GRACE DAVISON European Edition September 2009

CATALAGRAM®

5 - Year Anniversary of
EnhanceR FCC Catalysts

• 5 - Year Anniversary of EnhanceR FCC Catalysts

• Development of PremieR: A Third-Generation EnhanceR Catalyst for Coke-
Selective Bottoms Cracking
• Operating to Maximise LCO Yield in the FCC Unit
• Recycling Heavy Cycle Oils for Maximum LCO Applications
• D.A.I.S - Davison Automatic Injection System
• Grace Davison Co-sponsors the 2009 Murco Rugby Tournament in Paris
• 2008 South African FCC Technology Seminar
• Important Announcement: Grace Davison Catalyst Technology Conference,
Istanbul, September 2010
A message from the editor…

I’m very pleased to welcome you to the September 2009 edition of the Grace Davison
European Catalagram.

A year is a long time in the refining industry. When the last Grace Davison European
Catalagram was published crude oil prices had reached record levels, and the apparent
shift in the market from gasoline to diesel demand appeared to be at the forefront of
people’s minds. The subsequent global economic crisis hit oil demand, resulting in a
dramatic drop in crude oil prices and, in addition, somewhat dampened the growing
demand for diesel.

The consequent product shifts in the FCC market underline the benefits of a full and
diverse portfolio of FCC catalysts and additives. In this respect, the 5-year anniversary
of the Grace Davison EnhanceR Technology Platform, discussed on Page 2, is very
timely. This article describes the growth of the EnhanceR portfolio, including the third
generation of catalyst families that are now being commercialised; NACER provides
high activity for low-metal feeds, ResidCrackeR allows deep bottoms cracking for
resid-processing applications and DieseliseR generates highest LCO yields for FCC
units operating in the LCO maximisation mode.

In addition, we are pleased to announce the most recent addition to our EnhanceR
catalyst portfolio on Page 15. PremieR is a third-generation EnhanceR resid catalyst
family for coke-selective bottoms cracking, and will be commercialised later this
year.

Although diesel demand may have declined somewhat in comparison to this time last
year, there are still many refiners who are looking to increase LCO production in the
FCC unit. In addition, the OPEC World Oil Outlook 2009 report predicts that demand
for diesel will rebound after the current economic downturn. With this in mind, we
describe operating techniques to maximise LCO yield in the FCC unit on Page 16, and
also provide two European case studies.

LCO maximisation techniques involving reduced operating severity suffer from the
drawback of higher bottoms yield. The article on Page 24 discusses the effects on the
key product yields of recycling various product bottoms streams.

Regardless of operational strategy it is extremely important to be able to feed the

FCC unit with catalysts and additives in accurate and reliable doses. The Davison
Automatic Injection System (D.A.I.S), discussed on Page 30, does exactly this and
results in a more efficient and cost-effective usage of catalysts and additives, with
optimum product yields.

Finally on Page 33, we announce that the next Grace Davison Catalyst Technology
conference will take place in Istanbul in September 2010. We hope to see you there!
 GRACE DAVISON
CATALAGRAM®
European Edition September 2009

5 - Year Anniversary of
IN THIS ISSUE
EnhanceR FCC Catalysts

5-Year Anniversary of EnhanceR FCC Catalysts

2
~ by Gordon McElhiney and Colin Baillie, Grace Davison
• 5 - Year Anniversary of EnhanceR FCC Catalysts
• Development of PremieR: A Third-Generation EnhanceR Catalyst for Coke-
Selective Bottoms Cracking
• Operating to Maximise LCO Yield in the FCC Unit
• Recycling Heavy Cycle Oils for Maximum LCO Applications
• D.A.I.S - Davison Automatic Injection System
• Grace Davison Co-sponsors the 2009 Murco Rugby Tournament in Paris
• 2008 South African FCC Technology Seminar
• Important Announcement: Grace Davison Catalyst Technology Conference,
Istanbul, September 2010

September 2009
Development of PremieR: A Third-Generation EnhanceR
Catalyst for Coke-Selective Bottoms Cracking 15
by Gordon McElhiney and Colin Baillie, Grace Davison
Managing Editor:
Gordon McElhiney

Contributors:
Colin Baillie
Operating to Maximise LCO Yield in the FCC Unit

by Michel Melin and Colin Baillie, Grace Davison

16
Wu-Cheng Cheng
David Hunt
Ruizhong Hu
Larry Langan
Hongbo Ma
Gordon McElhiney
Recycle Strategies for Maximising FCC Light Cycle Oil

by David Hunt, Ruizhong Hu, Hongbo Ma, Larry Langan and

24
Michel Melin Wu-Cheng Cheng, Grace Davison
Maria Luisa Sargenti

Accurate and Reliable Control of FCC Catalyst and

Additive Addition 30
by Maria Luisa Sargenti, Grace Davison

Grace Davison Co-Sponsors the 2009 Murco Rugby

Tournament in Paris 32
Grace GmbH & Co. KG by Colin Baillie, Grace Davison
In der Hollerhecke 1
67547 Worms, Germany
T +49 (0) 6241 403-1425
+49 (0) 6241 403-1608
2008 South African Seminar

by Colin Baillie, Grace Davison

32
F +49 (0) 6241 403-1455
+49 (0) 6241 403-1240

www.grace.com
The information presented herein is derived from
Important Announcement: Grace Davison Catalyst
Technology Conference, Istanbul, September 2010 33
our testing and experience. It is offered, free
of charge, for your consideration, investigation
and verification. Since operating conditions
vary significantly, and since they are not under
our control, we disclaim any and all warranties
on the results that might be obtained from the
use of our products. You should not make any
assumption that all safety or environmental
protection measures are indicated or that
other measures may not be required.

© 2009 Grace Davison Refining Technologies Europe

Grace GmbH & Co. KG

Catalagram European Edition September 2009 1

 5-Year Anniversary of EnhanceR
FCC Catalysts
by Traditional Approach to catalysts were very successful
FCC Catalyst Development in coke- or gas-limited
Gordon McElhiney operations.
Director, Marketing and The combination of rare-
Business Development earth-exchanged USY (REUSY) These developments were
zeolite with a modified followed by a period of focusing
and Al-Sol binder matrix was the on zeolite technology, which
basis of some early Grace culminated in the development
Colin Baillie Davison FCC catalysts. These of new CSSN and CSX zeolites.
Marketing Manager catalyst systems increased Replacing REUSY with CSSN
the flexibility of the FCC unit and CSX zeolites provided FCC
Grace Davison by enabling control of the catalysts with superior stability,
Refining Technologies Europe extent of hydrogen transfer coke selectivity and activity.
through the adjustment of the
rare-earth exchange levels. There then followed a period
These catalysts were typically in which the R&D focus was
used by units in high octane on matrix technology. This
mode. resulted in the development of
TMA (Tunable Matrix Alumina)
The development of the SAM- and NMT (Novel Matrix
100 matrix provided higher Technology), which further
intrinsic bottoms cracking as improved the coke-selective
well as vanadium tolerance. This bottoms cracking performance
was followed by the SAM-200 of FCC catalysts.
matrix, which was developed
for nickel passivation. The These are only some of the
use of SAM-100 or SAM-200 technological advances in
matrices resulted in catalysts FCC catalysts made by Grace
that provided lower Delta Coke Davison. It can be seen that
and gas. The resulting FCC the FCC industry has benefited

2 www.e-catalysts.com
from alternating periods of to better match specific NOMUS, the partner first
zeolite and matrix technology processing requirements. generation EnhanceR catalyst
progress, each resulting in family for resid feeds, utilises
incremental performance •• ESS Technology results in the EAM and ESS Technologies
advances. However, as the higher compositional and to provide increased intrinsic
catalyst became more highly topographic integrity at bottoms cracking, which allows
developed it was increasingly both the micro and macro customers to crack deeper into
difficult to make further scales. ESS brings improved the bottoms, being therefore
progress, clearly showing the resistance to hydrothermal the catalyst family of choice
limits of this approach. deactivation. for those FCC units that are
circulation limited but have
Rather than making separate spare air capacity.
EnhanceR Approach to modifications to the zeolite
Catalyst Design and matrix components, NADIUS incorporates the EAMHT
the EnhanceR Plant enables and ESS Technologies and is the
A significant breakthrough processing of input materials, catalyst family that provides
in FCC catalyst design was intermediate products and high conversion with low-metal
subsequently achieved with end-product FCC catalysts. feeds.
the introduction of the Grace By this means the EnhanceR
Davison EnhanceR Technology Technologies avoid the
Platform. This platform antagonistic consequences Experience Using NEKTOR
involves the following four encountered when attempting at Refinery A
technologies: to achieve further performance
benefits using the separate Refinery A is located in
•• EPR Technology causes matrix/zeolite approach. Northern Europe and operates
physical restructuring of a Kellogg Side-by-Side FCC
mesopores, impacting unit and processes a heavy
pore connectivity and First Generation EnhanceR feedstock with some of the
pore-size distribution. EPR Catalysts highest contaminant metal
brings deeper bottoms levels observed in the European
cracking and improved The initial application of the region. To process resid feeds
coke selectivity. EnhanceR approach to catalyst more profitably, the refinery
design resulted in a first switched from a Grace Davison
•• EMR Technology pro- generation of catalyst families, KRISTAL to a NEKTOR catalyst.
vides improved contact NEKTOR, NOMUS and NADIUS. The key FCC unit objectives
of metal-passivation cat- The first two are specifically were to reduce dry gas yield,
alyst sites with metal- configured for resid and maintain LPG yield, increase
containing heavy feed the latter for clean-feed gasoline yield and decrease
molecules. EMR enables applications. bottoms yield. The main
chemical passivation of effects of the catalyst change
metal contaminants, pro- NEKTOR utilises the EPR and from KRISTAL to NEKTOR on
tecting the zeolite and EMR Technologies to provide the standard yields are shown
matrix functions while re- improved bottoms cracking in Table 1.
taining excellent catalyst through low Delta Coke. In
physical properties. resid processing NEKTOR Table 1 clearly demonstrates
customers are utilising the that the catalyst change from
•• EAM Technology involves superior coke selectivity and KRISTAL to NEKTOR resulted
altering surface chemistry metals tolerance to relieve air- in an increase in conversion of
profiles, modifying the blower constraints, increase 0.55 wt.% with improved yields.
number, type, strength the volume of feed processed For example, LPG yield was
and distribution of acid and improve bottoms cracking maintained and gasoline yield
sites. EAM enables the via increased cat-to-oil and/ was increased substantially.
customisation of catalytic or decreased regenerator This was accompanied by a
activity and selectivity temperature. reduction of dry gas and DCO

Catalagram European Edition September 2009 3

Table 1:
Averaged Test-Run Data at Between 85-100% Catalyst Change Out

KRISTAL NEKTOR
Dry Gas wt. % base -0.14
Total C3+C4 wt. % base +0.16
Gasoline (C5 - 221°C) wt. % base +0.91
LCO (221 - 350 °C) wt. % base -0.24
DCO (>350 °C) wt. % base -0.31
Coke wt. % base -0.36
Conversion wt. % base +0.55

yields. Furthermore, it is also To summarise, the NEKTOR The superior resid-processing

noteworthy that these yields catalyst used by Refinery ability resulted in lower dry gas
were obtained during a period A demonstrated improved make and Delta Coke, as well
in which e-cat Ni+V levels metals tolerance compared to as enhanced catalyst stability
increased sharply. By the time the previous KRISTAL catalyst. to contaminant metals.
that NEKTOR had reached 85-
100% change out, the e-cat
Figure 1:
Ni+V levels had increased
Unit Test-Run Data for Delta Coke Yield
from ca. 4,800 to 11,000 ppm,
giving a clear indication of the 1.35
excellent metals tolerance of
NEKTOR.
1.25
Delta Coke (wt. %)

Unit test run data comparing

NEKTOR with KRISTAL for Delta 1.15
Coke versus e-cat Ni equivalents
are shown in Figure 1. The 1.05
improved metals tolerance of
NEKTOR clearly enabled the
unit to run at significantly 0.95
KRISTAL NEKTOR
higher Ni-equivalent levels,
with no penalty in Delta Coke. 0.85
It is primarily this reduction in 2,000 3,000 4,000 5,000 6,000
the Delta Coke for NEKTOR that E-Cat Ni Equivalent (ppm)
allowed the refinery to process
feeds higher in contaminant Figure 2:
metals. Unit Test-Run Data for Hydrogen Yield

0.16
Hydrogen is the major
contributor to dry-gas yield,
0.14
and due to the excellent
Ni tolerance built into
0.12
NEKTOR considerably less
H2 (wt. %)

hydrogen was produced

0.10
compared to KRISTAL. This is
clearly demonstrated in
0.08
Figure 2, which compares
NEKTOR and KRISTAL unit test- 0.06
run data for hydrogen yield KRISTAL NEKTOR
versus Ni equivalent. 0.04
2,000 3,000 4,000 5,000 6,000
E-Cat Ni Equivalent (ppm)

4 www.e-catalysts.com
Table 2:
SR-SCT-MAT Testing of NOMUS
Catalyst Previous NOMUS-220P Delta
Conversion % 71 73 2
Cat-to-Oil g/g 3.1 2.5 -0.6
Hydrogen wt. % 0.20 0.14 -0.06
Total C1 + C2 wt. % 2.0 1.8 -0.2
LPG wt. % 18.5 17.3 -1.2
LPG Olefinicity % 65.8 64.8 -1.0
Gasoline wt. % 47.8 51.0 3.2
LCO (216-337 °C) wt. % 16.9 17.1 0.2
HCO (>337 °C) wt. % 11.7 9.7 -2.0
Coke wt. % 3.0 3.0 0.0

Experience Using NOMUS at On moving to NOMUS, e-cat Table 3 shows FCC unit data
Refinery B analysis revealed much higher from the transition period to
MAT (+ 4%) at the same specific NOMUS. The higher activity
Refinery B is located in the catalyst addition rate. In and stability of NOMUS allowed
Middle East and operates addition, a lower SAK number a 20% reduction in specific
a UOP High-Efficiency FCC was observed, which led to a catalyst addition rate, as well
unit in full-burn mode. The measurable improvement in as use of a more aromatic and
typical e-cat MAT is 70 wt.%, catalyst strippability, providing heavier feed (as indicated by a
whilst average Ni and V relief on the regenerator reduced UOP-K factor). In addi-
levels are 2,500 and 1,300 temperature limit and allowing tion, a significant increase in
ppm, respectively. Refinery B processing of heavier feed. conversion through improved
targeted maximum bottoms Table 2 shows SR-SCT-MAT bottoms conversion to gaso-
upgrading and gasoline yield, selectivity shifts using refinery line was observed. These im-
as well as maximising feed rate e-cats and feed. It can be seen provements were achieved
and residue content within the that, at constant coke, NOMUS with minimum coke penalty.
limitations of cat/oil ratio. In resulted in higher conversion, NOMUS allowed all of the tar-
order to meet these targets the lower gas, increased gasoline gets to be achieved at Refinery
refinery switched to a NOMUS- and lower bottoms yield. B and the trial was considered
220P catalyst. a complete success.

Table 3:
FCC Unit Data from Refinery B

Catalyst Previous NOMUS-220P

Feedrate m /h
3
base base + 1%
Feed UOP-K 12.0 11.8
RxT °C base base
C/O g/g base base - 0.2
SCAR kg/ton FF base base - 20%
Conversion wt.% base base + 3.0
Dry Gas wt.% base base
LPG wt.% base base - 0.5
Gasoline wt.% base base + 2.9
LCO wt.% base base - 1.4
MCB wt.% base base - 1.7
Coke wt.% base base + 0.6
E-cat MAT 67 71

Catalagram European Edition September 2009 5

Experience of Using NADIUS Second-Generation further reduction in Delta Coke.
at Refinery C EnhanceR Catalyst Families Users of NEKTOR-ULCC are
seeing further improvement
Refinery C in Northern Europe Whereas the first generation in coke selectivity, and are
operates an Ultra-Orthoflow of EnhanceR catalysts each uti- using this to increase con-
FCC unit with a capacity of 220 lised two technologies, further version at maximum feed-
m3/h, and they started up an development provided a second rate, achieving even bet-
ICR hydrocracking unit, which generation of catalyst families ter bottoms upgrading with-
delivered 193 m3/h of UCO feed that incorporated an additional out requiring additional air.
to the FCC unit. Compared to EnhanceR Technology. For ex- NOMUS-DMAX is formulated
the previous feedstock the UCO ample, NEKTOR-ULCC is for- with the EAMR and ESS Technol-
feed was severely hydrotreated, mulated with the EPR and EMR ogies used in NOMUS but also
and the CCR, metals, sulphur Technologies used in NEKTOR utilises the EPR Technology to
and nitrogen content were but also utilises the EAMR Tech- provide increased LCO yields,
close to zero. This resulted in a nology to provide even better and can be used in both resid
big challenge for the refinery in bottoms cracking through a and low-metal applications.
terms of maintaining the heat
balance of the unit. To address
this, Grace Davison worked in
Figure 3:
collaboration with the refinery
ACE Data Comparing Coke on Catalyst
by performing preliminary
studies to compare the new 0.8
UCO feed with the previous feed
0.7
to optimise the catalyst design.
Coke on Catalyst (wt. %)

Various NADIUS formulations 0.6

were prepared and tested with 0.5
the aim of maximising catalytic
Delta Coke when processing 0.4
the UCO feed. 0.3

0.2
As the ACE data in Figure 3
show, NADIUS-156HDC pro- 0.1 ULTIMA NADIUS
vided the necessary Delta
0.0
Coke increase that the refinery
3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5 8.0
required, and the refinery
subsequently switched from Cat to Oil
ULTIMA to the NADIUS
catalyst. Figure 4:
FCC Unit Data Comparing Delta Coke
Figure 4 shows FCC unit
operating data where the in- 1.1
creased coke-making tenden- 1.0 ULTIMA NADIUS
cy of the NADIUS catalyst was
clearly observed. Therefore, 0.9
Delta Coke (wt. %)

by using a suitably optimised 0.8

NADIUS catalyst it was possible
0.7
to maintain the heat balance
in the FCC unit despite the in- 0.6
troduction of the hydrotreated
0.5
UCO feed.
0.4

0.3
0.85 0.86 0.87 0.88 0.89 0.90 0.91
Feed SG (g/cm3)

6 www.e-catalysts.com
Experience Using NEKTOR- the period on KRISTAL-EMR was NEKTOR-ULCC resulted in the
ULCC at Refinery D compared with e-cat at 75% following yield shifts:
change out to NEKTOR-ULCC.
Refinery D, located in Northern The testing was performed •• Decreased coke yield
Europe, has a catalyst cooler, using feed from Refinery D.
and is operating in partial burn. The significant improvement in •• Decreased hydrogen yield
The operating objectives of the metals tolerance for NEKTOR-
FCC unit in the order of priority ULCC is demonstrated by •• Decreased dry gas
are as follows: Figures 5 and 6, which show
large reductions in Gas Factor •• Increased gasoline yield
•• Decrease clarified slurry and hydrogen yields.
oil and increase gasoline FCC unit operating data is
Data interpolated at constant shown in Table 4, which
•• Reduce Delta Coke to conversion showed that compares average daily data
enable increase in feed the switch from KRISTAL to for KRISTAL-EMR and NEKTOR-
rate

•• Maximise C3 and C4
olefins at the expense of
Figure 5:
C3 and C4 paraffins
MAT Testing - Gas Factor

•• Maximise gasoline octane, 6.00

in particular MON NEKTOR - ULCC > 75% Change Out
5.50

The FCC unit was constrained 5.00

by an air limit, particularly 4.50
Gas Factor

during the summer months. 4.00

In addition, LPG and LCO
3.50
processing was limited.
Previously the refinery was 3.00
using KRISTAL-EMR, an 2.50
enhanced version of KRISTAL.
2.00
At around this time, the refinery KRISTAL - EMR NEKTOR - ULCC
began to process heavier 1.50
3,000 3,200 3,400 3,600 3,800 4,000 4,200
crudes. Feed metals were not
Ni Equivalent (ppm) [Ni + V/4 - (Sb*0.40/0.33)]
considered to be a problem
in terms of catalyst addition
rate, but Concarbon and coke Figure 6:
(from Ni) were problematic due
MAT Testing - Hydrogen Yield
to the coke make / air-blower
0.45
limitation. NEKTOR - ULCC > 75% Change Out
0.40
Hydrogen Yield (wt. %)

Routine e-cat data showed

0.35
that at 75% change out the
NEKTOR-ULCC made less 0.30
coke, gas and hydrogen at the
same Ni-equivalent level. E-cat 0.25
ACE selectivity testing was
0.20
performed in the Grace Davison
laboratories to evaluate in 0.15
more detail the performance of
KRISTAL - EMR NEKTOR - ULCC
NEKTOR-ULCC versus KRISTAL- 0.10
EMR at the refinery. E-cat from 3,000 3,200 3,400 3,600 3,800 4,000 4,200
Ni Equivalent (ppm) [Ni + V/4 - (Sb*0.40/0.33)]

Catalagram European Edition September 2009 7

ULCC at 90% change out. It can than 90%, NEKTOR-ULCC To summarise, the cata-
be seen that feed properties increased conversion by over lyst switch from KRISTAL to
such as density, sulphur level, 1 wt.%. In addition, there was NEKTOR-ULCC was extremely
basic nitrogen, Conradson a decrease in the dry-gas successful, and the catalyst
Carbon and contaminant yield, a significant increase achieved its objectives provid-
metals were fairly similar for in the gasoline yield (by ca. 2 ing significant performance
both catalysts and, in addition, wt.%) and an improvement in benefits to the FCC unit opera-
the reactor and regenerator bottoms upgrading. Lower LPG tion. The increased conversion
operating conditions were yield was obtained because the and increased gasoline yields
also very similar. This allowed addition of the GRACE Davison provided a major increase in
a comparable performance OlefinsMax ZSM-5 additive was unit operating profitability, es-
evaluation of KRISTAL-EMR terminated during the NEKTOR- timated to be in the region of
versus NEKTOR-ULCC. At a ULCC period. 14 million USD per year.
change-out level of greater

Table 4:
FCC Unit Operating Data

KRISTAL-232EMR >90% Change Out

NEKTOR-ULCC 586S L
FEED PROPERTIES
Density g/cm3 base base
Sulphur wt.% base -0.05
Basic nitrogen ppm base 23
Micro carbon wt.% base 0.4
Na* ppm base 0.1
* Back-calculated

REACTOR
Combined Feed Rate t/day base 410
Atmos. residue wt.% base -5
Cat/oil base -0.14
Riser Outlet Temp. °C base base
Feed pre-heat °C base 3

REGENERATOR
Average bed temp °C base 2
Cat cooler duty MW base -1.2
Air Rate t/day base 72
% CO % vol base 0.5

YIELDS
Dry Gas wt.% base -0.2
LPG wt.% base -0.4
Gasoline wt.% base 1.8
LCO wt.% base 0.1
HCO + Slurry wt.% base -1.3
Coke wt.% base -0.3

Conversion wt.% base 1.2

8 www.e-catalysts.com
Figure 7:
SEM Images Showing Alumina Deposition on the Zeolite Surface

alumina
deposition

Experience Using NOMUS- a modified approach to the in the porosity, as shown in

DMAX in Several European standard EPR Technology. Figure 8. This boost in porosity
Refineries Macropores provide the primary is specifically targeted at pore
system of routes by which the sizes in the range of 100-600
NOMUS-DMAX has been feed molecules travel into and Angstrom in diameter, which
commercially proven to product molecules exit from provide the optimal gain in
increase LCO yield in the FCC the catalyst microspheres. As diffusivity.
unit. Experience using NOMUS- such, having the appropriate
DMAX is described in detail in pore size distribution is These two new EnhanceR treat-
the subsequent article in this key to preventing diffusion ment options have provided
Catalagram, which discusses constraints, which can limit the basis for the develop-
operating to maximise LCO. bottoms cracking and coke- ment of a third generation of
selectivity potential. The newly EnhanceR catalyst families,
developed modified Pore which will now be discussed
Third-Generation EnhanceR Restructuring Technology further.
Catalyst Families provides a dramatic boost

Further R&D work has been

carried out to investigate and
utilise the special, additional Figure 8:
process capabilities provided Modified Pore Restructuring Technology
by the EnhanceR Plant facilities.
0.7
By this means an alternative EPR Enhanced
approach to the standard 0.6
EAM Technology has been
Pore Volume (cm3/g)

developed, which includes a 0.5

material-deposition step in
0.4
which the surface of the zeolite
crystals in the catalyst is coated 0.3
with a thin layer of alumina, as
modified
shown by the Scanning Electron 0.2 EPR
Microscope (SEM) photographs
0.1
in Figure 7.
0.0
EnhanceR Plant processing has 10 100 1000
also enabled development of Pore Diameter [Å]

Catalagram European Edition September 2009 9

 NACER ResidCrackeR

Intended for use with NACER has now been To apply the new EnhanceR
hydrotreated/low-metals successfully commercialised. treatment options to the
feedstocks, NACER is designed At one refinery a higher activity, development of a third-
for high activity and bottoms better bottoms cracking, higher generation resid catalyst family,
upgrading as well as boosted C4 olefinicity and a (desired) it was essential to include
C4-olefin selectivity and increase in coke make have been metals-tolerance functionality.
tailored Delta Coke. The NACER observed upon switching from This has now been achieved
catalyst family is based on the a NADIUS catalyst to NACER. by developing versions of the
ESS and EAM Technologies At another refinery significant new EAM and EPR Technology
deployed in NADIUS grades. improvements have also been versions that are compatible
However, with NACER the novel obtaining by switching from with the EMR Metals Resistance
EAMHTD Technology (Acidity NADIUS to NACER. The benefits Technology. Use of EAMRD
Modification with alumina include higher conversion, (Acidity Modification with
Deposition technology for improved stability (15% lower alumina Deposition technology
Hydrotreated-feed applications) CAR), higher gasoline yield, for Resid applications) and EPRR
is used. NACER catalysts also and a (desired) reduction in (modified Pore Restructuring
incorporate EPRHT Technology coke make. for Resid applications)
(modified Pore Restructuring in combination with EMR
for Hydrotreated-feed Technology has resulted
applications). in ResidCrackeR, which by

Figure 9:
DCR Testing Comparing ResidCrackeR with NOMUS

Activity Total C4= Yield

80.0 8.0
79.5 7.9
79.0 7.8
Total C4= (wt. %)

7.7
Conversion

78.5
7.6
78.0
7.5
77.5
7.4
77.0 7.3
76.5 7.2
NOMUS-250 ResidCracker-250 NOMUS-250 ResidCracker-250
76.0 7.1
7 8 9 10 77 78 79 80
Cat to Oil Conversion (wt. %)

LCO Yield Bottoms Yield

18.0 7.0
17.5
6.5
17.0
Bottoms (wt.%)

6.0
LCO (wt. %)

16.5
16.0 5.5
15.5
5.0
15.0
14.5 4.5
NOMUS-250 ResidCracker-250 NOMUS-250 ResidCracker-250
14.0 4.0
77 78 79 80 76.5 77.0 77.5 78.0 78.5 79.0 79.5
Conversion (wt.%) Conversion (wt. %)

10 www.e-catalysts.com
Table 5:
Yields Interpolated at Constant Conversion

Catalyst NOMUS-250 ResidCrackeR-250

higher activity
Cat-to-Oil g/g 9.3 8.8

Conversion wt.% 79 79
Hydrogen wt.% 0.15 0.21
C1+C2 wt.% 3.0 2.9
Propene wt.% 5.9 5.9
Total C3 wt.% 6.9 6.9
C4-olefins wt.% 7.7 7.8
LPG Olefinicity 0.73 0.74
Gasoline wt.% 47.4 47.8
(C5-221 °C)
LCO higher LCO
wt.% 15.5 15.8
(221-371 °C)
Bottoms lower HCO
wt.% 5.5 5.2
(>371 °C)
lower coke
Coke wt.% 9.7 9.3

virtue of its powerful intrinsic DieseliseR which requires limiting the

bottoms-cracking ability is the cracking of LCO to gasoline.
successor to NOMUS. The newly developed EnhanceR
Treatments EAMRD and EPRR Until now, NOMUS-DMAX
DCR pilot plant testing at have also been applied in the has been the benchmark for
2000/3000 ppm Ni/V using development of DieseliseR, LCO maximisation, however,
CPS-3 deactivation was used a third-generation EnhanceR DieseliseR shows significant
to compare selectivities catalyst for LCO maximisa- improvements due to the
for ResidCrackeR against tion. An FCC catalyst for LCO use of the two new EnhanceR
NOMUS. Figure 9 shows maximisation needs to have Treatments EAMRD and EPRR.
that ResidCrackeR results in good bottoms-cracking perfor- Figure 10 shows how the
increased activity, improved mance. In addition, it must also controlled deposition of a
total C4 olefins and LCO yield, have the ability to maintain the thin layer of reactive alumina,
as well as improved bottoms cracked HCO molecules within resulting from EAMRD, facilitates
cracking. the LCO boiling-range fraction, bottoms cracking.

The overall yields interpolated

at constant conversion are Figure 10:
shown in Table 5. Effect of EAMRD on Bottoms Cracking

14
To summarise, ResidCrackeR
gives maximum intrinsic 12 EAM EAMRD
Heavy Cycle Oil (>371°C)

bottoms cracking with minimal

or no coke penalty. This will 10
result in significant operating
8
and economic benefits to the
increasing number of refiners 6
with FCC units processing
resid feeds. ResidCrackeR 4
is currently being trialled in
2
various European refineries.
0
64 66 68 70 72 74 76 78
Conversion (wt.%)

Catalagram European Edition September 2009 11

Figure 11:
Effect of EPRR on LCO Yield The increased pore volume
that results from EPRR enables
17 more effective release of
EPR EPRR LCO molecules from the acid
16 sites. This is highlighted by
Figure 11, which shows how
LCO Yield (wt. %)

EPRR minimises the undesired

15
cracking of LCO into gasoline
thus boosting LCO yield.
14
ACE and DCR pilot-plant
13 testing were used to compare
selectivities for DieseliseR
12 against NOMUS-DMAX. Figures
12 and 13 show ACE data at
64 66 68 70 72 74 76 78
1000/1500 ppm Ni/V using
Conversion (wt. %)
CPS-3 deactivation, and they
demonstrate that DieseliseR
Figure 12:
gives significantly higher LCO
ACE Data for DieseliseR - LCO Yield
yields, as well as improved
bottoms cracking.
18

Summarised DCR data at

17
Light Cycle Oil (wt. %)

1000/1500 ppm Ni/V with

16 CPS-3 deactivation are
provided in Table 6. It can be
15 seen that DieseliseR results
in a considerable increase in
14 middle distillates, a significant
reduction in bottoms and only
13 a slight increase in coke.
NOMUS-DMAX-520 DieseliseR-550
12 To summarise, DieseliseR is
62 64 66 68 70 72 74
a third-generation EnhanceR
Conversion (wt. %) catalyst for LCO maximisation.
ACE and DCR selectivity testing
Figure 13: confirm that DieseliseR gives
ACE Data for DieseliseR - Bottoms Cracking an increase in LCO yield and
improves bottoms cracking for
16 LCO applications. DieseliseR
will provide significant
14
Heavy Cycle Oil (371 °C)

operating and economic

advantages to refiners wishing
12 to maximise LCO yield without
making unit modifications.
10

6
NOMUS-DMAX-520 DieseliseR-550
4
62 64 66 68 70 72 74
Conversion (wt. %)

12 www.e-catalysts.com
Table 6:
DCR Data Interpolated at Constant Conversion

Catalyst NOMUS-520 DieseliseR-550

Cat-to-Oil g/g 7.4 7.0
Conversion wt.% 59 59
Hydrogen wt.% 0.35 0.33
C1+C2 wt.% 1.7 1.7
Propylene wt.% 4.2 3.9
Total C3 wt.% 5.5 4.9
C4-olefins wt.% 4.6 4.3
LPG wt.% 14.9 13.1
Light Naphtha (C5-160 °C) wt.% 35.0 36.0
higher middle
Heavy Naphtha (160-221 °C) wt.% 11.5 13.5
distillates

LCO (221-361 °C) wt.% 18.6 19.2

Bottoms (>361 °C) lower bottoms

wt.% 12.4 10.3

Coke wt.% 5.5 5.8

Conclusions generation EnhanceR cata- more trials to start in the near

lysts. Most recently, modified future. Both ResidCrackeR and
In contrast to traditional versions of the EnhanceR treat- DieseliseR are now undergo-
approaches to FCC catalyst ments have enabled a third ing commercialisation, and
development, the latest cat- generation of EnhanceR cata- samples are available for cus-
alyst families from Grace lysts, NACER, ResidCrackeR tomer R&D evaluation. Table
Davison are based on the and DieseliseR. NACER is de- 7 provides an overview of the
EnhanceR Technology Plat- signed for low-metal applica- entire EnhanceR catalyst fami-
form. Examples of first-gen- tions, ResidCrackeR has been lies at present. The boundaries
eration EnhanceR familes in- developed for deep-resid crack- of the EnhanceR Plant are how-
clude NEKTOR, NOMUS and ing, and DieseliseR is an LCO- ever still being explored and
NADIUS, with NEKTOR-ULCC maximisation catalyst. Various future innovation leading to
and NOMUS-DMAX being commercial trials of NACER further new developments can
further developed second- catalysts are now running, with be expected.

Table 7:
Summary of the EnhanceR Catalyst Portfolio

Catalyst Family EnhanceR Technologies Performance Characteristic Target Feed Type

First Generation:
NEKTOR EPR + EMR Low Delta Coke Resid
NOMUS EAM + ESS
R
Max bottoms upgrading Resid
NADIUS EAMHT + ESS High conversion HT

Second Generation:
NEKTOR-ULCC EPR + EMR + EAMR Lowest Delta Coke Resid
NOMUS-DMAX EAMR + ESS + EPR LCO Maximisation Resid/HT

Third Generation:
NACER EAMHTD + ESS + EPRHT High conversion, C4= HT
ResidCrackeR EAM RD
+ EMR + EPR R
Deep resid cracking Resid
DieseliseR EAMRD + ESS + EPRR LCO Maximisation Resid / HT

Catalagram European Edition September 2009 13

 Grace GmbH & Co. KG · 67545 Worms/Germany · e-mail: refining.catalysts@grace.com · www.gracedavison.com

14 www.e-catalysts.com
ResidCrackerAnz.A4.indd 1 08.10.2008 14:38:33 Uhr
 Development of PremieR:
A Third-Generation
EnhanceR Catalyst for
Coke-Selective Bottoms Cracking
by

Gordon McElhiney, Director, Marketing and Business Development

and Colin Baillie, Marketing Manager

Grace Davison
Refining Technologies Europe

The NEKTOR and NEKTOR-

ULCC catalyst families are The king of
coke-selective
the established benchmarks
in the resid feed sector.
Refineries are utilising their
superior coke selectivity and bottoms cracking
metals tolerance to relieve air
blower and regen temperature
constraints, which allows them
to improve bottoms cracking
via increased cat-to-oil severity.
This provides refiners with a
higher conversion at a constant
feedrate, or alternatively allows
an increase in feedrate or the
feed heaviness.

The Grace Davison Refining

Technologies Europe R&D
group is now at an advanced
stage in the development of
PremieR, a third-generation
EnhanceR resid catalyst family.
PremieR will be the most coke-

PremieR
selective bottoms-cracking
catalyst on the market, and is
due to be commercialised later
this year.
FCC Catalysts
~ Davison Refining Technologies Europe

Catalagram European Edition September 2009 15

Operating to Maximise
LCO Yield in the
FCC Unit

by Market Trends LCO Cutpoint Adjustment

Michel Melin Over the last five years the Adjustment of the main
Director Technical Service refining industry has been fractionator to reduce the gas-
seeing a pronounced shift oline endpoint and increase
and towards “dieselisation”. This is the LCO endpoint is one of the
highlighted in the OPEC World most effective ways to increase
Colin Baillie Oil Outlook 2008 Report, LCO yield in the FCC unit. The
Marketing Manager which predicts a troublesome ACE pilot-plant data highlight-
“trend toward tighter distillate ed in Figure 1 shows that at 63
Grace Davison and slacker gasoline markets” wt.% conversion increasing the
Refining Technologies Europe between now and 2030. LCO boiling range from 216 –
337 °C to 170 – 370 °C results
Although distillate demand in a 15 wt.% increase in LCO
varies somewhat from country yield. However, it must be tak-
to country, and can fluctuate en into account that the LCO
seasonally, it is generally initial boiling point is limited
being observed that Europe is by the flash point and possibly
seeing a fast growing market by a low main fractionator top
for diesel at the expense of temperature. In addition the
a diminishing demand for LCO final boiling point is limit-
gasoline. In particular, refiners ed by the cloud point, the HDS
with limited hydrocracking capacity and the T95 specifica-
assets are looking for ways tion of the diesel pool. It might
to capture distillate margin be obvious, but it is also worth
opportunities by upgrading pointing out that optimising
FCC light cycle oil to diesel. the separation of LCN, LCO
This article will discuss the and slurry in the main fraction-
options for maximising LCO ator can give a better control of
yield in the FCC unit. their overlap.

16 www.e-catalysts.com
Fundamentals of LCO Figure 1:
Maximisation Effect of LCO Cutpoints on the LCO Yield

LCO is an intermediate product

45
in the FCC unit, and is formed 216-337 °C
through the cracking of large 170-370 °C
40
feed molecules. Figure 2 shows

Light Cycle Oil (wt. %)

how the LCO yield increases
35
with conversion up to ca. 55
– 60 wt.% conversion levels.
30
At higher conversion the LCO 15 wt.%
yield drops quickly as the in- 25
termediate LCO molecules are
“overcracked” into the gasoline 20
range. As such, maximising
LCO yield is primarily a ques- 15
tion of optimising conversion 58 63 68 73 78
levels. Conversion (wt. %)

Figure 2:
Conversion levels are typically
LCO Yield as a Function of Conversion
lowered through a reduction in
operational severity, which can
involve using a lower Riser Out- 20
let Temperature (typically 485
– 510 °C), a lower cat-to-oil ra- 18
tio or a reduction in e-cat activ-
LCO Yield (wt. %)

ity. The effects of each of these

16
factors on LCO yield are shown
in Figures 3 – 5, respectively.
14 optimum
Although these factors can sig-
nificantly increase LCO yield
the lower conversion levels 12
inevitably result in increased
slurry yields. 10
50 55 60 65
Minimising the increased slurry Conversion (wt. %)
yields associated with the lower
conversion levels is a major fac- Table 1:
tor in LCO maximisation. This DCR Data of the Yield Structure from Cracking Pure HCO
can be achieved operationally
Product Yield (wt. %)
through recycling of slurry (the
Dry Gas 3.0
entire bottoms) or HCO (a cut
LPG 8.0
from the lighter part of the bot-
TCN 19.0
toms). Table 1 shows DCR pilot-
LCO (221-350) 33.0
plant data of the yield struc-
Slurry 30.0
ture obtained from cracking
Coke 7.0
pure HCO, the key point being
that approximately one-third •• ROT = 520 °C
of all recycled HCO is further •• C/O = 7
cracked into LCO. •• E-cat MAT = 72%
•• HCO Density = 1.0 kg/l
•• HCO Concarbon = 0.10%
•• Endpoint = 420 °C

Catalagram European Edition September 2009 17

In connection with the recycling Figure 3:
of slurry or HCO, a very impor- LCO and Slurry Yields as a Function of Riser Outlet
tant unit design consideration Temperature
is Mix Temperature Control 20
(MTC). The Mix Temperature 19
is defined as the adiabatic
18
equilibrium temperature be-
17
tween the regenerated catalyst
16

Yield (%)
and the uncracked vapourised
feed. The MTC approach is 15
well suited for units operating 14
in maximum LCO mode be- 13
cause it allows a reduction of 12 LCO
the Delta Coke and the poten- Slurry
11
tial coking risks in the reactor/
10
riser associated with the lower 495 500 505 510 515 520 525 530
ROT and the increased amount ROT (°C)
of non-vapourised feed. In an
FCC unit without MTC, the Mix
Figure 4:
Temperature (MT) is directly
LCO and Slurry Yields as a Function of Cat-to-Oil Ratio
related to the ROT by the fol-
lowing equation:
20
MT = ROT + 0.1 Hr [Hr = heat of 19
cracking (200 – 400 kJ/kg)] 18
17
However, in units with MTC, 16
Yield (%)

the Mix Temperature can be

15
adjusted independently of
14
the ROT. MTC is achieved by
13
injecting slurry/HCO a few
metres above the feed nozzles 12 LCO
into the riser. The ROT is still 11 Slurry
controlled by the regenerator 10
slide valve while the Mix 3 4 5 6 7
Temperature (measured Cat-to-Oil
slightly above the feed nozzles)
is controlled by the flow of Figure 5:
slurry/HCO. An increased flow LCO and Slurry Yields as a Function of Microactivity
of slurry/HCO will impose a
higher heat demand in the 20
reactor/riser and therefore a
19
higher catalyst circulation will
18
result at constant ROT and
17
feed preheat temperature. The
16
Yield (%)

increased catalyst circulation

gives a higher Mix Temperature 15
resulting in less non-vapourised 14
feed and a lower Delta Coke. 13
The riser temperature profile 12 LCO
with and without MTC is shown Slurry
11
in Figure 6.
10
59 60 61 62 63 64 65 66 67 68 69 70
MAT

18 www.e-catalysts.com
Figure 6: cyclic compounds need to be
Riser Temperature Profile With and Without MTC minimised whilst paraffins, or
cyclic rings with alkyl chains,
should be preserved.

MT A detailed analysis of the

cracking pathways involved
Riser Temperature

With MTC in LCO formation has been

MT
performed by Corma and
Sauvanaud,1 and their
conclusions for the cracking
No MTC of paraffins, one- and two-
ring compounds, as well as
ROT compounds containing three
or more fused rings will now
be briefly highlighted.
Riser Elevation
Feed Nozzles MTC
One would expect highly
paraffinic LCO precursors to
Feedstock Effects systems. The same is true for lead to highly paraffinic LCO
heavier feedstocks, however with a high cetane value.
When considering LCO yield with an increase in aromatic However, in the cracking of a
and quality, one of the most compounds, as well as an long-chain paraffin containing
important factors is the increase in three or more fused 36 carbons it was observed
feedstock. Standard VGO ring systems. that the majority of the
feedstocks consist of a complex products consisted of C3 to C5
mixture of compounds that Figure 7 shows the cetane index hydrocarbons, with much lower
can be classified as paraffins, for a series of hydrocarbons selectivity towards products
naphthenes or aromatics, of consisting of 10 carbons. with more than 6 carbons.
which the latter are typically Clearly in order to achieve a This means that paraffinic
one-ring or two-fused-ring higher LCO cetane the multi- feedstocks will provide high

Figure 7:
Cetane Index for 10-Carbon Components

naphthalene tetralin decalin

cetane = 5 cetane = 15 cetane = 35

butylbenzene butylcyclohexane decane

cetane = 50 cetane = 60 cetane = 75

Catalagram European Edition September 2009 19

conversions, and thus the LCO representative FCC conditions. naphthenoaromatic or wholly
yield will be low. In addition, The biggest difference between aromatic structures. Aromatic
the quality of LCO will depend the reaction mechanisms of structures do not crack under
on the quantity of cracked these compounds compared to FCC conditions, and after any
paraffins remaining in the LCO the one-ring compounds is the alkyl side chains have been
cutpoint. To minimise the loss increased amount of hydrogen- cracked the core ring ends
of LCO yield with paraffinic transfer reactions. Tetralin up in the LCO fraction. In
feedstock, it is necessary preferentially reacts (>80%) addition, naphthenoaromatic
to promote the H-transfer through hydrogen transfer compounds are known to
reactions of LCO-range to give naphthalene with a have a high hydrogen-transfer
carbocations to give LCO minority of alkylbenzenes rate compared with other
molecules and thus minimise produced. The major cracking cyclic compounds, therefore
cracking of the carbocations pathway of decalin is ring a large portion of compounds
into gasoline-range opening and subsequent with three-fused rings end up
compounds. beta scission, yielding a aromatising to anthracene,
mixture of paraffins, olefins, phenanthrene or fluorene. For
Examples of one-ring naphthenes and olefinic structures with three or more
compounds that are LCO naphthenes. In addition, a fused rings high selectivity
precursors are those with alkyl minor, but not insignificant, towards LCO may be achieved
chains with at least 12 carbon amount of hydrogen transfer by accumulation of aromatic
atoms. There are two competing occurs to yield tetralin and cores, but this will also result
reactions of such compounds, alkylaromatics. in the worst quality of LCO.
which are dealkylation (to
remove the entire alkyl chain) The maximum LCO yield that It can be concluded that the
and chain cracking (to remove a two fused ring compounds feedstock plays a vital role in
fragment from the alkyl chain). provide is similar to one-ring LCO yield and quality. Paraffinic
The ratio of chain cracking to compounds. However, while feedstocks have the potential to
dealkylation increases with alkyl the cracking of two fused provide the highest LCO quality,
length, and for alkyl chains of ring compounds at lower but it is not a particularly well-
over 15 carbons the dominant conversions (lower than 60% suited feedstock due to the low
reaction is chain cracking. feed conversion) results in LCO yield obtained. However,
Therefore, a somewhat naphthenic LCO, moving to LCO yield from paraffinic
simplified mechanism for the higher conversions results in feeds can be increased by
formation of LCO from one-ring a lower LCO yield, as well as promoting H-transfer reactions
compounds is that long alkyl increased aromaticity. Thus, of the resulting LCO-range
groups undergo progressive feedstocks high in two fused carbocations, thus terminating
chain cracking until one-ring ring compounds can provide the cracking reactions and
compounds with shorter alkyl the necessary combination preserving the molecules in the
groups (4 – 12 carbons) are of LCO yield and quality, LCO boiling range. Feedstocks
obtained. Importantly, the however it is necessary to containing one-ring and two-
maximum yield of these one- use a moderate conversion fused-ring structures are
ring LCO molecules is much and minimise the hydrogen- the most suitable for LCO
greater than the maximum yield transfer reactions that convert maximisation in terms of
of paraffinic LCO molecules, decalin-type compounds into balancing yield and quality. In
and that an acceptable LCO naphthalenes, which results in this scenario H-transfer needs
quality (mainly due to the a loss of cetane. to be minimised to avoid
paraffinic side chains) is still the formation of aromatic
obtained. Regarding compounds with naphthalenes with lower cetane
three or more fused rings it is values. Finally, feedstocks
To examine the role of probable that the chemistry is containing molecules with
compounds with two fused somewhat similar to structures three or more fused rings will
rings, the reactions of decalin with two-fused rings. provide the highest LCO yield,
and tetralin (see Figure 7) Compounds with three-fused but unfortunately also the
have been evaluated under rings are mainly comprised of worst quality.

20 www.e-catalysts.com
Operating Experience in LCO 3. Reduction of e-cat naphtha. It can also be seen
Maximisation activity through lower that although the slurry yield
catalyst additions was increased, the increase
The following section discuss- was manageable.
es two cases in which Grace 4. Increasing the ZSM-5
Davison has assisted refineries additive additions to A more detailed look into the
in Western Europe to maximise maintain LPG yield effect of ROT on the key yields
LCO yields in the FCC unit. for Refinery A is shown in Fig-
ure 8, which clearly shows an
These operating changes were increase in distillate yield at
LCO Maximisation at implemented and Table 2 the expense of naphtha when
Refinery A shows yearly average FCC unit moving to a lower ROT.
data before and after the move
Refinery A has a Kellogg de- to maximum distillate mode. It Upon confirmation that the
sign FCC unit, and they desired can be seen that although the new operating conditions had
an increase in distillates at the amount of residue feed pro- provided the expected increase
expense of naphtha. In order cessed increased somewhat the in LCO yield, the refinery took
to achieve this Grace Davison feed properties remained fairly a further step towards LCO
recommended the following constant. Most importantly, maximisation by switching
series of operating changes: the slurry recycle rate was in- from NOMUS to NOMUS-DMAX,
creased from 24 to 38 m3/h an FCC catalyst specifically for-
1. Reduction of ROT from and the reactor temperature mulated for LCO maximisation.
530 to 505 °C was decreased by 19 degrees To compare the performance
C. These operating changes of NOMUS with NOMUS-DMAX
2. Increase of the slurry/ had the desired effect on the (40% change out) an ACE e-
HCO recycle up to key product yields in that the cat study was performed, and
40 m3/h distillate yield was increased a significant increase in LCO
by 5.7 wt.% at the expense of yield was observed, as shown

Table 2:
FCC Unit Operating Data - Yearly Average

Former Operation Max Distillates Mode

Feed Properties:
SG 0.913 0.915
UOPK 12.1 12.0
Residue wt. % 2 8
Slurry Recycle m3/h 24 38

Operating Conditions:
Total Feed m3/h base 17
Reactor Temperature °C base -19
Regen Dense Temperature °C base -2

Produced Reactor Yields wt. %

Dry Gas wt. % base -1.1
C3 wt. % base -0.1
Propylene wt. % base -0.1
Total C4 wt. % base -0.3
Naphtha C5-220 wt. % base -5.5
Distillates wt. % base 5.7
Slurry wt. % base 1.8
Coke wt. % base -0.4

Catalagram European Edition September 2009 21

by Figure 9. This is in line with Figure 8:
what was seen in the FCC unit, The Effect of ROT on Distillate and Naphtha Yields
with Refinery A confirming at Refinery A
that even at 40% change out
NOMUS-DMAX had increased
LCO yield by 0.5–1.0 wt.%, as
well as decreasing slurry yield.

Yield (wt. %)
LCO Maximisation at
Refinery B

Refinery B is a major oil com-

Distillates
pany that has performed sev-
eral multi-million Euro projects Naphtha
to increase diesel production.
500 505 510 515 520 525 530 535
One such project involved in-
ROT (°C)
stallation of a mild hydroc-
racker to meet the demand for Figure 9:
middle distillates. As a result ACE E-Cat Study Comparing LCO Yield for NOMUS and
a new, lighter FCC feedstock NOMUS-DMAX at Refinery A
was generated, which required
a new FCCU operating philoso- 18
phy, involving the simultane-
Light Cycle Oil (wt. % ff)

17
ous optimisation of conditions
as well as the use of a new cat- 16
alyst formulated for maximum
distillates. 15

14
These changes were performed
in three steps. The optimum
13
operation was achieved by re- NOMUS NOMUS-DMAX (40% Change-Out)
ducing reactor temperature 12
from 540 to 502 °C, and using 59 61 63 65 67 69 71 73 75 77 79
a 12 vol.% slurry recycle. The
Conversion (wt. % ff)
lighter feedstock from the mild
hydrocracker resulted in very Figure 10:
high conversions, even at the FCC Unit Data for Refinery B
reduced reactor temperature of
LCO and Slurry (m3/h) vs Recycled Slurry
502 °C. Therefore, e-cat activ-
LCO Yield
ity had to be reduced through (NOMUS-DMAX)
lower catalyst additions. At the 65
same time Refinery B switched
55
to the LCO maximisation cata-
lyst NOMUS-DMAX. As well as LCO Yield
45
the primary objectives of maxi-
mising LCO and increasing 35
bottoms cracking, an increase
in catalyst Delta Coke was re- 25
quired to maintain the heat Slurry Yield
balance using the lighter feed. 15
FCC unit data is shown in Fig-
ure 10 showing how the use of 5
0 10 20 30 40 50 60
increasing slurry recycle result-
Recycle m /h
3

22 www.e-catalysts.com
ed in higher LCO yields as well essary increase in Delta Coke, resid cracking catalyst result-
as a decrease in slurry yields. as well as a boost in LCO yield ing in significant boosts in LCO
The additional beneficial effect and a decrease in slurry yield. yields. These two catalyst fami-
of using the NOMUS-DMAX cat- lies are currently being trialled
alyst in terms of improved LCO in various European refineries,
yield can also be observed. New Catalyst Developments and operating experience will
soon be provided to highlight
To summarise, the unit oper- As discussed in the previous how they are allowing refiners
ating constraints at Refinery B article, Grace Davison Refin- to maximise LCO production in
were severely impacted by the ing Technologies Europe has the FCC unit.
lighter FCC feedstock result- now developed a third gen-
ing from the new mild hydro- eration of EnhanceR catalyst
cracker. Therefore, Grace Davi- families, and two of these will References
son recommended a series of play a significant role in in-
changes to the operating con- creasing LCO yields. DieseliseR 1) A. Corma and L. Sauvanaud,
ditions, including a reformu- provides maximum LCO yields Fluid Catalytic Cracking VII:
lation to NOMUS-DMAX. The for use in FCC units operat- Materials Methods and Process
catalyst change was extremely ing in maximum LCO mode, Innovations, 2007, p 41.
successful, providing the nec- whilst ResidCrackeR is a deep

Searching for more freedom

for LCO maximisation?
DieseliseR - no strings attached

DieseliseR
FCC Catalysts
Catalagram European Edition September 2009 23
 Recycle
Strategies for
Maximising
FCC Light
Cycle Oil

by Introduction the temperature set points of

riser top, regenerator and feed
David Hunt, This article presents laboratory pre-heat. We obtained four bal-
FCC Technical Service Manager, results to quantify the effects anced runs with conversion lev-
N. America of various recycle streams on els of 54, 58, 68 and 75 wt.%.
product selectivities. A resid The DCR conditions, product
Ruizhong Hu, feedstock was cracked over a yields and boiling point distri-
Manager of Research & Technical low Z/M Grace Davison cata- bution of the bottoms fraction
Support, N. America lyst in Grace Davison’s circu- are listed in Table I.
lating riser pilot plant (DCR).
Hongbo Ma, The product bottoms were dis- The C5+ liquid products from
Research Engineer, N. America tilled to five recycle fractions each DCR run was first separat-
(650–750 ˚F, 650–800 ˚F, ed by atmospheric distillation
Larry Langan, 650–850 ˚F, >650 ˚F and to obtain the 650 °F+ fraction,
Research Engineer, N. America >750 ˚F), blended back at and each 650 °F+ fraction was
various levels with the original further separated by vacuum
and feedstock and cracked over the distillation to obtain the de-
low Z/M Grace Davison catalyst sired boiling fractions.
Wu-Cheng Cheng in the ACE unit.
Director of R&D, N. America Figures 1 and 2 show the API
gravity (proportional to the
Grace Davison DCR Pilot Plant Runs and crackability of a feedstock),
Refining Technologies Preparation of Recycle Conradson Carbon (propor-
Streams tional to the feedstock’s coke-
forming tendency), hydrogen
The deactivated catalyst was content and the mid boiling
charged in our DCR pilot plant, point (which can be used with
where cracking of a resid feed- the density to calculate the aro-
stock was conducted. Reaction maticity) of the various boiling
severity was varied by adjusting fractions.

24 www.e-catalysts.com
Table 1:
DCR Runs to Generate Recycle Feedstock

Conversion, wt. % 54 58 68 75
Rx Exit Temp, °F 950 950 971 970
Regenerator Temp, °F 1350 1350 1270 1270
Feed Temp, °F 701 574 700 299
C/O Ratio 4.3 5.0 5.9 9.4
Dry Gas, wt. % 2.0 1.9 2.6 2.2
LPG, wt. % 8.2 8.9 11.4 13.3
Gasoline, wt. % 38.4 42.0 48.0 51.9
LCO, wt. % 22.2 21.7 19.2 16.7
Bottoms, wt. % 24.0 20.0 12.8 8.6
Coke, wt. % 5.2 5.3 5.9 7.1
Boiling Point Distribution of 650 °F+ Bottoms
650-700 °F 5.3 4.8 3.5 2.5
700-750 °F 4.8 4.2 2.9 2.0
750-800 °F 4.3 3.6 2.2 1.4
800-850 °F 3.6 2.9 1.6 1.1
850-900 °F 2.5 2.0 1.2 0.7
900-950 °F 1.6 1.2 0.8 0.5
950 °F+ 1.9 1.4 0.8 0.4
650-750 °F 10.1 9.0 6.3 4.4
650-800 °F 14.4 12.6 8.5 5.9
650-850 °F 18.0 15.5 10.1 6.9
650 °F+ 24.0 20.0 12.9 8.6
750 °F+ 13.9 11.0 6.5 4.1

Figure 1:
Properties of Recycle Feedstocks Obtained from DCR Run at 54% Conversion

˚API Gravity Conradson Carbon, wt.%

16
20
12
15
8

10 4

5 0
50% vol.% ˚F Hydrogen, wt.%
Data

1000
12
900

11
800

700 10

600 9
65 eed

65 0˚F

65 0˚F

F
F+

F+

F+

F+

F
F+

F+

F+

F+
0˚

˚
50

00

50
0˚

0˚

0˚

0˚

Fe

0˚

0˚

0˚

0˚
75

80

85
F

65

75

80

85

8
65

75

80

85
sh

0-

0-

0-

0-

0-

0-
es

65

65

65
e
Fr

Fr

Feed ID

Catalagram European Edition September 2009 25

Figure 2:
Properties of 650-750 °F Recycle Fraction Obtained from DCR Runs
API Gravity @ 60% ˚F Conradson Carbon, wt.%

20
4.8

15 3.6

2.4
10
1.2

5 0.0
Data

Hydrogen, wt.% 50% vol.% ˚F

900
12
800
11
700
10

9 600

8 500
on

on

on

on
on

on
on
ed

on
ed
C

C
C

C
C
Fe

C
Fe
%

%
%

%
%
%
h

54

h
68

75

68
58

75
58
54
es

es
@

@
Fr

@
@

Fr

@
@
@
F

F
F

F
F
F
0˚

0˚

0˚

0˚
0˚

0˚
0˚
0˚
75

75

75

75
75

75
75
75
0-

0-

0-

0-
0-

0-
0-
0-
65

65

65

65
65

65
65
65

Feed ID
ACE Pilot Plant Testing of blending various boiling-range various boiling-range fractions
Recycle Blends fractions back into the starting obtained at 54 wt.% conversion.
resid feedstock. These feed The other group consists of sets
To simulate bottoms and HCO blends, listed in Table 2, can of blends made using a single
(a cut from the lighter part be separated into two groups. boiling range, 650–750 ˚F, but
of the bottoms) recycle feed One group consists of sets of obtained from the DCR runs at
samples were prepared by recycle blends made with the various conversion levels.

Table 2:
Feeds Used in ACE Study
Conversion, wt. % Recycle Stream, °F Blend Ratio wt. % Original Feed wt. % ° API
100.0 20.60
54 650-750 8.3 91.7 20.42
54 650-750 6.3 93.7 20.39
54 650-800 11.7 88.3 20.37
54 650-800 9.7 90.3 20.38
54 650-850 13.4 86.6 20.29
54 650-850 11.4 88.6 20.30
54 650+ 14.7 85.3 19.83
54 750+ 7.1 92.9 19.87
58 650-750 8.3 91.7 20.29
58 650-750 6.3 93.7 20.29
68 650-750 7.3 92.7 19.95
68 650-750 5.3 94.7 20.03
75 650-750 5.4 94.6 19.72
75 650-750 3.4 96.6 19.93

26 www.e-catalysts.com
Table 3:
Interpolated Yields of Base and Combined Feeds at 70% and 55% Conversion
Recycle Boiling Range 650-750 650-750 650-800 650-800 650-850 650-850 650 °F+ 750 °F+
None None
°F °F °F °F °F °F
Recycle Ratio 0.0% 0.0% 8.3% 6.3% 11.7% 9.7% 13.4% 11.4% 14.7% 7.1%
Wt. % Conversion 70 55 55 55 55 55 55 55 55 55

Cat-to-Oil Ratio 6.0 3.4 3.5 3.5 3.6 3.6 3.7 3.6 3.7 3.6

Hydrogen, wt. % 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1

Total C1’s & C2’s, wt. % 1.4 1.0 1.0 1.0 1.1 1.1 1.1 1.1 1.0 1.1

Propylene, wt. % 3.3 2.1 2.2 2.1 2.2 2.2 2.2 2.2 2.1 2.0

Total C3’s, wt. % 3.9 2.4 2.5 2.4 2.5 2.5 2.6 2.5 2.4 2.4

Total C4=’s, wt. % 5.1 3.9 3.9 4.2 3.8 3.9 4.0 4.0 3.9 3.8

Total C4’s, wt. % 8.5 5.6 5.7 6.0 5.6 5.7 5.9 5.8 5.8 5.5

C5+ Gasoline, wt. % 49.4 40.6 40.8 40.4 40.2 40.1 39.8 39.8 39.9 40.0

RON 89.6 89.5 89.3 89.6 89.5 89.5 89.4 89.5 89.5 89.3

MON 78.7 77.6 77.6 77.7 77.7 77.7 77.8 77.7 77.8 77.6

LCO, wt. % 20.5 24.7 25.8 25.5 25.6 25.5 25.1 25.0 25.0 24.7

Bottoms, wt. % 9.5 20.3 19.2 19.5 19.4 19.5 19.9 20.0 20.0 20.3

Coke, wt. % 6.7 5.6 5.6 5.6 5.7 5.6 5.7 5.7 6.1 6.1

Relative Feed Rate

Coke Burn Limited 1.00 1.20 1.20 1.21 1.18 1.20 1.18 1.19 1.11 1.10

Wet Gas Limited 1.00 1.53 1.49 1.46 1.49 1.48 1.44 1.45 1.48 1.54

Catalyst Circulation Limited 1.00 1.76 1.72 1.71 1.70 1.68 1.62 1.69 1.63 1.68

Fresh Feed Rate

Coke Burn Limited 1.00 1.20 1.10 1.13 1.04 1.08 1.02 1.05 0.95 1.03

Wet Gas Limited 1.00 1.53 1.36 1.37 1.32 1.33 1.25 1.29 1.26 1.43

Catalyst Circulation Limited 1.00 1.76 1.58 1.60 1.50 1.52 1.40 1.50 1.39 1.56

A commercially available Grace 55% conversion, as well as the The calculated theoretical
Davison FCC catalyst was de- yields of the combined feeds at yields derived from the sec-
activated, without Ni or V, at 55% conversion. The yields are ond-pass cracking of each of
1465 °F for 20 hours, using expressed as wt.% of the total the pure recycle streams at
the Advanced Cyclic Propyl- feed (fresh + recycle). 55% conversion are shown in
ene Steam protocol. After de- Figure 4. The recycled streams
activation, the catalyst had 94 To better illustrate the are less crackable than the
m2/g zeolite surface area, 83 contribution of each recycle base feed, as indicated by the
m2/g matrix surface area, and stream, the yields of LCO, higher cat to oil ratios. This is
a unit cell size of 24.30 Å. The bottoms, coke, and gasoline expected, as the easy to crack
ACE runs were conducted us- are plotted in Figure 3 as a material of the recycle streams
ing the same laboratory deac- function of the recycle ratio, has been cracked in the first
tivated catalyst as in the DCR defined by the composition of pass. As expected, the 650–
run, as well as the same base the blends in Table 3. With 750 ˚F stream made the most
feedstock. All ACE runs were the exception of the >750 ˚F LCO and gasoline and the low-
conducted at a reactor temper- recycle feed, all recycle-con- est coke for a given conver-
ature of 950 ˚F. taining feeds made higher LCO sion, when comparing yields
and lower bottoms than the among the recycle streams.
original feed. With the ex- The trends in LCO and gasoline
Effect of Recycle Streams ception of the 650–750 ˚F re- yields from the lightest stream
cycle feed, all recycle-contain- to the heaviest stream appear
Table 3 shows the interpolat- ing feeds made higher coke to gradually decrease, whereas
ed ACE yields of the original and lower gasoline than the the increase of coke appears
feed, with no recycle, at 70 and original feed. to be very gradual up to the

Catalagram European Edition September 2009 27

Figure 3:
Interpolated Yields at 55% Conversion vs. Recycle Ratio

LCO, wt.% Bottoms, wt.%

25.8 20.4

25.5 20.1

25.2 19.8

24.9 19.5

24.6 19.2
Coke, wt.% C5+ Gasoline, wt.%
40.8
6.00

40.4

5.75

40.0

5.50
0.00 0.04 0.08 0.12 0.16 0.00 0.04 0.08 0.12 0.16

Recycle Ratio

650-750˚F 650-800˚F 650-850˚F 650+ 750+

Figure 4:
Interpolated Yields at 55% Conversion vs. Recycle Ratio

Cat-to-Oil Ratio C5+ Gasoline, wt.%

6
40
5
35
4 30

3 25

2 20
Data

LCO, wt.% Coke, wt.%

40
12

30 10

8
20 6

4
10
se

F+

F+

se

F+

F+
0˚

0˚

0˚

0˚

0˚

0˚
Ba

Ba
0˚

0˚

0˚

0˚
75

80

85

75

80

85
65

75

65

75
0-

0-

0-

0-

0-

0-
65

65

65

65

65

65

Feed ID

28 www.e-catalysts.com
Table 4:
Yields on Fresh Feed Basis at a Relative Constant Coke Production Rate

Max.
Base No
Gasoline 650-750 °F 650-800 °F 650-850 °F 650 °F+
Recycle
Base
Conversion, wt. % 70.0 55.0 61.2 64.2 65.2 64.7
Recycle Ratio 0 0 0.10 0.14 0.16 0.15
Maximum recycle available 0.10 0.14 0.18 0.24
Cat-to-Oil Ratio 6.05 3.43 3.48 3.56 3.59 3.60
Hydrogen, wt. % 0.11 0.09 0.10 0.11 0.12 0.12
Total C1’s & C2’s, wt. % 1.4 1.0 1.1 1.3 1.4 1.4
C3=, wt. % 3.3 2.1 2.4 2.6 2.7 2.7
Total C3’s, wt. % 3.9 2.4 2.7 2.9 3.1 3.1
Total C4=’s, wt. % 5.1 3.9 4.5 4.5 4.7 4.8
Total C4’s, wt. % 8.5 5.6 6.6 6.6 6.9 7.0
C5+ Gasoline, wt. % 49.4 40.5 44.6 46.8 47.0 46.4
RON 89.6 89.2 89.4 89.5 89.5 89.7
MON 78.6 77.3 77.7 77.8 77.7 77.9
LCO, wt. % 20.5 24.7 28.9 30.2 29.9 29.3
Bottoms, wt. % 9.5 20.2 9.9 5.6 5.0 6.0
Coke, wt. % 6.7 5.6 6.1 6.5 6.7 6.7
Relative Combined Feed Rate Const Coke 1.00 1.20 1.23 1.21 1.18 1.18
Relative Fresh Feed Rate 1.00 1.20 1.10 1.04 1.00 1.00
Relative Coke Production Rate 6.7 6.7 6.7 6.7 6.7 6.7

650–850 ˚F stream and be- stream. The next highest LCO streams. Consequently, it can
comes stepwise higher for the yield of 29.9% was achieved be concluded that it is advan-
>650 ˚F and >750 ˚F streams. with 16% recycle of the 650– tageous to recycle HCO rather
This suggests that during first- 850 ˚F HCO stream. Even than bottoms.
pass cracking, coke precursors though the theoretical yields of
in the boiling range of >850 ˚F LCO for second-pass cracking
are formed, which are respon- (Figure 4) were the highest for Conclusions
sible for coke production dur- the 650–750 ˚F stream, when
ing second-pass cracking. it was limited to a maximum Recycle can be employed to
recycle ratio of 10%, the com- fully maximize LCO at reduced
bined feed with the 650–750 conversion, while maintaining
Operating at Maximum ˚F stream made only 28.9% bottoms equal to a traditional
Recycle LCO and much higher bottoms. maximum gasoline operation.
In the case of the >650 ˚F The 650–750 ˚F stream, when
The goal of this calculation bottoms stream, due to coke recycled, produces the most
was to maximize recycle ratio limitation, only 15% out of the LCO and gasoline and the low-
of each recycle stream until the available 24% recycle stream est coke for a given conver-
coke yield of the base feed at could be recycled. The opera- sion. However, the 650–800
70% conversion was reached. tion recycling 650 ˚F bottoms ˚F or 650–850 ˚F recycle
As shown in Table 4 the therefore provided lower LCO stream produces the highest
highest LCO yield of 30.2% was yield and higher bottoms than LCO when recycled against a
achieved with maximum recy- the operation with recycling the coke-burn constraint.
cle of 14% for the 650–800 ˚F 650–800 ˚F and 650–850 ˚F

Catalagram European Edition September 2009 29

 Accurate
and Reliable Control
of FCC Catalyst
and Additive Addition

by Maria Luisa Sargenti, Technology Coordination Manager,

Grace Davison Refining Technologies Europe

D.A.I.S is needed next to the hoppers, in D.A.I.S units is specifically

simplifying transportation and designed for FCC operations,
The Davison Automatic installation. and ease of programming.
Injection System (D.A.I.S) is Only two parameters need
designed to allow continuous, to be entered to start the
controlled, reliable and fully Accuracy automatic operation, namely
automatic dosing of catalyst the total amount to be injected
and additives into the FCCU. For an average FCCU operation, per day and the desired
Since its introduction to the the shots of catalyst are typically amount per injection. Many
market in 1995 more than 100 between 20 and 55 kg each. To typical operational events can
units around the world have enable the maximum accuracy be managed by the software.
used the D.A.I.S to achieve a the shots are individually dosed For example, if a pressure
stable and steady operation, in the 120- or 230-liter shot drop in transport air occurs,
resulting in more efficient and pot. Such dosing leads to DAIS resulting in reduced discharge,
cost-effective usage of FCC accuracies of 99.9%. the computer will control
catalysts and additives. the valves until the required
amount of catalyst or additive
Ease of Installation and fills the shot pot.
Practical Design Operation
The operator terminal installed
One advantage of the D.A.I.S is D.A.I.S units are delivered with the D.A.I.S unit displays
its practical design consisting completely pre-assembled and data for various parameters,
of a base skid (see top right are easy to install. The shot including daily addition rate,
picture) on which the weighing pot is designed for long life, alarms and log files. These can
shot pot is installed. The and allows safe injection of easily be sent to other data-
D.A.I.S was developed to fit the catalyst or additive into the handling systems (DCS) within
common dimensions of most FCC unit. Because the unit the refinery.
refinery structures, and due can be installed under an
to the compact design D.A.I.S existing storage hopper and
units can be very easily installed the operation is at atmospheric Ease of Maintenance
below existing hoppers. pressure, there is no need for
Therefore, unlike other addition lengthy pressurising steps. Using our extensive experience
systems, no extra floor space The exclusive software used with D.A.I.S units, the design

30 www.e-catalysts.com
has been optimised so that it during regular operation be •• Model C and CXL designed
only uses the minimum quantity required, technical support is to load catalysts directly
of moving parts. The compact readily available. from the refiners storage
dimensions make it easy to hoppers.
perform scheduled service work
on the base unit without the Model Options Most recently an innovative
need for scaffolding or ladders. version was developed to allow
In addition, all connections The core of each D.A.I.S the simultaneous addition of
are flanged so that they are model is the base skid to catalyst and up to three further
leak free and all components which other elements can be products. This new model is
are sandblasted and finished incorporated above to achieve called the D.A.I.S QUATTRO,
with special dual-layer coating a refinery-specific solution. which can be customised and
(inside and outside) for For applications that require tailored to the users needs.
optimum corrosion resistance. separate additive additions two The D.A.I.S QUATTRO layout is
All D.A.I.S units are Lloyd’s D.A.I.S options are available: shown in Figure 1.
Certified to be in compliance
with the Pressure Equipment •• Model A, includes a
Directive PED 97/23/EC. storage hopper with an Exclusivity
incorporated vacuum
pump to facilitate the Every D.A.I.S model is
Technical Support loading from big bags manufactured exclusively
or drums. for Grace Davison Refining
Each D.A.I.S unit is delivered Technologies by Pneumix, a
only after completing a 48- •• Model B, designed to load worldwide company with 20
hour operation test. Specialised additives from a 1 m3 flow years experience of providing
professionals follow the bin, which can be placed specialised bulk handling
commissioning, start up and on top of the base skid. solutions for the refining and
training for each individual chemical industry.
unit at the refinery site. Should,
unexpectedly, troubleshooting

Davison
Figure 1:
The D.A.I.S Quattro

~ Davison Catalyst

er fins
SupOX Ole ra
U l t
DE S

3
CP-

Catalagram European Edition September 2009 31

 Grace Davison Co-Sponsors the 2009
Murco Rugby Tournament in Paris
by Colin Baillie, Marketing Manager,
Grace Davison Refining Technologies Europe

Grace Davison Refining Technologies Europe

was a co-sponsor in the recent Murco Rugby
tournament that took place in Paris in February
2009. The Murco squad consisted of 40 people
from the Milford Haven refinery, and they played
an invitational game against a local French team.
The Murco team also took the opportunity to
attend the France versus Wales game in the Six
Nations Tournament, and French-Welsh relations
were firmly established during the cultural tour
of Paris afterwards.

2008
South African Seminar
by Colin Baillie, Marketing Manager,
Grace Davison Refining Technologies Europe

Grace Davison Refining Technologies training programme and presentations on the

Europe held its 5th South African FCC most recent advances in FCC catalysts and
Seminar in Cape Town during December additives technology. Some of the topics included
1 - 5, 2008. Over 20 delegates attended the were FCC catalyst fundamentals, operating to
seminar representing four refineries from South maximise LCO, resid-processing issues and
Africa. The seminar included a comprehensive extensive FCC troubleshooting. In addition, there
was short session in which the refineries gave
their own technical presentations.

After the technical programme various social

events were arranged, including an organised
tour of the waterfront and a panorama tour in the
Kruger area. The combination of the technical and
social programmes enabled the participants to
share their particular experience and knowledge.
Grace Davison Refining Technologies Europe is
very much looking forward to hosting the next
South African Seminar in 2010.

32 www.e-catalysts.com
Davison