristics.
105% of the compacted bulk density (CBD) of a However, both methods do not supply completely
catalyst. Differing diameter particles of the same reliable estimates for bed pressure drop predic-

4 April 2018 www.digitalrefining.com/article/1001491


Catalyst particle properties3,5,9

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, %

sure drop relative to alterna- 100


tive options. Coupled with more
90
attractive bulk physical prop-
erties for TL-shaped particles 80
which lead to less breakage, TLs
remain the primary preferred 70
shape for hydroprocessing cata-
lysts since their introduction to 60
)

)
m

the market in the 1970s. While


m

m
.5

.5

.5

.5

.5

QL particles are used in com-


(2

(2

(2

(2

(2
H

YL

TL

mercial hydroprocessing appli-


Q

AT
SP

cations, their use is generally


limited to small layers of an Figure 5 Pressure drop relative to TL particle shape

www.digitalrefining.com/article/1001491 April 2018 5


astounding. The shape was developed in part Commercial performance of ATX catalysts
to provide hydrocracking units with an option Hydrocracking units have recently gained high
to reduce pressure drop and allow significant visibility in the North American refining sec-
increases in feed rates for units facing hydraulic tor due to their capability to produce high value
limitations. However, there are several advan- product streams from low cost, readily availa-
tages offered by the ATX shape for cracking ser- ble hydrogen streams. These units have gained
vice. All of Criterion’s new generation modern significant favour in the global refining sector
hydrocracking catalysts can be manufactured in to satisfy a multitude of challenges, including
the ATX shape, allowing all hydrocracking appli- increasingly stringent environmental regulations,
cations the flexibility to benefit from significant higher conversion of low value heavy petroleum
performance and capacity increases. fractions, and to satisfy the growing demand for
The ATX shape is a modified TL shape with higher quality middle distillate fractions. The
higher particle surface area and slightly lower demand from existing refining assets and the
particle volume. Catalysts manufactured in the growing market of new assets in the hydrocrack-
ATX shape demonstrate lower bulk density when ing application space has led many refiners to
loaded by creating increased catalyst bed void. target the highest performance catalyst products
This significant increase in bed void is essential that offer advantages in operability and flexibility
to improving system pressure drop as the parti- for their reactor systems.
cle does have a slightly lower effective particle The following two commercial examples
hydraulic diameter than the conventional TL. The demonstrate the influence of Criterion’s expert
net effects from changes in bed void and effective technical services and the power of ATX-shaped
particle hydraulic diameter provide a reduction products applied in two of several independent
in catalyst bed pressure drop of 15-20% in com- hydrocracking units to unlock additional capac-
mercial applications relative to conventional TL ity, creating significant increases in profitability.
catalysts of the same particle diameter depending
on loading methods. Commercial performance:
Lower bulk density also provides a significant Case 1 (Marathon Garyville)
reduction in the catalyst weight required to fill One of the highest capacity hydrocracking units
reactor vessels, aiding in reducing the total fill in the world, operated by Marathon Petroleum
cost for a catalyst system design. The ATX shape Company (MPC) at the Garyville refinery in
also provides a large boost in individual particle Louisiana, leverages the advantage of ATX-
performance due to reduced effective diffusion shaped catalysts to maximise unit capacity
lengths which leads to a higher catalyst effec- and performance. Over two operating cycles,
tiveness factor. The resulting impact of higher the Garyville hydrocracker transitioned to
effectiveness leads to an advantage in system Criterion’s ATX catalysts to reduce unit pres-
activity performance despite the reduction in sure drop. While only ~30% of the overall cur-
catalyst mass. For hydrocracking applications, rent catalyst load is now ATX-shaped cracking
this performance advantage also translates to catalysts, the unit has been capable of increas-
improved selectivity when considering reactions ing throughput by 35%. The unit processes a
like over-cracking which continue to propagate combined feed stream of heavy vacuum gas-
as reactants exit the catalyst particles, causing the oil (HVGO), coker gasoil (CGO) and, intermit-
formation of light ends. tently, deasphalted oil (DAO). Consistently,
The additional void space created in the reac- feed rate is pushed to higher limits as the refin-
tor from the ATX shape also permits increased ery has a very high margin on the ULSD prod-
gas circulation rates to stabilise reactor temper- uct as well as high value unconverted oil which
ature profiles and minimise peak temperatures. is processed in the FCC. Overall, conversion and
The minimisation of peak temperatures is key in yields have remained extremely stable through-
hydrocracking service since this leads to stable out both operating cycles with extremely stable
product yields for extended periods of the cycle cracking reactor operating temperatures. Figure
and the minimisation of light ends production 6 illustrates the effect of ATX shape on normal-
at higher reactor weighted average bed tempera- ised pressure drop across the guard reactor sec-
tures (WABT). tion as well as the overall reactor normalised

6 April 2018 www.digitalrefining.com/article/1001491


pressure drop. It is clear that
the material in the guard reac-
tor which remains loaded as

Normalised pressure drop


the typical standard TL-shaped
particles has retained the same 20% reduction
normalised pressure drop,
while the hydrocracking reac- Previous cycle
tor has seen a reduction in nor- with conventional Current cycle
trilobe shape wih ATX shape
malised pressure drop by ~20%
sourced from the change in cat-
alyst shape loaded. Guard RX
HC RX
Guard RX nDP HC RX nDP
Figure 7 shows the massive Time on stream, days
increase in feed rate to the unit
over the transition from the first Figure 6 MPC Garyville normalised reactor pressure drops
cycle with conventional TL to
the current cycle loaded with
ATX catalysts. The feed rate
between the two trains in the
unit now supports one of the 35% increase
Total feed rate

highest capacity hydrocracking


units in the world. This increase
Previous cycle
in feed rate is largely supported with conventional Current cycle
trilobe shape wih ATX shape
by the advantages offered from
the ATX shape which permits
sufficient activity and yields
retention to achieve the desired
performance from the MPC
Garyville operating team. Time on stream, days
MPC operates the unit in a
manner that stabilises reac- Figure 7 MPC Garyville total unit feed rate
tor temperatures and max-
imises gas rates to maximise
product quality and yields.
The resulting hydrocrack- Train 1
ing reactor WABTs obviously Train 2
increased as a function of the
significant increase in feed Previous cycle
rate shown in Figure 8, but with conventional
WABT, ºF

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

www.digitalrefining.com/article/1001491 April 2018 7


reactor beds with stable control
of equal bed temperature rise
HC bed 1
from cycle to cycle. The excess
HC bed 2
HC bed 3
gas circulation provides a sig-
Cracking bed ∆T, ºF

HC bed 4 nificant advantage to stabilise


bed temperature control as well
Previous cycle
as hydrogen availability in the
with conventional Current cycle cracking reactors which pro-
trilobe shape wih ATX shape
vides the most stable cracking
system available. Excess hydro-
gen reduces the coking poten-
tial and minimises deactivation
Time on stream, days in the cracking beds. Figure 10
shows the retention of excess
gas rates from cycle to cycle
Figure 9 MPC Garyville cracking reactor bed ΔTs despite the significant increase
in feed rate. Ultimately, this
advantage is made possible
with the improvements in reac-
tor pressure profile via the ATX
shape.
Regardless of operating sta-
Gas/oil ratio, SCFB

bility and reactor pressure


drop, the key performance
from hydrocracking units is
ultimately measured in the
Previous cycle product yields. Figure 11 illus-
with conventional Current cycle
trilobe shape wih ATX shape trates the stability of yields that
MPC has enjoyed from cycle to
Train 1 cycle from a total liquid volume
Train 2 perspective. Note that the total
liquid volume yield is retained
Time on stream, days despite the increase in feed rate
which implies that while the
Figure 10 MPC Garyville cracking reactor gas to oil ratios percentage volume yields have
remained similar, the total vol-
ume yield has increased in an
equivalent manner to the total
feed rate. This demonstrates
the activity advantage from
Total liquid yield, %volFF

ATX-shaped catalysts, provid-


ing excellent selectivity and
performance. Figure 12 also
highlights the advantages with
Previous cycle regard to light ends produc-
with conventional Current cycle
wih ATX shape tion. While the cracking reactor
trilobe shape
temperatures have increased
on an absolute basis, the light
ends production has remained
very stable, demonstrating the
Time on stream, days reduced over-cracking poten-
tial and yields selectivity.
Figure 11 MPC Garyville total liquid volume yield

8 April 2018 www.digitalrefining.com/article/1001491


Commercial performance:
Case 2 (Shell Scotford) Previous cycle C1
with conventional Current cycle
The Shell Scotford refinery wih ATX shape C2
trilobe shape
operates a large Shell licensed C3
hydrocracking unit that pro- iC4
cesses a combined feed stream nC4

of oil sands derived straight run

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

unit. In addition to increasing ATX cycle


unit profitability and potential
capacity, the catalyst load also
offered a reduced fill cost as
a result of lower loading den-
sity. While the unit has only 10−15%
recently leveraged the advan- reduction
tages of the specialised ATX- 10−15%
shaped catalyst in the current reduction
operating cycle to increase feed
rates, Scotford has been able 0 100 200 300 400 500 600 700 800
to increase operating severity Time on stream, days
to produce a set of improved
product streams. The Scotford Figure 13 Shell Scotford normalised reactor pressure drop
hydrocracker operation has
been referenced in a previ-
ous publication by Sharpe
et al where the product streams
from the unit benefited sig-
Normalised pressure drop

nificantly in terms of het-


eroatom concentration from
catalytic advances. Namely,
Scotford targets production of
blend quality product streams
for their distillate pool which
requires both highest activ-
ity pretreatment catalysts
and exceptional selectivity in
conversion.
Figure 14 highlights the per- 0 100 200 300 400 500 600 700 800
centage reduction in normalised Time on stream, days
pressure drop for the Scotford
hydrocracking reactor, which Figure 14 Shell Scotford normalised reactor pressure drop reduction

www.digitalrefining.com/article/1001491 April 2018 9


decrease in temperature due to
the improved performance of the
Standard trilobe cycle
Cracking reactor WABT catalyst despite the reduction in
ATX cycle
catalyst mass loaded.

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%

catalyst products has revolution-


ised the performance potential
of hydrocracking units, enabling
capacity increases and expand-
ing the world’s largest cracking
units.

Standard trilobe cycle


MPC makes no endorsement of the
ATX cycle
products described in this article. MPC’s
0 100 200 300 400 500 600 700 800 opinions and conclusions are limited to its
Time on stream, days own experiential data included here.

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
the stability of the catalyst system with a transi- Publishers B.V., Amsterdam, 1988, 253-276.
tion from standard TL particles to ATX-shaped 3 Brunner K M, Perez H D, Peguin R P S, Duncan J C, Harrison
particles. The hydrocracking reactor WABT L D, Bartholomew C H, Hecker W C, Effects of particle size and
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
4 Worstell J H, Improve Fixed-Bed Reactor Performance without
catalyst effectiveness factor which inherently Capital Expenditure, CEP Magazine, Jan 2004.
improves the reactor performance in a similar 5 Ancheyta J, Muñoz J A D, Macias M J, Experimental and
operating regime with regard to space velocity. theoretical determination of the particle size of hydrotreating
This advantage occurs along with the reduction catalysts of different shapes, Catalysis Today 109, 2005, 120-
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performance is achieved with less overall cata- 6 Worstell J, Adiabatic Fixed-Bed Reactors; Practical Guides in
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10 April 2018 www.digitalrefining.com/article/1001491


particle shape and size effects on hydrodynamic parameters of margin improvement opportunities. She also coordinates
of trickle beds, Chemical Engineering Science 61, 2006, 5534- Criterion’s Hydrocracking Technical Service Pilot Plant Testing in
5543. Houston and instructs the Hydrocracking Catalyst Fundamentals
8 Nemec D, Levec J, Flowthrough packed bed reactors: 1. Single- portion of the Criterion University Hydrocracking Seminar.
phase flow, Chemical Engineering Science 60, 2005, 6947-6957.
9 Afandizadeh S, Foumeny E A, Design of packed bed reactors:
guides to catalyst shape, size, and loading selection, Applied
Thermal Engineering 21, 2001, 669-682. LINKS
Adrienne Van Kooperen is a Senior Hydrocracking Technical More articles from: Criterion Catalysts & Technologies
Service Engineer with Criterion Catalysts and Technologies in More articles from the following categories:
Houston, Texas. Her primary responsibility is providing technical Catalysts and Additives
support to Criterion’s customers: unit performance evaluation and Hydroprocessing
optimisation; troubleshooting; start-up support; and evaluation

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