Overcoming clean fuels challenges

Improvements in FCC pretreat catalyst systems enable refiners to meet ultra-

low sulphur gasoline regulations and increase diesel output

George Anderson Albemarle

R
efiners increasingly need to produce ultra- product yields, selectivities and operations; or
low sulphur gasoline and increase diesel c. Increase the conversion of vacuum gas oil
fuel output, which can be challenging. FCC (VGO) feed to diesel-range products.
pretreatment (FCC-PT) units are, therefore, In addition to these objectives, controlling
more important than ever, and they require FCC-PT catalyst fill costs and achieving target
robust and reliable catalyst systems to give them cycle lengths are high priorities for most refiners.
high activity and good stability while meeting Existing FCC-PT units are designed and oper-
specific operating goals. ated to meet specific operating strategies and
However, no single FCC-PT unit caters equally objectives. They can generally be characterised
to all clean fuels hydrotreating needs. FCC-PT by operating objectives and hydrogen partial
unit operations span a wide range of operating pressure (ppH2). ‘Low’ pressure units operate
conditions and process many types of heavy, with inlet ppH2 <55 bar (800 psi); ‘moderate’
dirty oil feedstocks with differing compositions pressure units operate with inlet ppH2 between
and contaminants. An individual refiner’s 55 and 90 bar (800-1300 psi); and ‘high’ pres-
primary operating objectives can also vary from sure units operate at ppH2 >90 bar (1300 psi).
targeting constant product sulphur to maximis- Units in Europe, the Middle East and India
ing hydrodenitrogenation (HDN) and operate mostly in the low to moderate pressure
hydrodearomatisation (HDA), and/or increasing range. These units are typically operated to
conversion to produce more diesel fuel. Given achieve deep HDS and, in some cases, to increase
these wide ranges of operating conditions, feed conversion of VGO feed to diesel product. North
properties and operating objectives, Albemarle American units fall primarily into the moderate to
has determined that VGO Stax–FCC-PT technol- high pressure range. More than 50% of the
ogy is a preferred solution to enable refiners to world’s moderate pressure FCC-PT units and
meet their FCC-PT challenges. more than 75% of the high pressure units are in
North America. While many of these units focus
FCC-PT on deep HDS, maximising HDN/HDA is also a
FCC-PT is an increasingly important refinery major focus. With the US Environmental
process. Unlike processes that produce clean fuel Protection Agency (EPA) implementing its Tier 3
products directly, its economic value is largely ULSG regulations in 2017, many of these FCC-PT
derived from how well it improves FCC unit units will need to operate at even deeper HDS,
product yields, product qualities and operations. especially those units in refineries that do not
Depending on the refinery, the key objectives for have FCC naphtha post-treat capabilities.
FCC-PT operations may be to: Relatively fewer units in the Americas currently
a. Maintain a low product sulphur level with strive to increase diesel yield compared with the
high hydrodesulphurisation (HDS) to ultimately rest of the world.
meet environmental regulations on gasoline
sulphur content and FCC unit SOx emissions; Leveraging VGO Stax-FCC-PT technology
b. Reduce nitrogen and aromatics levels by Albemarle has a track record in supplying
maximising HDN and HDA to improve FCC unit cobalt-molybdenum (CoMo) and nickel-co-

www.digitalrefining.com/article/1001201 PTQ Q1 2016 1

 Zone 1

Zone 2

Zone 1 Zone 2
(30-60%vol) (40-70%vol)

H2 partial pressure Higher Lower

Main HDS reaction Direct HDS Direct + hydrogen

Reaction zones vary in length
Main HDS inhibitor Organic nitrogen and position during cycle.
Main HDN/HDA reaction Hydrogenation Hydrogenation Catalyst application strategy
organic nitrogen aromatics organic nitrogen aromatics must account for:
Main HDN/HDA inhibitor
Zone 1 growth
HDS reaction rate Fast Slow throughout the cycle
HDN/HDA reaction rate Very slow Slow Zone 2 shrinkage
throughout the cycle
Preferred catalyst types CoMo (low to medium P) CoMo (<55 bar ppH2) The operating conditions
(general guidance: may (Ni) CoMo (medium P) (Ni) CoMo (medium ppH2) and constraints
vary for specifc cases)
NiMo (high P) NiMo (>90 bar ppH2) Product targets

Figure 1 The VGO STAX–FCC-PT reaction zone concept

balt-molybdenum (NiCoMo) catalysts into low to (ULSD) Stax technology has been successful in
moderate pressure FCC-PT units where the applications with three reaction zones for over
primary objective is to achieve low product 10 years. VGO Stax–FCC-PT technology has
sulphur targets. In recent years, product sulphur been successfully applied for the past six years.
targets have become even lower, thus increasing However, it comprises only two reaction zones,
the need for more active and stable catalysts. In as FCC-PT operations currently do not go deep
addition, for moderate to high pressure FCC-PT enough in HDS/HDN to achieve the reaction
units, the need for deeper HDN and greater conditions experienced in Zone 3. Figure 1 illus-
HDA to improve FCC yields and selectivities has trates the basic concepts of VGO Stax–FCC-PT
increased. technology by showing the types of reactions
To better meet these broad market needs, occurring in each zone and the inhibitors slow-
Albemarle has conducted research across the ing these reactions.
spectrum of operations to assess how to help Most low to moderate pressure units have
refiners meet their needs. During this research, constant HDS as their primary objective. In Zone
it became clear that the wide variations in 1, the top portion of the reactor, where direct
FCC-PT operating conditions, unit objectives desulphurisation (DDS) is the predominant reac-
and constraints make it practically impossible tion, CoMo and NiCoMo catalysts are ideal for
for a single catalyst to meet every objective. boosting HDS reaction rates. HDN reaction rates
Therefore, we concluded that Stax systems for tend to be limited by lower pressure, and nitro-
FCC-PT are preferable for almost all gen inhibition further slows HDN and HDA rates
applications. in Zone 1. When intermediate product sulphur
Stax is Albemarle’s proprietary process tech- and nitrogen fall to certain levels, Zone 2 is
nology for designing a catalyst system to meet achieved. HDS reactions can occur via a combi-
unit objectives within given operating conditions nation of DDS and hydrogenation (HYD)
and constraints. This technology accounts for reactions at an overall slower rate than in Zone 1.
the chemical reactions and reaction environ- Due to the lower concentration of nitrogen, HDN
ments encountered in the different zones of the and HDA reactions will be faster compared with
reactor and matches the catalyst benefits with Zone 1, though still relatively slow. Thus, NiCoMo
each zone to optimise the overall catalyst catalysts, with their balance of HDS and HDN
system’s performance. Ultra-low sulphur diesel reactions, can be very beneficial in this part of

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the reactor, especially at moder-
101.0 410
ate ppH2. The conversion of HDS
VGO feed to lighter products in 100.5 WABT 400
these units is essentially due to
390
thermal conversion caused by 100.0

WABT, ºC
HDS, %
increased temperature, although 380
97.5
different catalysts can also stim-
370
ulate different amounts of 95.0
cracking. 360
Units operating at moderate 92.5
350
to high pressures may have any
90.0 340
of the three primary operating 0 500 1000 1500 2000 2500
objectives. As ppH2 increases, Run time, days
achieving increased HDN/HDA
tends to become increasingly 800
Actual
important. For applications 750 Projection
where overall catalyst system 700
HDS activity is the primary
650
WABT, ºF

objective, using CoMo and/or

NiCoMo catalysts in both Zones 600
KF 905
1 and 2 can still be effective for 550
KFR 22
meeting unit objectives. To 500 KF 857
KF 647
achieve moderate levels of HDN Deactivation = 2.5ºF/month
450 >40-month cycle
and HDA, using NiCoMo cata-
lyst in Zone 2 with CoMo or 400
0 200 400 600 800 1000 1200 1400
NiCoMo catalyst in Zone 1 may Days on stream
be sufficient. Achieving deep
levels of HDN/HDA will gener- Figure 2 Temperature increases throughout cycles for commercial examples
ally require NiMo catalyst in 1 and 2
Zone 2, and possibly in Zone 1
as well. However, for units that are HDS activi- produce FCC gasoline with 10 ppm sulphur. Its
ty-limited in any way, CoMo and/or NiCoMo Stax catalyst system is designed with CoMo and
catalysts are beneficial in Zone 1 and, in some NiCoMo Stars Type II catalysts and achieves a
cases, the upper portion of Zone 2 as well. nearly six-year cycle length.
To bolster VGO Stax–FCC-PT technology The second example is a high-pressure FCC-PT
applications, Albemarle has a proprietary unit that processes a feed blend of heavy VGO
process model that gives reliable performance (HVGO) and heavy coker gas oil (HCGO) that has
estimates and is used to generate and assess 3 wt% sulphur, 1500 ppm nitrogen and 2 ppm
catalyst loading design recommendations for nickel plus vanadium. Its inlet ppH2 is about 100
refinery units. bar (1450 psi), and the objectives are to produce
FCC feed with 1500 ppm sulphur and <600 ppm
Optimised application nitrogen while achieving a four-year cycle length.
VGO Stax–FCC-PT technology solution has had Based on process model projections, Albemarle
numerous successful applications in FCC-PT designed a guard catalyst system to remove
units around the world. Two different commer- nickel, vanadium and silicon and to protect
cial application examples will illustrate the against polymerisation causing pressure drop
principle and the results. The first example is a build-up. A VGO Stax–FCC-PT NiCoMo/NiMo
low pressure unit with an inlet ppH2 of 53 bar Stars catalyst system was applied for hydrotreat-
(770 psi) that processes a straight run VGO feed ing. As Figure 2 shows, this catalyst system is
with 2 wt% sulphur and 1600 ppm nitrogen. approaching three years on oil, and its actual
This unit runs in constant product sulphur performance corresponds well with the process
mode, targeting 200 ppm FCC feed sulphur to model projections.

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 older catalysts in this zone.
KF 907 has similar high HDS
NiMo STAX Systems including KF 860 and HDN RVAs to KF 780.
HDN and Arosat activity Because KF 907 is a Type I cata-
KF 861 lyst, Albemarle primarily
KF 851 recommends it in units where
STAX Systems: start-up constraints such as
(Ni)CoMo coupled with NiMo temperature limitations for VGO
feed introduction and/or the
need to use gas phase sulphid-
ing make Type I catalysts
(Ni)CoMo STAX Systems
preferable. However, because
KF 757 KF 780 KF 905 KF 905N KF 907 KF 907 HDS and HDA RVAs
Type I Type II increase as operating severities
HDS activity increase, the catalyst can also
show significant performance
Figure 3 Albemarle’s FCC-PT catalysts benefits in Zone 2.
For moderate to high pressure
FCC-PT catalysts commercialised in 2013-2014 applications, (Ni)CoMo catalysts
in Zone 1, coupled with NiMo
Process Pressure Unit catalysts in Zone 2, are often
Catalyst Sizes Type objective range sales the preferred system compo-
KF 780 1.3Q, 2Q CoMo STARS HDS Low to moderate 6
KF 861 1.3Q, 2Q NiMo STARS HDN/HDA Moderate to high 1
nents, especially if HDN and
KF 905N 1.3Q, 3Q; 1.5E NiCoMo STARS HDS/HDN Low to high 11 HDA are key objectives. KF 861
KF 907 1.3Q, 2Q; 1.5E NiCoMo Type I HDS Low to moderate 4 Stars is the NiMo catalyst with
the highest HDN activity of
Table 1 these FCC-PT catalysts, gener-
ally 20% higher HDN RVA than
Wider ranging options KF 851 or KF 857 Stars. It also
Given the increasingly challenging process objec- has relatively low loading density and provides
tives they face across the spectrum of FCC-PT attractive fill costs.
feed properties and operating objectives, refiners KF 905N Stars catalyst is a special purpose,
require catalyst systems with superior activity trimetallic catalyst with superior HDS activity
and stability. US refiners also have to contend coupled with high HDN activity that meets or
with the upcoming Tier 3 ULSG regulations exceeds all of the NiMo catalysts except for KF
beginning in 2017, an especially daunting chal- 861. Because of its high HDS and HDN RVAs
lenge for those refineries that do not have FCC across all operating pressures, its performance
naphtha post-treaters. can be very good in Zone 1 and the upper part of
Albemarle’s four newest FCC-PT catalysts (see Zone 2.
Table 1) provide technology solutions to custom-
ers with units spanning the full range of FCC-PT Conclusion
application sub-segments. When utilised in Stax As refiners face stiffer challenges in FCC-PT
catalyst systems (see Figure 3), the individual operations, they need to have reliable and robust
benefits of these Ketjenfine (KF) catalysts can be catalyst systems available that give them high
leveraged to meet multiple objectives and activity and good stability. Albemarle’s technol-
constraints simultaneously. ogy portfolio has been revamped with new CoMo,
For reaction Zone 1, CoMo or NiCoMo cata- NiCoMo and NiMo catalysts that individually
lysts are the preferred Stax catalyst components have high activity and stability, but can give opti-
to promote DDS at essentially all pressure levels. mised performance in Stax catalyst systems.
KF 780 Stars, with its high relative volume activ-
ity (RVA) for HDS and HDN and its low loading VGO STAX–FCC-PT, STARS and Ketjenfine are marks of Albemarle
density, gives 10–20% higher HDS RVA than Corporation.

4 PTQ Q1 2016 www.digitalrefining.com/article/1001201

George Anderson is a Global Hydroprocessing Specialist with
Albemarle Corporation, providing technical support to the LINKS
company’s global Clean Fuels Technology catalyst business in a
variety of hydroprocessing applications. He was previously with More articles from: Albemarle Corporation
ExxonMobil Research & Engineering Company for 30 years, with More articles from the following categories:
various responsibilities in process and catalyst development for Catalysts and Additives
refining and synthetic fuels. He holds BS and M.Eng degrees Fluid Catalytic Cracking
in biomedical and chemical engineering from Rensselaer Sulphur Removal, Recovery and Handling
Polytechnic Institute, and a PhD in chemical engineering from
Rice University.

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