Grace Davison European Edition November 2010

Catalagram®

▪▪ The Development of Rare-Earth Free Catalysts

▪▪ Maximising FCC Profitability at the Holborn Refinery
▪▪ TOTAL Success
▪▪ Maintaining LPG Yields for FCC Units Optimising LCO
▪▪ Reducing SOx Emissions Using Super DESOX®: European Case Study
▪▪ Reducing NOx Emissions Using XNOx® at Galp Energia Sines
▪▪ Middle East Refining Technologies Conference
We don’t just make FCC catalysts,
we make FCC catalysts for you.
Only Grace Davison offers refiners a full portfolio of high technology, state-of-the-art FCC catalysts and additives.
Driven by our world-class research and development in the U.S. and Europe, only Grace Davison can customize products
designed specifically to optimize your operation.

Our industry-leading technical service provides support including unit monitoring and troubleshooting, backed by our high
level of analytical services including Ecat, spent catalyst and fines analysis.

We have been the leader in FCC catalysis since inventing the first FCC catalyst over 65 years ago and we are committed to
the future of the refining industry.

Have Grace Davison design your optimal catalyst. Contact us.

Grace Davison Refining Technologies
W.R. Grace & Co. Conn.
7500 Grace Drive
Columbia, MD 21044 USA
Phone: +1 (410) 531-4000
Grace Davison W.R. Grace Singapore PTE Ltd.
Grace GmbH & Co. KG 501 Orchard Road
In der Hollerhecke 1 #07-02 Wheelock Place
67547 Worms, Germany Singapore 238880
Phone +49 (6241) 403-00 Phone +65 6737-5488

www.grace.com · www.e-catalysts.com
 November 2010 IN THIS ISSUE
Managing Editor:
Colin Baillie
Gordon McElhiney The Development of Rare-Earth Free Catalysts

by Ralf Bergsträsser, Edgar Jordan and Gordon McElhiney,

3
Contributors: Grace Davison
Colin Baillie
Ralf Bergsträsser
Stefan Brandt
Edgar Jordan

10
Renaud Kieffer Maximising FCC Profitability at the Holborn Refinery
Gordon McElhiney
Michel Melin by Andreas Krause, Holborn Refinery and Matthias Scherer,
Fernando Sanchez Grace Davison
Maria Luisa Sargenti
Matthias Scherer

Guest Contributors:
Anne-Lies van den Eynde,
TOTAL Success

by Anne-Lies van den Eynde and Tom Knaepkens, TOTAL Antwerp

17
TOTAL Antwerp Refinery Refinery and Michel Melin, Grace Davison

Jose Fernandes Inverno,

Galp Energia Sines

Tom Knaepkens,
TOTAL Antwerp Refinery
Maintaining LPG Yields for FCC Units Optimising LCO

by Stefan Brandt, Grace Davison

20
Andreas Krause,
Holborn Refinery

Tania Lopes,
Galp Energia Sines Reducing SOx Emissions Using Super DESOX®:
European Case Study 23
Layout / Design: by Colin Baillie, Renaud Kieffer and Maria Luisa Sargenti,
Katrin Lohr Grace Davison

Coverpage:
The coverpage is a still of

26
our FCC Animation Reducing NOx Emissions Using XNOx® at Galp Energia Sines
created by
by Jose Fernandes Inverno and Tania Lopes, Galp Energia Sines and
Kreativ Studio Hauck Fernando Sanchez and Maria Luisa Sargenti, Grace Davison
www.studiohauck.com

Grace GmbH & Co. KG

Middle East Refining Technologies Conference

by Nagib Haidar, Grace Davison

30
In der Hollerhecke 1
67547 Worms, Germany
T +49 (0) 6241 403-1425
+49 (0) 6241 403-1608
F +49 (0) 6241 403-1455
+49 (0) 6241 403-1240

www.grace.com
© 2010
Grace GmbH & Co. KG

1
 REsolution
FCC Catalysts

Grace Davison Refining Technologies introduces REsolution,

a rare-earth free catalyst for hydrotreated / low-metal feed applications
 Ralf Edgar Jordan
Bergstraesser
Grace Davison Grace Davison
Refining Technologies Europe Refining Technologies Europe
The Development of
Rare-Earth Free
Rare-earth metals are a key raw material for many strategic
industries, with applications ranging from military devices
to electronic components. In addition, they are essential
constituents in newly evolving green technologies, such as
hybrid cars and wind turbines. Rather ironically, rare-earth
metals are not so rare, however they tend to be concentrated
in hard to extract ore deposits. As a result, the world’s supply
comes from only a few sources; China alone accounts for
95% of the world’s rare-earth metal output. Recent export
quota restrictions on rare-earth metals from China have
caused the price of rare-earth metals to rapidly rise. Because
of these new market forces, we present here our progress in
the development of rare-earth free catalysts.
Rare-earth metals have been used to stabilise the zeolite-Y
component of FCC catalysts since the 1960’s, and rare-
earths remain a key ingredient in FCC catalysts today.
However, in 1997 Grace Davison developed Z-21, a rare-
earth free stabilised zeolite-Y as a lower cost option through.
Based on this new technology the NEXUS catalyst family
Gordon
McElhiney
Grace Davison
Refining Technologies Europe
Catalysts
was commercialised in 1997, as a rare-earth free catalyst
family for HT/low-metal applications. NEXUS combined the
Z-21 zeolite with the Grace Davison proprietary Selective
Active Matrix (SAM) systems, and NEXUS has since been
used in 10 applications.
Commercial Experience Using NEXUS
One such application of NEXUS was at Refinery A, which in
2008 decided to perform a back-to-back catalyst evaluation
comparing NEXUS-346 with a conventional rare-earth based
FCC catalyst from a competitor. Table 1 shows the feed
properties and operating parameters for both trial periods,
both of which were similar. The e-cat Gas Factors and
Hydrogen Factors during the back-to-back testing are shown
in Figures 1 and 2, respectively. As can be clearly seen, at
constant nickel equivalents NEXUS-346 showed lower Gas
Factors and Hydrogen Factors compared to a conventional
FCC catalyst from a competitor.
3
Figure 1: Figure 2:
E-Cat Gas Factors E-Cat Hydrogen Factors
3.5 0.25
3.0
0.20
2.5
2.0 0.15

1.5 0.10
1.0
NEXUS-346 0.05 NEXUS-346
0.5
Competitor Competitor
0.0 0.0
600 700 800 900 1,000 1,100 1,200 1,300 1,400 600 700 800 900 1,000 1,100 1,200 1,300 1,400
Ni equivalents (Ni+ V/4), ppm Ni equivalents (Ni+ V/4), ppm

The FCC product yields obtained during back-to-back testing
are shown in Table 2. NEXUS-346 provided higher conversion
(2.8 wt.%), lower hydrogen yield (0.04 wt.%), a lower dry
gas yield (0.5 wt.%) and a higher gasoline yield (5 wt.%). To
summarise, Refinery A considered the NEXUS-346 trial to be
a complete success and reverted to this catalyst system after
the back-to-back trial. Economic analysis showed a benefit to
Refinery A of approximately 1 million €/year, and the refinery
continue to use NEXUS-346 to this day.

Table 1:
Feed Properties and Operating Parameters

NEXUS-346 Competitor Delta

Feed Properties

Feed density, g/cm3 0.916 0.916 0.000

VABP, °C 454 442 -12

Feed Distillation:

IBP, °C 335 283 52

T90%, °C 521 512 9
Sulfur, wt.% 1.87 1.95 -0.08
Ni, ppm w 0.3 0.3 0
V, ppm W 0.5 0.6 -0.10

Operating Parameters

Fresh Feed Rate, t/d 1992 2172 -180

Recycle, t/d 107 111 -4
Feed preheat, °C 211 217 -6
ROT, °C 515 518 -3
Regenerator dense bed temperature, °C 669 673 -4
Regenerator dilute phase temperature, °C 680 684 -4
Afterburn, °C 11 11 0
Reactor Pressure, kg/cm 2
2.5 2.6 -0.1
Regenerator Pressure, kg/cm 2
3.2 3.4 -0.2
Specific stripping steam rate, kg/MT Cat 2.43 2.19 0.24
Specific riser steam rate, wt.% FF 1.95 1.63 0.32
Catalyst circulation rate, MT/h 655 685 -30
Catalyst/Oil ratio kg/kg 7.55 7.21 0.34

4
Table 2:
FCC Product Yields

NEXUS-346 Competitor Delta

Product Yields

H2 0.03 0.07 -0.04

Dry Gas (-H2S) 3.60 4.12 -0.52
LPG 16.25 18.19 -1.94
Gasoline C5-210 °C 50.16 45.20 4.96
LCO 210-360 °C 15.62 18.72 -3.10
MCB 360+ °C 7.98 7.68 0.30
Coke 4.72 4.56 0.16
Conversion 76.39 73.60 2.79

REsolution Catalyst Family
In 2008, following a spike in rare-earth prices, Grace Davison
renewed efforts to develop rare-earth free catalyst options,
with the R&D group focusing on three main options:
▪▪ Further formulation development based on rare-earth
free Z-21 zeolite
▪▪ D
evelopment of a new, improved rare-earth free route
to zeolite stabilisation
▪▪ A
pplication of EnhanceR technologies to rare-earth free
catalysts
After successfully combining the Z-21 zeolite with a new
matrix (the classical pre-EnhanceR approach), attention
turned to developing an improved rare-earth free route to
zeolite stabilisation. This has now resulted in Z-22, a state-of-
the-art rare-earth free zeolite, prepared using a proprietary
stabilisation process and a unique treatment step to boost
acidity. The Z-22 zeolite has been successfully deployed
in the EnhanceR manufacturing plant resulting in two new
rare-earth free EnhanceR catalyst families designed for
hydrotreated/low-metal feed applications, which will now be
discussed in more detail.

REactoR: A First-Generation EnhanceR Catalyst

The formulation development route using the Z-21 zeolite with for Low-Metal Feed Applications
a new matrix quickly provided promising results, and resulted
in the development of the new catalyst family REsolution. NADIUS is a rare-earth based first-generation EnhanceR
Rare-earth free REsolution catalysts are intended for catalyst for low-metal feed applications. The Acidity
hydrotreated/low-metal feed applications, and represent a Modification (EAMHT) and Structure Stabilisation (ESS)
further improvement on NEXUS performance. Within each functionalities utilised in NADIUS have now been applied to
family of REsolution catalysts, the ability to independently a catalyst containing the newly developed Z-22 zeolite. This
adjust the activity and selectivities of the Z-21 zeolite and has resulted in REactoR, a rare-earth free first-generation
the new matrix, as well as the ratio of zeolite/matrix activity EnhanceR catalyst low-metal feed applications. The
allow for a tremendous degree of formulation flexibility. For
hydrotreated/low-metal applications REsolution catalysts Figure 3:
will match/improve the performance of standard rare-earth EnhanceR Technologies Utilised in REactoR
based catalysts in terms of:
EAMHT Technology
▪▪ Activity
Z-22
▪▪ C4 olefinicity
SRAs
▪▪ Gasoline yield Matrix Aluminas
EnhanceR
REactoR
▪▪ Bottoms upgrading TMAs Plant
Matrix Aluminas

▪▪ Coke yield Al-Sol

Binder

ESS Technology

5
manufacturing route to REactoR is shown in Figure 3.
Table 3:
REactoR catalysts will provide similar performance benefits
ACE Testing Comparing NADIUS with REactoR
to NADIUS catalysts in terms of:
CPS-3 deactivation, metals free
▪▪ High conversion in low metals / hydrotreated feed
applications. NADIUS REactoR

▪▪ High product olefinicities with low gas yields. Conversion, wt.% 75 75

▪▪ Bottoms upgrading. C1+C2, wt.% 1.9 2.0
Propylene, wt.% 6.0 6.2
C4 Olefins, wt.% 8.6 9.1
ACE Pilot plant testing has been used to compare NADIUS Gasoline, wt.% 51.0 50.3
with REactoR, and the key selectivities interpolated at 75
Bottoms, wt.% 10.3 10.3
wt.% conversion are shown in Table 3. Both catalysts show
Coke, wt.% 1.7 1.6
similar selectivities in terms of dry gas, coke and bottoms
upgrading, whilst REactoR does provide higher yields of Figure 4:
LPG olefins at the expense of some gasoline yield. EnhanceR Technologies Utilised in REplaceR

EAMHTD Technology EPRHT Technology

REplaceR: A Third-Generation EnhanceR Catalyst
Z-22
for Low-Metal Feed Applications
SRAs
Matrix Aluminas
EnhanceR
NaceR is a rare-earth based third-generation EnhanceR REplaceR
TMAs Plant
catalyst for low-metal feed applications. The Acidity Matrix Aluminas

Modification (EAM HTD

), Pore Restructuring (EPRHT), and Al-Sol
Binder
Structure Stabilisation (ESS) functionalities utilised in NaceR
can also be applied to a catalyst that contains the Z-22 ESS Technology
zeolite. This has resulted in REplaceR, a rare-earth free third-
generation EnhanceR catalyst low-metal feed applications.
Figure 5:
The manufacturing route to REplaceR is shown in Figure 4.
Conversion
ACE Pilot plant testing has been used to compare NaceR
with REplaceR. The key selectivity curves obtained after 83
Standard Conversion [wt.% ff]

81
metals-free CPS-3 deactivation are shown in Figures 5-9. 79
77
75
To summarise the ACE pilot plant testing, REplaceR catalysts 73
will provide the following performance benefits compared to 71
69
NaceR catalysts: 67 REplaceR
65 NaceR
▪▪ Similar, high activity. 63
3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5 8.0
▪▪ Slightly higher LPG olefins yield Cat to Oil [-]
▪▪ Slightly lower gasoline yield
Figure 6:
▪▪ Similar bottoms upgrading.
LPG Olefins Yield
▪▪ Similar coke yield

16
C3 + C4 Olefins [wt.% ff]

15
Within the REactoR and REplaceR catalyst families the
14
matrix type as well as the zeolite/matrix ratio can be varied.
Additional formulation flexibility is provided by variation in the 13

degree of EAMHT, EPRHT and ESS enhancement, enabling 12

fine tuning of the catalyst to suit FCCU-specific requirements 11 REplaceR
NaceR
regarding activity and selectivity. REactoR and REplaceR 10
are also manufactured with the proprietary Grace Davison 63 65 67 69 71 73 75 77 79 81 83

alumina-sol binder system, which ensures low particulate Standard Conversion [wt.% ff]

6
emissions due to its excellent attrition resistance. However,
due to the incorporation of the Z-22 zeolite modifications to our
manufacturing plant are necessary, and therefore REactoR
and REplaceR will be commercialised in early 2011.
A Rare-Earth Free EnhanceR Catalyst for Resid
Feed Applications
Due to the additional demands placed on the zeolite stability,
the development of rare-earth free catalysts for the resid feed
sector is much more challenging than for the low-metal feed
sector. However, the EnhanceR Metals Resistance (EMR)
technology has now been successfully applied to a catalyst
system containing the Z-22 zeolite, resulting in the REduceR
catalyst. Although not fully equivalent to the performance of
benchmark pure rare-earth based resid catalysts, REduceR
can be used as a blending component with a rare-earth
based resid catalyst, thus reducing the overall rare-earth
requirement. Figures 10 to 12 show ACE pilot plant testing
comparing a rare-earth based NEKTOR resid catalyst and
the same catalyst containing 30% of the new rare-earth
free resid catalyst REduceR (after CPS-3 deactivation at
3000/2000 ppm V/Ni levels). To summarise, REduceR, a
rare-earth free resid catalyst can be blended with a rare-
earth based resid catalyst to provide similar performance in

Figure 7: Figure 10:

Gasoline Yield Conversion

53 85

Standard Conversion [wt.% ff]

52 83
Gasoline [wt.% ff]

51 81
50
79
49
77
48
47 75
REplaceR 70% NEKTOR / 30% REduceR
46 73
NaceR NEKTOR
45 71
63 65 67 69 71 73 75 77 79 81 83 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5 8.0
Standard Conversion [wt.% ff] Cat to Oil [-]

Figure 8: Figure 11:

Bottoms Yield Bottoms Upgrading
Heavy Cycle Oil 337 °C [wt.% ff]

Heavy Cycle Oil 337 °C [wt.% ff]

19 12
REplaceR 70% NEKTOR / 30% REduceR
17 11
NaceR NEKTOR
15
10
13
9
11
8
9
7 7
5 6
63 65 67 69 71 73 75 77 79 81 83 71 73 75 77 79 81 83
Standard Conversion [wt.% ff] Standard Conversion [wt.% ff]

Figure 9: Figure 12:

Coke Yield Coke Yield

5.0 8
4.5 70% NEKTOR / 30% REduceR
7 NEKTOR
4.0
Coke [wt.% ff]

Coke [wt.% ff]

3.5 6
3.0 5
2.5 4
2.0
REplaceR 3
1.5 NaceR
1.0 2
63 65 67 69 71 73 75 77 79 81 83 71 73 75 77 79 81 83
Standard Conversion [wt.% ff] Standard Conversion [wt.% ff]

7
the key areas of activity, bottoms upgrading and coke yield.
Of course, R&D work is still ongoing to develop a rare-earth
free catalyst with the stability and performance to allow the
complete elimination of rare-earth based grades in resid
applications.

Summary

In 1997 Grace Davison Refining Technologies developed

NEXUS, a rare-earth free catalyst family for low-metal feeds,
which has since been used in 10 applications. In 2008 due to
increasing rare-earth prices, R&D activities were intensified
to develop rare-earth free catalysts. This has resulted in the
following three new catalyst families for the low-metal feed
sector:

▪▪ REsolution: contains rare-earth free Z-21 zeolite in

combination with a new matrix
▪▪ R
EactoR: contains the newly developed rare-earth free
Z-22 zeolite with the application of the first-generation
EnhanceR technology used in NADIUS
▪▪ R
EplaceR: contains the newly developed rare-earth
free Z-22 zeolite with the application of the third-
generation EnhanceR technology used in NaceR

Grace Davison has also developed REduceR, a rare-earth

free resid catalyst, which can be blended at a 30% level
into rare-earth based resid catalysts without significant
performance deterioration in resid applications.

Whilst the REsolution catalyst is available immediately

for trials, the commercialisation of REactoR, REplaceR
and REduceR will take place in early 2011 as they require
modifications to our manufacturing plant.

Grace Davison Refining Technologies has responded quickly

to the issues of rare-earth price and availability, by developing
these new rare-earth free catalysts, in order to relieve the
cost pressure on customers without incurring performance
penalties.

8
 REplaceR

REplaceR
FCC Catalysts

Grace Davison Refining Technologies introduces REplaceR,

a rare-earth free third-generation EnhanceR catalyst for
hydrotreated / low-metal feed applications
 Maximising FCC Profitability at the
Holborn Refinery
Andreas Krause

Holborn Refinery

Matthias Scherer

Grace Davison
Refining Technologies Europe

Holborn Refinery ing units and are able to selectively decide the type and
severity of the desulphurisation needed for each product
The Holborn refinery is located in the north of Germany close stream. Holborn’s FCC unit was originally engineered dur-
to the city of Hamburg. The crude throughput is about 5 mil- ing the early 1950’s and has since seen three generations of
lion tons per year, and the crude is processed under a ser-
vice contract with Holborn European Marketing, Cyprus. The
Table 1:
refinery is connected with a self-owned 140 km long crude
Typical Feed Properties at the Holborn FCC Unit
pipeline to a German deep water crude terminal, which is the
only deep water terminal in Germany. The Holborn market is Test Method Units Feed to the Cracker
characterized by high motor fuels and heating oil demand.
Specific gravity g/cc 0,916 ± 0,007
Holborn operates a crude distillation unit (CDU) followed by Conradson Carbon wt% 0,75 ± 0,13
two vacuum units. The resulting VGO is fed to the FCC, to- Basic nitrogen ppmwt 553 ± 300
gether with the 4th side stream from the CDU. Depending Sulphur wt% 0,59 ± 0,23
on the operating strategy (maximum gasoline or maximum Distillation °C SIMDIS
distillate mode), Holborn processes atmospheric residue or 0% °C 192
recycles HCO with a throughput ratio between 1.04 and 1.1. 10% °C 343
Table 1 shows the typical feed qualities processed at Hol- 30% °C 413
born’s FCC unit. The FCC unit in Holborn is at the heart of 50% °C 450
the operation, where the highest profits from the upgrading of 70% °C 490
heavy feedstock to higher value products is achieved. 80% °C 553
100% °C 625
Holborn’s strategic operation plan is based on two operation Ni ppm 0,55 ± 0,23
modes, maximum gasoline or maximum distillate. Down- V ppm 0,95 ± 0,42
stream of the FCC unit Holborn operates several hydrotreat- Na ppm 0,14 - 0,15

10
modifications, in which the throughput
has increased by 320% to a current
Table 2:
throughput of 145 m³/h. The cata-
Hardware Constraints of the Holborn FCC Units
lyst inventory is about 45 tons, and Constraints in the FCC Lower Limit Upper Limit Eng Unit
the current catalyst addition rate is
about 1 ton/day. The regenerator is Reactor temperature 490 505 °C
designed for a coke burn capacity of Regenerator temperature 660 705 °C
4.5 tons/h. Two types of additive are Cat circulation 7 8.5 t/min
typically used in Holborn’s FCC unit, Catalyst addition - 1.8 t/d
a nickel passivator (max. ratio Sb/ Total air 28000 34460 Nm3/h
Ni 0.15), and an anti-fouling additive Heater outlet temperature 300 425 °C
(Heat Exchanger/Thermoflow). CO - Value 6 8.6 vol%
Cyclone Velocity 16 22 m/s
Holborn’s FCC unit is an Exxon Model Reactor pressure 1.1 1.6 barg
IV, as shown in Figure 1, which op- Gasoline amount 35 70 m3/h
erates at more or less constant cata- atm. Residue addition 0 15 m3/h
lyst circulation. In order to increase Slurry draw off 3 7 m3/h
conversion, e-cat microactivity can
be independently controlled, as well as throughput (to ad- Operating Modes at Holborn’s FCC Unit
just the Cat/Oil ratio), throughput ratio and feed pre-heat (to
adjust reactor temperature). Each of these parameters are The preferred FCC unit operation at Holborn is for maximum
adjusted according to Holborn’s prevailing targets, in order distillates, and the unit runs in this mode for the majority of
to maximise profit at the given air limitation. The limitations the time. The comparison and evaluation is performed using
and constraints of the Holborn FCC unit are shown in Table a standard simulation model and the Flash 5.0 Program. To
2. These are the values used in the simulation to monitor unit optimise distillate production at minimum bottoms yield the
performance in the subsequent discussion. following operational and catalyst features are utilised:

▪▪ Reduction of feed temperature to decrease Reactor

Figure 1: temperature.
Schematic Diagram of the Exxon Model IV ▪▪ O
ptimised throughput ratio at maximum throughput
FCC Unit at Holborn (minimum Cat/Oil).
▪▪ Adjustment of cut points for products and FCC feed.
▪▪ Reduction of e-cat activity
Transferline (lower fresh catalyst addition).
Slide Valve
▪▪ P
rocessing of heavier feed (residue) to decrease
conversion.
▪▪ U
se of a Grace Davison alumina-sol FCC catalyst,
Cyclones
Cyclones specifically tailored for Holborn’s operation.

Reactor The other operating mode at the Holborn FCC unit is maxi-
Regenerator
Overflow
Distribution Grid
mum gasoline mode. To increase the gasoline production the

following operational and catalyst features are utilised:

Riser
Steam
▪▪ Increased feed temperature to raise Reactor temperature.
Stripper
▪▪ M
aximisation of throughput ratio at adequate fresh feed
Slide Valves processing (maximum Cat/Oil).
▪▪ Adjustment of cutpoints accordingly.
▪▪ I ncreased e-cat activity, through increased fresh
Slide Valves catalyst addition.
▪▪ Processing of a more paraffinic feed to increase
Coked Cat
conversion.
▪▪ U
se of a Grace Davison alumina-sol FCC catalyst,
Regenerated Cat U-Bend specifically tailored to upgrade bottoms into gasoline at
 a constant or only slightly lower LCO yield.

11
Over the recent years, Holborn has been able to optimise Table 3:
these two operating modes, which has provided the flexibility Recent Catalyst History at the Holborn FCC Unit
to react quickly to the market demand. Due to the flexibility of
both operating modes, Holborn’s LCO yield covers a range of
Date Catalyst Run Time (days)
29-45 wt.%, with naphtha yields between 27-37 wt.% (both of
which are uncorrected yield windows). 08.04.2003 Distimax-244 337
10.03.2004 Distimax-233N 336
09.02.2005 Brilliant-327 EHH 1080
Maximising FCC Profitability Through Improved 25.01.2008 Brilliant-336 ER 327
Monitoring 17.12.2008 NOMUS-DMAX 227 369
21.12.2009 DieseliseR-276 343
In order to efficiently control yield structure and thus unit
profit (for both operating modes) Holborn uses proprietary uct prices cannot be influenced. Therefore, for the refinery
tools, including: to achieve its targeted profit then this can only be achieved
when the processes run at optimised conditions. This in-
▪▪ Standard FCC Simulations-Model volves:
▪▪ Flash 5.0 Program (Two-Phase Flash Programs)
▪▪ Monitoring the mass, energy and heat balance
▪▪ LP-Model (PIMS Model)
▪▪ Continuous calibration of orifices
▪▪ Data Validation Program
▪▪ D
aily considerations of the best settings to push the
unit to the limits regarding the optimum operation
In addition to Holborn’s simulation programmes, Grace Da-
▪▪ E
stablishing and monitoring of actual product yields/
vison also uses a simulation model and the results are fre-
patterns in combination with effective communication
quently exchanged and discussed. Regarding day-to-day between production and planning
monitoring, the main difficulty is within the calibration of these
▪▪ Tailored FCC catalyst
programmes. It is very important to note that the results ob-
tained from the programmes are only as accurate as the in-
puts provided. Once a week a test run is conducted and thus Maximising FCC Profitability Through an
a whole set of samples of the entire FCC unit are taken and Optimised Catalyst
analysed. This analysis and process data is used as input for
simulation models. In Figure 2 a typical daily monitoring life To achieve profit maximisation it is also vital to have an opti-
cycle is shown. mised catalyst. When such a catalyst was designed for Hol-
In order to further enhance value creation to maximise profit born, the following requirements were considered:
at Holborn’s FCCU, the refinery operates the FCC unit on a
day-to-day basis bearing in mind the prevailing economics ▪▪ Stability
and market demand. Economics can be improved slightly by ▪▪ Flexibility for use in both gasoline and diesel modes
careful selection of opportunistic crudes, but refinery prod-
▪▪ High bottoms upgrading
▪▪ Excellent metals tolerance
Figure 2:
A Typical Daily Optimisation and ▪▪ Low delta coke
Monitoring Life Cycle ▪▪ Gasoline with high octane
▪▪ Low FCC emissions

FCC Refinery Flash

Process FCC Model SeparationTool
Holborn has used FCC catalysts from the three major suppli-
ers over the last few decades, but during recent times Grace
Davison has been the supplier. Table 3 shows the catalyst
Vector
history in Holborn since 2003 and it can be seen that Grace
Set points
Generation
Target‘s
Model Davison has continually made innovations in catalyst tech-
nology, which Holborn have applied to maximise profits.
LP-Model
Currently DieseliseR-276, which is a catalyst for distillate
maximization, is being used at Holborn, and the switch from
the previous catalyst NOMUS-DMAX 227 to DieseliseR will
Product and crude oil prices
now be discussed.

12
Holborn Experience Using DieseliseR These results confirmed that DieseliseR, through a lower
delta coke and a further enhanced metals tolerance, pro-
Holborn received the first shipment of DieseliseR-276 by the vided Holborn with a significantly higher flexibility to process
end of 2009, and DieseliseR started to enter the unit at the all types of feed (currently atmospheric residue), minimising
end of January 2010. Before the use of DieseliseR the re- main column bottoms. Moreover, by tailoring the unit opera-
finery started to operate with HCO recycle (throughput ratio tion parameters and/or the DieseliseR e-cat activity as need-
1.04 – 1.1) and also the processing of atmospheric residue. ed, Holborn has the choice to either upgrade the bottoms into
The quantity of HCO recycled and/or atmospheric residue the LCO range or by applying a higher conversion to upgrade
used (both either processed together with VGO and/or single it even further into the naphtha range.
with VGO) was decided at given point in time by the corre-
sponding operating strategy team, based on the prevailing Gasoline Mode
economics.
The gasoline mode is set by operating the FCC unit at high
The typical e-cat metals levels in this FCC unit are usually Cat/Oil ratio (lower throughput) and targeting a high e-cat
between 5000 up to 8000 ppm V+Ni, and there is often the activity. With the change to DieseliseR-276, and the subse-
possibility that there are high iron concentrations on the e- quent lower delta coke, the unit had less of an air constraint.
cat (depending on crude slate used). Therefore, a highly Holborn used this flexibility to either maximise HCO recycle
important catalyst requirement has always been to display or to process atmospheric residue with the FCC unit feed.
excellent metals tolerance. Thus, the
DieseliseR-276 formulation used in Hol-
born was not only selected based on
Table 4:
the capability to even further maximise
E-Cat Physical and Chemical Properties
distillates at minimum bottoms but also
because of the further improved met-
als tolerance compared to the previous Sample NOMUS-DMAX 227 DieseliseR-276
NOMUS-DMAX 227 catalyst.
MAT, wt.% 70 69
Gas Factor 3.7 3.2
ACE (Advanced Catalyst Evaluation)
H2 Yield, wt.% 0.35 0.26
Pilot Plant testing was carried out with
Coke Factor 1.5 1.5
e-cat samples from Holborn, represent-
CRC, wt.% 0.135 0.125
ing the unit’s typical deactivation pattern.
Ni, ppm 2495 2214
The DieseliseR-276 sample was taken
V, ppm 2826 3142
at an 80% change-out level, and the test
was performed using the actual refinery RE2O3, wt.% 2.9 3.2

feed. As shown in Table 4, both samples Al2O3, wt.% 50.3 50.4

had a similar activity level and the same
overall metals content. Table 5:
ACE Pilot Plant Testing at Constant Coke
Table 5 shows the resulting yield pattern
at constant coke yield. DieseliseR-276 DieseliseR-276,
Sample NOMUS-DMAX 227 80% Change Out
further improved the performance com-
pared with NOMUS-DMAX 227 by pro- Cat to Oil [-] 5.33 6.21
viding: Standard Conversion [wt.% ff] 74.7 75.3
Hydrogen [wt.% ff] 0.34 0.31
▪▪ A higher conversion (the lower Total C1+C2 [wt.% ff] 2.53 2.60
delta coke enabled a higher Cat/ Total C3+C4 (LPG) [wt.% ff] 19.5 19.5
Oil)
Gasoline [wt.% ff] 48.3 48.8
▪▪ Increased gasoline and LCO yield Light Cycle Oil [wt.% ff] 14.9 15.2
▪▪ Significantly lower bottoms yield Heavy Cycle Oil 337°C [wt.% ff] 10.4 9.5

▪▪ Higher gasoline octane Coke on catalyst [wt.% ff] 0.77 0.66

Coke [wt.% ff] 4.10 4.10
Motor Octane Number 82.3 82.8
Research Octane Number 93.5 94.0

13
Table 6:
FCC Yields and Operating Data in the Gasoline Operating Mode*
NOMUS-DMAX 227 DieseliseR-276 Deltas
(Dec 2009) (April to Aug 2010)
Throughput ratio 1.08 1.08 0.00
V ppm 2191 3692 1501
Cat/Oil Ratio 3.6 3.9 0.3
Standard Fresh Feed Conversion <221 °C, wt.% 63.6 65.6 2.0
Standard Total Naphtha <221 °C 49.3 50.0 0.7
Standard Light Cycle Oil 221-343 °C 22.1 21.6 -0.5
Standard Clarified Oil >343 °C 14.3 12.8 -1.5
LCO over Slurry, Ratio 1.55 1.69 0.14
Delta Coke 0.93 0.84 -0.09
* For an appropriate comparison, in the following the yields for gasoline, LCO and bottoms were corrected as follows:
▪▪ Gasoline cut, < 221°C
▪▪ LCO cut, 221 °C – 343°C
▪▪ Bottoms cut, > 343°C

Table 7:
FCC Yields and Operating Data in the Distillate Operating Mode*
NOMUS-DMAX 227 DieseliseR-276 Deltas
(Dec 2009) (April to Aug 2010)
Throughput ratio 1.04 1.04 0.00
V ppm 1903 3128 1225
Cat/Oil Ratio 3.7 3.9 0.2
Standard Fresh Feed Conversion <221 °C, wt.% 62.2 62.0 -0.2
Coke, wt.% 3.2 2.8 -0.4
Standard Total Naphtha <221 °C 46.9 48.0 1.1
Standard Light Cycle Oil 221-343 °C 23.2 23.6 0.4
Standard Clarified Oil >343 °C 14.6 14.4 -0.2
LCO over Slurry, Ratio 1.59 1.64 0.05
* The same cut points were used as in the gasoline operating mode

Figure 3: Figure 4:
FCC Unit Data Showing Improved FCC Unit Data Showing Bottoms Upgrading for
LCO/Bottoms Ratio for DieseliseR DieseliseR

2.0 30
DieseliseR-276 28 DieseliseR-276
1.8 NOMUS-DMAX 227
NOMUS-DMAX 227
Bottoms, wt.% >342 °C

26
LCO / Bottoms Ratio

1.6
24
1.4 22
1.2 20
1.0 18
16
0.8
14
0.6 12
0.4 10
45 50 55 60 65 70 50 52 54 56 58 60 62 64 66 68 70
Conversion, wt. % <221 °C Conversion, wt. % <221 °C

14
As a result, the regenerator temperature increased and the
resulting CO burning improved. Using DieseliseR, a higher
Cat/Oil could be achieved than with the previous NOMUS-
DMAX 227 catalyst, which resulted in a higher conversion.
In addition, the unit operation became even more stable, and
because the unit is operating at constant catalyst circulation
(depending on fluidisation air and delta p) the higher regen-
erator temperature at a given feed temperature meant that a
higher reactor temperature could be achieved for DieseliseR.
Typical results for the gasoline mode comparing DieseliseR
versus NOMUS-DMAX are shown in Table 6.
To summarise, DieseliseR-276 provided:
▪▪ A significantly higher conversion, which is
predominantly due to the higher Cat/Oil achieved.
▪▪ Higher gasoline yields
▪▪ Lower lower slurry yields.
▪▪ Higher LCO to slurry ratio.
Distillate Mode
The distillate mode is generally characterised by a lower Cat/
Oil ratio, whilst processing maximum available fresh VGO in
combination with a low throughput ratio and a lower e-cat ac-
tivity. This results in a lower severity but still enough gasoline
is produced at maximum LCO yield. Table 7 shows typical
data comparing DieseliseR-276 with the previous NOMUS-
DMAX 227 catalyst in diesel mode.
To summarise, DieseliseR-276 provided:
▪▪ A
lower conversion in the distillate mode than for
the gasoline mode (due to lower Cat/Oil, lower e-cat
activity)
▪▪ A
higher Cat/Oil in the distillate mode compared to
NOMUS-DMAX (due to lower delta coke)
▪▪ B
etter bottoms upgrading into gasoline and/or LCO
(ratio depends on the conversion) in the distillate mode
compared to NOMUS-DMAX
▪▪ A
higher LCO to slurry ratio in the distillate mode
compared to NOMUS-DMAX (even though conversion
is lower)
Overall, DieseliseR-276 delivered a substantially higher
LCO/bottoms ratio and lower bottom yields, as shown in
Figures 3 and 4, respectively. This can be mainly attributed
to the higher Cat/Oil achieved due to the specific properties
of the DieseliseR catalyst, and appropriate adjustment of
throughput. Based on yield patterns, a calculation of the re-
sulting economics using actual product prices revealed that
the change from NOMUS-DMAX to DieseliseR significantly
increased FCC unit profitability.
Conclusion
The Holborn refinery uses various monitoring tools to oper-
ate their Model IV FCC unit within their constraints and limi-
tations either in a gasoline or distillate mode. In the gasoline
mode the unit is operated with the available VGO but the
spare capacity is used to process atmospheric residue. In
distillate mode the unit is pushed to maximum VGO process-
ing, with a throughput ratio as high as possible, recycling
HCO. In addition, Holborn use a tailored DieseliseR catalyst
from Grace Davison with excellent bottoms upgrading via en-
hanced matrix functions, low delta coke and enhanced met-
als resistance. This provided the refinery with the flexibility
to process either HCO or atmospheric residue with the fresh
VGO feed, in order to achieve the maximum unit profitability.
To summarise, the following shifts were observed:
▪▪ By adjusting the Cat/Oil ratio, via the throughput ratio
and/or processing of atmospheric residue, the resulting
product streams could be easily adjusted to either
produce more gasoline or achieve a higher LCO/slurry
ratio, at a reduced bottoms yield.
▪▪ The improved metals tolerance of the DieseliseR
catalyst, allowed the processing of atmospheric residue
without debits on the gas and coke make.
▪▪ Gasoline RON & MON increased.
▪▪ T
he expected yield shifts were confirmed for the
change from NOMUS-DMAX to DieseliseR.
▪▪ The data and yield shifts monitored in the FCC unit
are in line with the results obtained from a side by
side e-cat testing, comparing NOMUS-DMAX and
DieseliseR.
Important Note:
The DieseliseR technology is available thanks to a collabo-
ration project between Grace Davison and REPSOL after
intensive work was performed by the R&D groups of both
companies. In parallel to this article REPSOL is concluding
its positive results observed with DieseliseR, and the result-
ing performance data will be published soon.
15
 Searching for more freedom
for LCO maximisation?
DieseliseR - no st rings attached

DieseliseR
FCC Catalysts

Grace Davison Refining Technologies introduce DieseliseR,

a third-generation EnhanceR FCC catalyst for LCO maximisation
 Success
Anne-Lies van Tom Knaepkens
den Eynde
TOTAL Antwerp Refinery TOTAL Antwerp Refinery
This article describes how the TOTAL Antwerp FCC unit
(FCC 1) has improved the unit yield structure by using
NEKTOR-ULCC, which is an FCC catalyst based on the
Grace Davison EnhanceR Technology Platform. A brief
description of the catalyst technology will be followed by a
discussion of the commercial trial of NEKTOR-ULCC at the
TOTAL Antwerp refinery. FCC unit operating data and ACE
pilot plant data is provided to highlight the positive changes
in yield structure and the resulting economical benefits
provided by NEKTOR-ULCC.
NEKTOR-ULCC
A significant breakthrough in FCC catalyst design was
achieved with the introduction of the Grace Davison
EnhanceR Technology Platform. This platform involves the
four technologies EPR (Pore Restructuring), EMR (Metals
Michel Melin
Grace Davison
Refining Technologies Europe
Resistance), EAM (Acidity Modification) and ESS (Structure
Stabilisation). Rather than making separate modifications
to the zeolite and matrix components, the EnhanceR Plant
enables processing of input materials, intermediate products
and end-product FCC catalysts.
Whereas the first generation of EnhanceR catalysts each uti-
lised two technologies, further development provided a sec-
ond generation of catalyst families that incorporated an addi-
tional EnhanceR Technology. For example, NEKTOR-ULCC
is formulated with the EPR and EMR technologies used in
NEKTOR but also utilises the EAMR Technology to provide
even better bottoms cracking through a further reduction in
delta coke. Users of NEKTOR-ULCC are seeing further im-
provement in coke selectivity, and are using this to increase
conversion at maximum feedrate, achieving even better bot-
toms upgrading without requiring additional air.
17
 Table 1:
TOTAL Antwerp Refinery
FCC Unit Operating Conditions
With a refinery capacity of 18 million MT per NEKTOR-676 NEKTOR-ULCC
year of crude, TOTAL Antwerp is the sec-
ond largest refinery in Europe. Two FCC Feed rate (m³/h) 173 179
units produce a total throughput of 700 m³/h ARDS resid content (%) 54 54
(106,000 bpd) and process up to 70% of hy- Feed preheat temperature (°C) 242 252
drotreated atmospheric residue. The FCC 1 ROT (°C) 512.5 516
unit was built in 1956, and is a UOP stacked Regenerator bed temperature (°C) 755 760
design, and it is the smaller of the two units Delta coke (wt.%) 1.10 1.11
with a capacity of 175 m³/h. It was revamped Reactor pressure (barg) 1.51 1.61
in 2001 by TOTAL/Stone&Webster to include
Table 2:
Stone&Webster elevated radial feed nozzles,
Feed Quality
a packed stripper and an external riser termi-
nated by a simple catalyst separation device. NEKTOR-676 NEKTOR-ULCC
The air blower capacity is supplemented by
oxygen addition and an ESP was installed Specific gravity 0.9243 0.9270

a little later behind the CO boiler. The FCC Conradson carbon (wt.%) 2.78 2.71
units are operated in partial burn without a Basic nitrogen (ppm) 568 ~600
catalyst cooler. The feedstock processed H content (wt%) 12.30 12.32
contains a high content of contaminant met- KUOP 11.87 11.92
als, as demonstrated by the nickel and va- T90 (°C) 603 605
nadium levels on the e-cat, which typically
Table 3:
reach levels of 10,000 ppm. Consequently,
E-Cat Properties
the refinery required an extremely coke-se-
lective FCC catalyst making it an ideal can- NEKTOR-676 NEKTOR-ULCC
didate for assessing the performance of the
MAT activity (wt.%) 70.5 72.5
NEKTOR-ULCC catalyst.
CRC 0.21 0.32
Coke factor 1.15 1.0
Commercial Trial Gas factor 1.75 1.7
Ni (ppm) 2077 2061
The trial of the Grace Davison NEKTOR- V (ppm) 3878 3620
ULCC catalyst began in February 2008 in the
Table 4:
FCC 1 unit. It replaced the NEKTOR-676T
FCC Unit Yields
catalyst, which was introduced successful-
ly on the market at the end of 2003 on the NEKTOR-676 NEKTOR-ULCC
same unit. During the catalyst trial the oper-
1

H2 (wt.%) 0.05 0.05

ating objective was to use the improved coke
H2S (wt.%) 0.27 0.23
selectivity of NEKTOR-ULCC to increase ei-
C1+C2’s (wt.%) 2.35 2.57
ther the feed concarbon content or the con-
version (by operating at higher e-cat MAT) C3= (wt.%) 3.78 3.68
depending on the relative economic benefits. iC4= (wt.%) 1.21 1.43
The performance of the NEKTOR-ULCC nC4= (wt.%) 3.70 4.09
catalyst was assessed using FCC unit check Total LPG (wt.%) 13.04 13.48
run data, as well as ACE pilot plant testing on LCN C5-150 °C (wt.%) 31.72 33.13
equilibrium catalyst. HCN 150-221 °C (wt.%) 14.93 14.61
TCN (wt.%) 46.65 47.74
LCO 221-350 °C (wt.%) 17.19 15.09
Slurry 350+ °C (wt.%) 14.69 15.42
Coke (wt.%) 5.76 5.55
Conversion 221 °C vol% 69.40 71.3
221 °C TBP wt% 68.12 69.49

18
 Table 5:
FCC Unit Check Run Data
E-Cat Characterisation
To allow an accurate and fair evaluation of NEKTOR-676 NEKTOR-ULCC
the performance of NEKTOR-ULCC in com-
parison to NEKTOR-676, good quality and MAT (wt.%) 69.5 69.5
representative check runs were selected Gas Factor 2.1 2.0
from operating periods in which the operat- H2 Yield (wt.%) 0.160 0.143
ing conditions were similar in terms of feed Coke Factor 1.3 1.1
quality and unit severity. Tables 1-4 show the Zeolite SA (m²/g) 115 116
FCC unit operating conditions, feed quality, Matrix SA (m²/g) 26 27
e-cat properties and FCC unit yields, respec- Unit Cell Size (Å) 24.32 24.31
tively. Ni (ppm) 2552 2485
V (ppm) 4931 4931
During the trial period, the unit was operated Na (wt.%) 0.26 0.305
with an e-cat activity that was 2 wt.% higher Fe (wt.%) 0.335 0.27
(Table 3). This was possible due to the bet- Sb (ppm) 373 321
ter intrinsic delta coke of the NEKTOR-ULCC Cu (ppm) 10 7
catalyst. As a result, a gain in conversion of
RE2O3 (wt.%) 3.7 3.6
1.4 wt.% (221 °C TBP) was observed when
Al2O3 (wt.%) 51.0 51.7
using the NEKTOR-ULCC catalyst (Table 4).
This translated into a 1.1 wt.% increase in Table 6:
the Total Cut Naphtha yields, and a 0.4 wt.% ACE Pilot Plant Yields at Constant Coke
increase in LPG yield.
NEKTOR-676 NEKTOR-ULCC

Standard conversion (%) 73.6 75.1

ACE Pilot Plant Test Data Cat to Oil (g/g) 5.9 6.4
Hydrogen (wt.%) 0.360 0.320
ACE pilot plant tests were carried out using e- Total C1 + C2 (wt.%) 3.0 3.1
cat samples collected from the Antwerp FCC Propene (wt.%) 4.9 5.1
unit during the periods of NEKTOR-676T and Total C3 (wt.%) 6.5 6.8
NEKTOR-ULCC catalyst usage. The charac-
C4-Olefins (wt.%) 6.1 6.2
terisation data for these samples are sum-
Total C4 (wt.%) 11.6 12.0
marised in Table 5, and it can be seen that
Total C3 + C4 (LPG) (wt.%) 18.2 18.8
at similar metals levels NEKTOR-ULCC pro-
LPG Olefinicity (%) 60.6 60.1
vides lower Gas and Coke Factors, as well
Gasoline, 28 - 216°C (wt.%) 45.7 46.5
as a lower hydrogen yield.
LCO, > 216 - 337°C (wt.%) 15.3 14.6
HCO > 337°C (wt.%) 11.1 10.3
The ACE study yields at constant coke yield
Coke (wt.%) 6.5 6.5
are shown in Table 6, and it can be seen
Coke-on-catalyst (%) 1.10 1.02
that compared with NEKTOR the NEKTOR-
ULCC catalyst provides an increase of 1.5
wt.% conversion. This provided a slight increase in LPG yield to 2.0 million USD per year. The commercial trial was consid-
of 0.6 wt.%, and an increase of gasoline yield by 0.8 wt.%. ered a complete success, and the refinery decided to contin-
This is consistent with the FCC unit yields shown in Table 4. ue using NEKTOR-ULCC. Currently there are 11 FCC units
in the EMEA region using NEKTOR-ULCC.

Conclusion
References
Assuming a margin of 1 USD per MT of feed per wt.% con-
version gain, the additional profit achieved with the move to 1 S. Rousseau, M. Bories, M. Melin,
NEKTOR-ULCC in the TOTAL Antwerp FCC 1 unit amounted Hydrocarbon Engineering, November, 2005.

19
 Maintaining LPG Yields for
FCC Units Optimising LCO

Introduction

In this so-called period of “dieselisation”, maximising distillate

production is currently a hot topic for refiners. Consequently,
operators are increasingly looking at optimising LCO yield in Stefan Brandt
the FCC unit. LCO yields in the FCC unit are influenced by
the following variables:

Grace Davison
▪▪ Conversion level (operating severity)
Refining Technologies Europe
▪▪ Recycle ratio
▪▪ Catalyst composition
▪▪ Feedstock composition

Of these variables, optimising operating severity is usually ProfiMax

the first step taken to increase LCO yield. By using a lower
Riser Outlet Temperature (ROT), typically 485 – 510 °C,
conversion levels will decrease resulting in increased LCO
yields due to less cracking of LCO into gasoline-range mol-
ecules. Therefore the lower ROT results in reduced gasoline
yields, which is also accompanied by increased slurry yield.
In addition, due to the decrease in gasoline, which provides
LPG precursors, lower LPG yields are observed. This article
will highlight how Refinery A in Europe utilised ProfiMax, a
ZSM-5 additive from Grace Davison, to maintain LPG yields
whilst operating at lower ROT.
Developments made by Grace Davison Refining Technolo-
gies have resulted in ZSM-5 additives with increased intrin-
sic activity, which are providing refiners with the most cost-
effective solution for boosting light olefin yields. ProfiMax is
a ZSM-5 additive with enhanced activity and stability, and
leads to improved LPG olefins production. The ZSM-5 pref-
erentially cracks low octane gasoline paraffins and olefins to
lighter C3 and C4 olefins. At the same time the low octane
linear olefins are isomerised to obtain more highly branched,
higher octane olefins.

20
Figure 1: Figure 2:
Activitiy Ranking of ZSM-5 Additives FCC Unit LPG Yields

28
OlefinsUltra® ProfiMax 26
24
OlefinsMax®
Propylene Yield

decreased
22
ROT

wt. %
20
18
Base Catalyst ProfiMax
16
14
12
0 56 112 168 224 280 336
Conversion Day

Figure 3:
Using ZSM-5 additives from Grace Davison will increase FCC Unit Propylene Yields
overall gasoline octane. RONC and MONC have been dem-
8.0
onstrated to increase by 1 – 3 and 0.5 – 1.0 numbers, re-
7.5
spectively with no change in coke, dry gas or bottoms yield decreased
7.0 ROT
occurring. The octane improvements achievable do depend
6.5
on the feedstock and unit severity.
wt. %
6.0
5.5
ProfiMax
Figure 1 shows that within the Grace Davison portfolio of 5.0
ZSM-5 additives, ProfiMax is positioned between Olefins- 4.5
Max® and OlefinsUltra® in terms of activity. 4.0
0 56 112 168 224 280 336
Day

Maintaining LPG Yield at Low ROT

Figure 4:
FCC Unit Isobutylene Yields
In March 2008, Refinery A reduced the cracking severity by
lowering the ROT by 25 degrees C in order to increase LCO 2.5
yields. As expected, conversion decreased from ca. 84 to 76 2.4
2.3
wt.% and bottoms yield increased from ca. 5 to 7 wt.%. In ad-
2.2
dition, LPG dropped from ca. 24 to 18 wt.% (Figure 2). decreased
2.1 ROT
wt. %

2.0
1.9
Based on a proposal from Grace Davison, Refinery A decid-
1.8
ed to perform a ProfiMax trial with a target steady state level 1.7
ProfiMax
of 3 wt.%. The ProfiMax additive was preblended at a level 1.6
1.5
of 6 wt.% to the fresh FCC catalyst, which is twice the target
0 56 112 168 224 280 336
steady state level, to highlight the additive response and en-
Day
able the steady state level to be reached faster.
Figure 5:
Figure 2 also shows the influence of the ProfiMax ZSM-5 FCC Unit Total C4 Olefin Yields
additive on LPG yields. After LPG yield dipped below 18
9.0
wt.% due to the lower ROT, the subsequent addition of Profi-
8.5
Max immediately had a positive effect. LPG yield increased
decreased
by over 3 wt.% at the expense of gasoline yield, which de- 8.0 ROT
creased from ca. 53 to 50 wt.%. 7.5
wt. %

7.0
ProfiMax
Figure 3 shows the effect of reducing ROT on propylene. A 6.5
reduction of ca. 2.5 wt.% was observed, which was subse- 6.0
quently counteracted by the use of ProfiMax additive. It can 5.5
0 56 112 168 224 280 336
be seen that addition of ProfiMax had a significant effect on
Day
propylene, and the yield quickly increased by 1.5 wt.%.

21
ProfiMax also gave a major boost to the production of isobu-
tylene. As seen in Figure 4, isobutylene yield decreased by
ca. 0.5 wt.% when the lower severity conditions were em-
ployed, but this deficit was entirely recovered by the use of
ProfiMax. As a result a substantial improvement in the MTBE
yields was obtained.
As shown in Figure 5, a significant increase of more than 1
wt.% of total C4 olefin yields was observed with the addition
of ProfiMax. As a result, Refinery A achieved substantial im-
provements to the alkylate production.
In addition to the boost in C4 olefin yields, ProfiMax also in-
creased the isobutane yield by 1 wt.%.
Conclusion
In order to increase the LCO yield Refinery A reduced ROT
by 25 degrees C in their FCC unit. As expected, the ROT
reduction caused the LPG yield to decrease, but this was
subsequently brought back to similar levels through the use
of ProfiMax, a ZSM-5 additive from Grace Davison. The
22
addition of ProfiMax to the inventory at an estimated level of
ca. 2.2 wt.% resulted in various changes to the yield struc-
ture. The increase in LPG was mainly due to a gain in LPG
olefins, with both propylene and C4 olefins benefiting. Higher
isobutane yields were also observed. These shifts were at
the expense of the naphtha yield, which decreased accord-
ingly. In addition, naphtha RON/MON increased with the use
of ProfiMax. No impact on other yields, including dry gas,
was observed.
The unit data confirm the outstanding performance of the
ProfiMax additive in the FCC unit at Refinery A. The very high
LPG olefins yields achieved enabled the available capacity in
the Gas Concentration Unit (GCU) to be filled. The changes
in the yield structure resulted in significant increases in re-
finery grade propylene rundown, MTBE rundown and alky-
late rundown. LPG yields were quickly returning to the levels
observed before the reduction in ROT. However, Refinery A
stopped the Profimax additions due to a drop in demand for
refinery grade propylene. However, Refinery A considered
the trial to be a complete success, and will soon continue
ProfiMax additions as demand for propylene has started to
increase again.
 Reducing SOx Emissions
Using Super DESOX®:
European Case Study Colin Baillie

Grace Davison
Refining Technologies Europe

Renaud Kieffer Maria Luisa

Sargenti
Grace Davison Grace Davison
Refining Technologies Europe Refining Technologies Europe

Reducing FCCU SOx Emissions Figure 1:

Magnesium-Alumina Spinel Structure of
Although the amount of SOx emitted from FCC units is Super DESOX®
relatively small, it still accounts for most of the SOx released
from oil refineries. The use of FCC additives to reduce SOx
emissions is often the preferred route taken by refiners,
because they require very little capital investment and are
extremely effective in reducing SOx emissions.

Super DESOX® – The Technology

Super DESOX is based on a patented magnesium-alumina

spinel structure (Figure 1), which has been successfully used
by more than 70 refiners worldwide. Super DESOX has the
highest SOx reduction activity on the market and has quickly
become the industry standard.

In the FCCU regenerator, sulphur contained in the coke is

oxidised to SO2 and SO3. Both of these sulphur oxides are
absorbed on the SOx additive, where SO2 is further oxidised
to SO3 in the presence of oxygen and an oxidation catalyst
in the additive. The SO3 reacts with magnesium oxide in the
alumina spinel and is converted to magnesium sulphate. 

23
Compared to free magnesium oxide, the spinel in Super
DESOX is extremely effective for this sulphate formation and
a stable sulphate is formed under regenerator conditions.
In the FCCU reactor the magnesium sulphate is reduced
by hydrogen to form magnesium sulphide. Super DESOX
plays an important role here too because the magnesium in
the alumina spinel is less basic than free magnesium oxide
thereby making the sulphate easier to reduce. In addition,
vanadium on the spinel structure further decreases the
stability of the magnesium sulphate especially under reducing
conditions, and in the presence of steam. The magnesium
sulphide is then hydrolysed to a magnesium oxide in the
stripper, which then returns to the regenerator to complete
the catalytic cycle.
Case Study of Super DESOX® at a European
Refinery
Due to the various operating variables that can affect
SOx additive performance it is necessary to establish
a baseline of uncontrolled SOx emissions to be able to
calculate the true SOx reduction caused by the additive.
Such a baseline is calculated by performing correlations for
every relevant parameter based on pre-trial unit data. To
establish a baseline for Refinery A approximately 3 months
of pre-trial unit data was used. A high value of R (86.9) was
obtained, which signified an extremely good correlation.
Refinery A decided to use Super DESOX at 0.8 wt.% without
using a baseloading period. The effect of Super DESOX
was immediate with average SOx reductions of 24%
Figure 2:
Flue Gas SO2 Emissions Before and During Super DESOX® Additions
1400
Correlated SO2 (3% O2)
Measured SO2
1200
1000
SO2 (mg/Nm3)
800
600
400 0.8 wt.% Super DESOX
24% SOX reduction
200
0
21.10.08
18.11.08
16.12.08
13.01.09
24
observed (Figure 2). This can be effectively considered as a
baseloading period during which a stationary concentration of
additive is reached in the inventory. Even though the refinery
then decided to reduce Super DESOX pre-blending levels
to 0.5 wt.% for a short period, the average SOx reduction
during this period remained high at 29%. The refinery then
decided to increase Super DESOX pre-blending levels to 1.5
wt.% to gain an idea of just how much SOx reduction could
be achieved, which resulted in an average SOx reduction
of 54%. The pre-blending levels of Super DESOX was then
increased to 1.8 wt.% due to increased feed and slurry
sulphur levels, resulting in extremely impressive average
SOx-reduction levels of 66%.
As can be seen in Figure 2, the SOx values measured over
time were somewhat volatile. This is due to the variations in
feed and slurry sulphur content during the trial period, which
is also reflected in the calculated SOx levels. As shown in
Figure 3, feed sulphur varied between 0.31 and 0.52 wt.%,
while slurry sulphur varied between 0.6 and 0.9 wt.%.
During the period where Super DESOX was added at 1.5 wt.%
a serious inventory deactivation occurred due to increasing
vanadium contamination of the e-cat, as shown in Figure 4.
It is testament to the superior performance of Super DESOX
that even with the dramatically increased e-cat vanadium
levels, and the subsequent drop in MAT activity, excellent
2
levels of SOx reduction were still achieved.
In terms of retention levels of Super DESOX the refinery
acknowledged excellent performance. Indeed, Super
DESOX is recognised in the market for its excellent retention
properties.
1.8 wt.% Super DESOX
66% SOX reduction
0.5 wt.% Super DESOX
29% SOX reduction 1.5 wt.% Super DESOX
54% SOX reduction
10.02.09
10.03.09
07.04.09
05.05.09
02.06.09
30.06.09
28.07.09
25.08.09
22.09.09
20.10.09
17.11.09
15.12.09
 MAT (%) Sulphur content (%)

55
57
59
61
63
65
67
69
71
73
75
0.30
0.40
0.50
0.60
0.70
0.80
0.90
1.00

Figure 4:
Figure 3:

21.10.08 21.10.08

18.11.08 18.11.08

16.12.08 16.12.08

13.01.09 13.01.09

10.02.09 10.02.09
Feed and Slurry Sulphur Content

10.03.09 10.03.09

07.04.09 07.04.09

05.05.09 05.05.09

Inventory Deactivation by Vanadium Contamination

02.06.09 02.06.09

30.06.09 30.06.09

28.07.09 28.07.09

25.08.09 25.08.09

22.09.09 22.09.09

20.10.09 20.10.09
Feed sulphur
Slurry sulphur

MAT activity (%)

17.11.09 17.11.09

Vanadium on e-cat (ppm)

15.12.09 15.12.09

1000
1500
2000
2500
3000
3500
4000

Vanadium (ppm)

25
 Reducing NOx Emissions Using
XNOx® at Galp Energia Sines

Reducing FCCU NOx Emissions

Increasing environmental legislation

Jose Fernandes Tania Lopes is forcing refiners to reduce their NOx.

Inverno The FCCU regenerator is typically the

Galp Energia Sines
single largest source of NOx within a re-
finery and can account for as much as
40-50% of total refinery NOx emissions.
Galp Energia Sines
These NOx emissions are the result of
nitrogen impurities in the feed depositing
on the catalyst during the cracking reac-
tion. When the coke is burned off in the
regenerator, a portion of the nitrogen is
converted into NOx. FCC additives are
becoming an increasingly popular option

Fernando Maria Luisa

amongst refiners to reduce NOx emis-
sions as they require no additional infra-
Sanchez Sargenti structure or chemical reactants. Indeed,
NOx-reducing additives are now consid-
Grace Davison Grace Davison ered to be Best Available Technique from
Refining Technologies Europe Refining Technologies Europe the Integrated Pollution Prevention and
Control Directive.

26
XNOx®, a Non-Platinum Low- Figure 1:
NOx Combustion Promoter Establishing a Baseline for Uncontrolled NOx Emissions

Traditional Pt-based combustion pro- 2.0

moters are extremely effective at re- 1.8
NOx measured
NOx correlated
ducing CO, but unfortunately also dra-

Normalized NOx emissions

1.6
matically increase NOx emissions due
1.4
to the fact that platinum catalyses the
1.2
oxidation of intermediate nitrogen spe-
1.0 Average uncontrolled
cies, such as ammonia and cyanide emissions

gases. Low-NOx combustion promot- 0.8

ers were introduced to alleviate this 0.6

problem by retaining the CO oxidation 0.4

function while controlling the sharp 0.2
increase in NOx. XNOx is a non-Pt 0.0
based low-NOx combustion promoter -98 -94 -87 -80 -74 -67 -60 -53 -41 -27 -21 -11
Days
developed by Grace Davison, which
with a dual functionality actually re-
duces NOx levels at the same time as Figure 2:
retaining the CO oxidation function. Flue Gas NOx Emissions Before and During XNOx® Additions

A Case Study of XNOx® at the 2.0

Galp Energia Sines Refinery 1.8 NOx measured
NOx correlated
1.6
Normalized NOx emissions

In order to be able to accurately evalu-

1.4
ate the effect of the XNOx additive on
1.2
reducing NOx emissions, it is neces-
1.0 Average uncontrolled

sary to establish the corresponding

emissions

0.8 XNOx
XNO
baseline NOx levels that would have Start

been obtained without using the addi- 0.6

tive. Therefore the flue gas composi- 0.4

tion in the FCC stack, as well as other 0.2
Controlled NOx emissions

relevant operative variables, was mon- 0.0

-98 -87 -74 -60 -41 -21 1 11 37 50 67 84 95 109
itored for four months prior to the addi-
Days
tive trial. Excellent unit data was pro-
vided by the refinery for the four-month
pre-trial period, which enabled a cor- Figure 3:
relation to be generated using a linear Flue Gas NOx Emissions and Nitrogen Levels in Feed
regression analysis. A high value of R2
(84.7) confirms that the measured NOx
1.0 1.0
values and the NOx values obtained Average uncontrolled
emissions
0.9 0.9
using the correlation are well aligned,
0.8 0.8
Normalized Nitrogen in feed
Normalized NOx emissions

as shown in Figure 1.
0.7 0.7

The objective of the XNOx trial for the 0.6 0.6

refinery was to evaluate the extent to 0.5 0.5

which the NOx emissions could be low- 0.4 0.4
ered using an additive. The previous 0.3 0.3
combustion promoter was replaced 0.2 0.2
with XNOx on a 1:1 ratio (wt.%), which 0.1 NOx measured in stack 0.1
was preblended with the catalyst. The Nitrogen in feed
0.0 0.0
effect of XNOx was immediate with 2 10 22 42 52 65 78 87 98 107 116
Days
average NOx reductions of 40% ob-

27
 served during the first weeks (Figure
Figure 4: 2). In addition, the large scatter of NOx
CO2 Emissions Before and After the XNOx® Trial values observed in the pre-trial period
were dramatically reduced, leading to
1.3 a very stable and smooth operation.
As the additive level increased in the
1.2 inventory, the NOx emissions were re-
Normalized CO2 emissions

duced by more than 85%.

1.1 It is also important to comment that
during the trial period, a high variation
1.0
of the nitrogen levels in the feedstock
was observed. Despite this variation it
0.9
was possible to maintain very low and

0.8
stable NOx emissions (Figure 3).

0.7 Another important element when eval-

-98 -82 -67 -49 -21 3 21 45 67 86 102 uating low-NOx combustion promoters
Days
is to consider their performance to con-
trol afterburn and keep the FCCU run-
Figure 5: ning at the same operative conditions
Regenerator Afterburn Before and After the XNOx® Trial as when using the Pt-based combus-
tion promoters. Changes in CO and
CO2 in flue gas are the first indicators
Normalized Dilute Upper ΔT and Dilute Lower ΔT

1.6
of changes in the combustion reaction.
1.4
As can be seen in Figure 4, the use of
1.2 XNOx did not affect the CO2 emissions,
which were within the typical values for
1.0
the FCCU operation.
0.8

0.6 Combustion promoters accelerate the

CO combustion in the dense phase
0.4
and minimise temperature upsets that
Dilute - Lower Δ T
0.2 can occur as a result of afterburning
Dilute - Upper Δ T
0.0 in the dilute phase. Therefore proper
-98 -88 -74 -60 -39 -27 -21 -11 4 18 38 50 67 81 91 101 115 control of the afterburn is needed to
Days
ensure the temperatures during the
operation do not exceed the tolerance
Table 1: limits of the metallurgy of the regenera-
Summary of the XNOx® Trial at the Galp Sines Refinery tor internals. During the XNOx trial the
CP-3 XNOx Trial XNOx Trial afterburn was also monitored. The val-
ues oscillated slightly within the typical
intermediate
Pre-trial Last month range for the Galp FCCU operation,
months
Average Last Results
Average
but no significant changes were ob-
Feed Basic N (% wppm) Base 111% 136% served in the dilute phase temperature
% Reduction (Figure 5).
71% 87%
(based on N2 correlation)

Operating Data Table 1 shows a summary of the XNOx

O2 (%) Base Base - 0.7% Base -0.9% trial, in which up to 87% NOx reduc-
CO2 (%) Base Base Base -0.2% tions were achieved.
CO (ppm) Base Base Base
Feed Density gr/cc Base Base +0.003 Base -0.002
Feed Rate (m3/h) Base 98% Base 99% Base
% Atmospheric Residue Base Base +3% Base -6%
Average Reactor Temp. Base Base -1 °C Base

28
 Low-NOx
Combustion Promoter

NOx Reduction Additive

SOx Reduction Additive

XNOx®, DENOX®,
Super DESOX®
FCC Additives

Grace Davison introduces XNOx®, DENOX® & Super DESOX®,

the most effective additives to control environmental emissions
 Middle East
Nagib Haidar Refining Technologies
Conference
Grace Davison
Refining Technologies Europe
October 4th-7th 2010
Abu Dhabi
The Middle East Refining Technolo-
gies Conference organised by Grace
Davison and ART, took place at the Yas
Hotel between October 4th-7th, 2010 in
Abu Dhabi. The first two days of the
conference were chaired by Grace
Davison and focused on new FCC
technology, whilst the third, and final,
day was chaired by ART and was en-
tirely dedicated to catalysts and process
technologies for hydroprocessing.

The conference venue was the

Yas Hotel in Abu Dhabi

30

The key-note presentation was given by Iain McAlpine,
Wood Mackenzie
Iain McAlpine, Vice President Energy Consulting, Wood
Mackenzie, gave the key-note presentation on “Perspectives
on the Refining Industry in the Middle East”. He discussed
how the Middle East is a hot spot of refining activity, and
explained some of the advantages that refiners in the Middle
East have compared to the rest of the world, which are ex-
pected to continue to support investment. Iain then went on
to explain how the future investment drivers will depend on a
range of external influences. For example:
▪▪ how gasoline demand growth in the Middle East region
could either result in local FCC capacity additions or
favour imports from the EU as a lower cost option.
▪▪ the effect of rapid gasoline demand growth in China on
the Middle East export market.
▪▪ how government support for
labour-intensive downstream
petrochemical industries could
incentivise propylene production
from existing FCC capacity.
▪▪ how adoption of IMO’s proposals
for clean bunker fuels may drive
conversion of FCC capacity
to maximum distillate/heavy
feedstock mode.
Grace Davison then presented a com-
pany overview, highlighting its initiatives
and strong commitment to the Middle
East market. The session then proceed-
ed with a focus on resid processing. The Jeff Knight from UOP described the commercialisation of RxCatTM
Grace Davison FCC catalyst portfolio for technology
resid applications was briefly described,
as well in-house experience on the tech-
nical challenges when processing resid.
This was proceeded by a UOP pre-
sentation from Jeff Knight, Technology
Manager for UOP’s FCC and Hydroflu-
oric Alkylation processes. Jeff described
the commercialization of UOP’s RxCatTM
technology for low delta coke.
Lokesh Verma, Process Specialist
FCCU at Bapco, discussed how the
Bapco FCC unit has been revamped to
process vacuum resid with only modest
investment. He described how the use of
a Mix zone Temperature Control (MTC)
system as well as a new Packed Strip-
per, has allowed Bapco to operate one
of the highest feed concarbon processing units in the world
without a cat cooler. Lokesh also highlighted the importance
of choosing the most suitable FCC catalyst, and described
how the Grace Davison NEKTOR catalyst has provided the
Bapco unit with the high metals tolerance (the FCC unit e-cat
Ni+V levels are ca. 10,000 ppm), excellent bottoms cracking
performance and coke selectivity required.
The session was closed by a presentation from Björn As-
seln, the Business Manager of Central and Eastern Europe
for Tracerco. He discussed how gamma scans, advanced
tracer technology and non-intrusive detectors can be applied
to identify process conditions and the mechanical integrity of
the key sections of the FCCU such as the riser, reactor, strip-
per, regenerator and stand pipes.
31
The second day of the conference was
mainly related to maximising propylene
yield in the FCC unit. Grace Davison
presented catalyst and additive technol-
ogy that can enable refiners to increase/
maximise propylene yields, and in-house
experience was discussed on the tech-
nical issues that refiners must consider
to achieve this. This was followed by
a presentation from Axens by Romain
Roux, who is Deputy Product Line Man-
ager for Catalytic and Thermal Cracking
in Axens’ Technology Department. Ro-
main described the operation of Resid
to Propylene using R2R technology, as
well as PetroRiserSM technology for re- Lokesh Verma from Bapco Discussed the Revamp to Process
cycling of light cracked naphtha. Flex- Vacuum Resid
EneTM technology was also discussed, in
which less-reactive light olefins can be converted into longer
olefins, which are highly reactive and crack selectively
toward propylene in FCC.
A presentation on salt dispersants and slurry loop anti-foul-
ing agents was provided by Gianluca Guagnetti, who is the
Deputy Process Technological Unit Manager at Chimec. The
FCC session was then closed with a presentation on reduc-
ing SOx emissions in the FCC unit, which described an ex-
tremely successful trial of Super DESOX (a Grace Davison
SOx-reduction additive) at KNPC in Kuwait.
The final day was dedicated to catalysts and process tech-
nologies for hydroprocessing. An ART overview was given,
which was followed by a detailed presentation on SmART
and ApART catalysts for hydrotreating distillates. SmART
is Sulfur minimisation by ART for production of ULSD while
efficiently using available hydrogen resources. ApART is
Advanced pretreat by ART for improving FCC economics
by maximising reduction of sulfur, nitrogen, and aromatics
in FCC feedstocks. The final presentation of the conference
was given by Gerrit Polhaar, Technology Marketing Man-
ager, from Chevron Lummus Global (CLG), a global leader
in technology licensing for refinery hydroprocessing. Gerrit
discussed various hydroprocessing technologies, including
ISOCRACKING, ISODEWAXING, ISOFINISHING, Residue
Desulfurization (RDS, VRDS, OCR, UFR) and Residue Hy-
drocracking (LC-FINING).
As well as the high quality presentations, a key feature of the
conference was the extensive Q&A sessions, which gener-
ated a lot of interesting discussions. These discussions often
even continued into the social dinners
that were held in the evenings. The
gala dinner was held at the Yas Links
Golf Club, and was also attended by
Gregory E. Poling Vice President, W.
R. Grace & Co. President, Grace Davi-
son. Throughout the conference Grace
Davison and ART described its initia-
tives and strong commitment to the
Middle East market. We hope that the
exchange of information combined with
the social program made this confer-
ence an extremely useful and enjoy-
able event for all participants.

Romain Roux from Axens Discussed Propylene Maximisation

Technology

32
 The breakthrough in
deep resid cracking has arrived

ResidCrackeR
FCC Catalysts

Grace Davison Refining Technologies introduce ResidCrackeR,

a third-generation EnhanceR FCC catalyst for intrinsic bottoms cracking
©
2010 Grace GmbH & Co. KG

Catalagram®, Grace®, Grace Davison®, XNOx®,

DENOX®, Super DESOX®, OlefinsMax® and OlefinsUltra®
are registered trademarks in the United States and/or other
countries, of W.R. Grace & Co. Conn.

Grace Davison® is a business unit of W.R. Grace & Co. Conn.

This trademark list has been compiled using available

published information as of the publication date of this brochure
and may not accurately reflect current trademark ownership.

The information presented herein is derived from 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
which might be obtained from the use of our products. You should make no assumption that all safety
or environmental protection measures are indicated or that other measures may not be required.