IN THIS ISSUE

NACER - The Newest EnhanceR Catalyst Family for

Hydrotreated / Low Metals Feedstock 2
by Gordon McElhiney, Grace Davison

May 2008

Managing Editor: Grace Davison Celebrates 25 Years of

FCC Manufacture in Europe 7
by Stephen Addison, Grace Davison
Gordon McElhiney

Contributors:

Stephen Addison
Flying the Flag for RFCC in Central / West Africa:
An Application of Grace Davison Resid FCC Catalysts 9
Colin Baillie by Emmanuel Kwaku Darko, Tema Oil
Stefan Brandt
Emmanuel Kwaku Darko
Pietro Greco
David Hunt
Gordon McElhiney
European Region FCC E-Cat Trends: A Ten-Year Review
by Marilyn Moncrief, David Hunt, Kelly Stanford, Colin Baillie,
Grace Davison
13
Marilyn Moncrief
Kelly Stanford
~

ENI Commercial Experience with NEKTOR-ULCC

by Pietro Greco, Grace Davison 18

Grace GmbH & Co. KG

What Six Sigma Can Do for You
by Stefan Brandt, Grace Davison 22
In der Hollerhecke 1
67547 Worms, Germany
T +49 (0) 6241 403-1425
+49 (0) 6241 403-1608
F +49 (0) 6241 403-1455
19th World Petroleum Congress in Madrid
24
+49 (0) 6241 403-1240

www.grace.com
The informatiom contained herein is based

~
on our testing and experience and is offered
for the user’s consideration, investigation and
verification. Since operating and use conditions
vary and since we do not control such
conditions, we must DISCLAIM ANY WARRANTY,
EXPRESSED OR IMPLIED, with regard to results
to be obtained from the use of this product.
Test methods are available on request.
Grace Davison Refining Technologies Europe
© 2008
Grace GmbH & Co. KG

Catalagram European Edition May 2008 1

 NACER
The Newest
EnhanceR Catalyst Family
For Hydrotreated/Low
Metals Feedstocks

by Gordon McElhiney
Director, Marketing and Business Development
Grace Davison Refining Technologies Europe

T
he introduction of the
EnhanceR Technology
Platform in 2003
signalled a new approach to
FCC catalyst formulation and
manufacture. Rather than
making separate modifications
to the zeolite and matrix
components, the EnhanceR
Plant enabled processing
of intermediate and end-
product material. By this
means the four EnhanceR
Technologies can be deployed
synergistically, avoiding the
antagonistic consequences
frequently encountered when
using the separate matrix /
zeolite approach. The first
been gained manufacturing
catalysts in the EnhanceR Plant.
In addition, further R&D
projects have been carried out
to investigate and utilise the
special capabilities provided
by the EnhanceR Plant facilities
to develop modified versions
of the EnhanceR treatments.
These efforts have been
Figure 1:
The Excellent Market Acceptance of NEKTOR, NOMUS
and NADIUS
48
44
40
36
successful and now make
possible the introduction of
a new catalyst family, NACER,
a further evolution of NADIUS
for use with hydrotreated, low
metals feedstocks. NACER is
designed for high activity and
bottoms upgrading as well as
boosted C4 olefin selectivity
and tailored Delta Coke.
NADIUS (HT feeds)
NOMUS (resid)
NEKTOR (resid)

EnhanceR catalyst families 32

No. of FCC Units

to be commercialised were 28

NEKTOR and NOMUS for 24

resid, and NADIUS for clean, 20

hydrotreated feedstocks. _ 16

12

8
In the meantime these families
4
have enjoyed excellent market
0
acceptance (Figure 1) and
07

07

07

08
03

04

04

04

04

05

05

05

05

06

06

06

06

07

considerable experience has

20

20

20

20
20

20

20

20

20

20

20

20

20

20

20

20

20

20
2Q

3Q

4Q

1Q
4Q

1Q

2Q

3Q

4Q

1Q

2Q

3Q

4Q

1Q

2Q

3Q

4Q

1Q

2 www.e-catalysts.com
Figure 2:
SEM (Scanning Electron Microscopy) Clearly Shows Alumina Deposition on the Zeolite Surface

Before EAM HTD treatment After EAM HTD treatment

EAM HTD

Novel Acidity Modification  for the deposition feature.
A modified approach to the
standard EnhanceR Acidity
Modification (EAM) used in
NADIUS has been developed,
which also includes a material
deposition step. As a result the
surface of the zeolite crystals
in the catalyst is coated with
a thin layer of alumina, as can
be seen in Scanning Electron
Microscope photographs in
Figure 2. This novel treatment
is now designated EAMHTD, with
the HT indicating that it is for
hydrotreated / low feed metals
applications and the D standing
Figure 3:
Novel EPRHT Pore Restructuring Boosts Porosity
Novel EnhanceR Pore Restructuring
0.7
0.6
0.5
Pore Volume (cm³/g)
The alumina deposited on the
zeolite crystal surface is active
and, in view of its open porosity,
facilitates pre-cracking of large
feed molecules. This provides
higher activity, improved
bottoms cracking performance
and, due to the high cracking
to hydrogen transfer ratio,
contributes to increased C4
product olefinicity.
Novel Pore Restructuring
The macropores provide the
primary system of pathways
by which the feed molecules
NADIUS Enhanced
travel into and product mole-
cules exit from the catalyst mi-
crospheres. As such, having the
appropriate pore size distri-
bution is key to preventing
diffusion constraints which can
limit, in particular, bottoms
cracking and coke selectivity
potential.
Pore Restructuring is one of
the basic set of four EnhanceR
Technologies and finds use in
the NEKTOR, NEKTOR-ULCC
and NOMUS-DMAX families.
EnhanceR Pore Restructuring
is not used in NADIUS and it
was necessary to develop a
novel route for pore restructur-
ing that can be deployed with
the modified Acidity Modifica-
tion treatment for hydrotreated
/ low metals feeds described
above. This has been success-
fully achieved, with the novel
EPRHT pore restructuring pro-
viding a dramatic shift in the
pore size distribution, as shown
in Figure 3. The shift in po-

0.4 rosity is specifically targeted

at pore sizes in the range of
0.3 100-600 Angstrom diameter,
EPRHT which provide the optimal boost
0.2
in diffusivity.
0.1

0
10 100 1000
Pore Diameter [Å]

Catalagram European Edition May 2008 3

NACER the Newest Figure 4:
EnhanceR Catalyst Family The Route to NACER FCC Catalysts

Intended for use with

hydroteated/low metals feed-
stocks, the new NACER catalyst
NACER FCC Catalyst Family
family is based on the Structure
Stabilisation and Acidity EAM HTD Technology EPRHT Technology
Modification Technologies Zeolite
deployed in NADIUS grades.
SRAs
However, with NACER the Acidity Matrix Aluminas EnhanceR
Modification used is the novel
EAMHTD variant, with alumina TMAs Plant NACER
deposition. NACER catalysts Matrix Aluminas

also incorporate an additional, Al-Sol

third, EnhanceR Technology, Binder
namely the EPRHT developed
ESS Technology
expressly for this purpose. This
approach is summarised in Figure 5:
Figure 4. Conversion Response Surfaces for NADIUS and NACER

With such complexity in the

composition and manufacturing
route, and in view of the
importance of interactions,
which are inevitable, it is
necessary to take advantage
of statistical methods in
experimental design when
evaluating the robustness of
the formulation and identifying
the optimum. Two examples
of this are shown in Figures 5
and 6, which plot the response
surfaces for the key parameters
conversion and bottoms
upgrading. These figures
Figure 6:
show the improvements over
Bottoms Upgrading Response Surfaces for NADIUS and NACER
NADIUS achieved with NACER
by using the advanced EAMHTD
and additional EPRHT EnhanceR
treatments.

A key feature of NACER when

compared with NADIUS is the
improved C4 olefin yield, as
shown in Figure 7. A major
contribution to this is provided
by the active alumina layer
generated via the EAMHTD
treatment. C4 olefins are high
value products for those FCC
operations in which the feed
has been hydrotreated.

4 www.e-catalysts.com
Figure 7: Performance assessments of
Olefinicity Response Surface for NADIUS and NACER new NACER catalysts using
ACE pilot scale testing with
hydrotreated feedstock con-
firmed the targeted benefits
when compared with NADIUS
grades. An example of this is
shown in Figure 8, where the
higher conversion, higher C4
olefin yield and better bottoms
cracking are clearly evident.
The increased coke yield is
also deliberate and a benefit in
closing the heat balance with
such clean feed.
The first commercial trial of a
NACER catalyst is now running,
with more trials to start in the
Figure 8: near future.
Selectivity Benefits for NACER by ACE Testing, Metals Free,
CPS-3, HT Feed with Yields Interpolated at Constant Cat-to-Oil Summary
NADIUS 770 NACER 700
By combining the flexibility of
Cat-to-Oil 5.5 5.5
the holistic EnhanceR concept
Standard Conversion 76.2 higher conversion 77.7
with the capabilities of the
Hydrogen 0.07 0.11
special, purpose-built EnhanceR
Total C1 + C2 2.1 2.3
Plant it has been possible to
Propene 6.0 6.3
develop novel approaches to the
Total C3 7.0 7.4
Acidity Modification and Pore
C4-Olefins 8.6 higher C4= 8.9
Restructuring Technologies.
Total C3 + C4 (LPG) 20.7 21.6
These two Technologies, EAMHTD
Gasoline 50.6 50.3
and EPRHT, together with the ESS
Light Cycle Oil 14.3 14.0
Structure Stabilisation required
Heavy Cycle Oil > 337°C 9.5 lower HCO 8.2
to prevent hydrothermal
Coke 2.8 higher coke 3.4
degradation, now form the
basis of the newest EnhanceR
Figure 9: catalyst family, NACER, which
The EnhanceR Catalyst Portfolio, Developed for the Resid and is designed for high activity
Hydrotreated / Low Metals Feed Scenario and bottoms upgrading as well
as boosted C4 olefin selectivity
and tailored Delta Coke with
hydrotreated / low metals
Catalyst EnhanceR Performance Target Feed
feedstocks.
Family Technologies Characteristic Type
NACER is now undergoing
commercialisation, and com-
NEKTOR EPR + EMR Low Delta Coke Resid plements the EnhanceR
NEKTOR-ULCC EPR + EMR + EAMR Lowest Delta Coke Resid portfolio as shown in Figure 9.
The boundaries of the
NOMUS EAMR + ESS Max bottoms upgrading Resid additional, novel EnhanceR
NOMUS-DMAX EAMR + ESS + EPR LCO maximisation Resid manufacturing capabilities are
still being tested and further
NADIUS EAMHT + ESS High conversion HT new and interesting options are
NACER EAMHTD + ESS + EPRHT High conv., C4=, LCO/HCO HT under development.

Catalagram European Edition May 2008 5

6 www.e-catalysts.com
Grace Davison Celebrates 25 Years
of FCC Manufacture in Europe
by Stephen Addison
Director Manufacturing
Grace Davison Refining Technologies Europe
I
n October 2007, Grace
Davison celebrated the 25th
anniversary of FCC catalyst
production in Europe. The
construction and start up of a
dedicated FCC manufacturing
facility on the Worms site
in 1982 was an important
milestone because it was a
major step in establishing the
Refining Technologies Europe
Product Line. Whilst celebrating
the 25th anniversary we reflect
on a quarter of a century that
has seen continual growth in
the manufacturing capacity of
the site, including several plant
expansions. In addition, 4 years
ago the EnhanceR manufacturing
plant was commissioned,
allowing the development of new
catalyst families based on the
EnhanceR Technology Platform.
A scheduled maintenance
turnaround resulted in a busy
2007 for the Worms site. Such
maintenance turnarounds are
performed every 4 years on the
Grace Davison Worms site, to
allow the necessary inspection
and renewal of equipment to
ensure that we can consistently
manufacture products to the
highest quality standards.
The Refining Technologies
manufacturing facilities on
the Grace Davison Worms
site underwent the scheduled
maintenance turnaround from
the 17th to 24th April 2007.
During this period over 40
contractor companies were
present on site, generating an
increase of 50% on the usual
working population.
Catalagram European Edition May 2008
This turnaround also involved:
•• the overhaul and mainte-
nance of plant equipment
which cannot be serviced
during operation.
•• the completion of manda-
tory requirements, e.g.
pressure vessel testing and
maintenance of high volt-
age switch gear.
•• major plant alterations,
with installation or tie-in of
new or modified process /
equipment.
Maintenance work requires
management through good
planning and scheduling.
Planning for the 2007 Worms
site maintenance turnaround
started 12 months prior to the
event.
7
A major consideration during
the planning phase is safety.
This involves training con-
tractor personnel in safety
requirements, coordination of
work groups and activities,
and potential access for rescue
services. Production scheduling
and inventory planning ahead
of a maintenance turnaround
is critically important. It is vital
to continue the timely supply
of products to our customers
8 www.e-catalysts.com
during this period. In fact the
turnaround should be invisible
to customers.
The maintenance turnaround
was a complete success.
The start up of the process
plant took place in a timely
fashion, and the entire
turnaround proceeded smooth-
ly without incident. Deliveries
to customers remained on
schedule with no delays, and
the turnaround has ensured that
Grace Davison can comfortably
provide a regular supply of the
highest quality of products over
the intervening years until the
next maintenance shutdown.
This is planned for 2011 and it
will help maintain the success
of the Refining Technologies
Europe Product Line as we
approach our 30th anniversary.
 Flying the Flag for RFCC in Central / West Africa:
An Application of Grace Davison Resid
FCC Catalysts
by Emmanuel Kwaku Darko
Senior Process Engineer
Tema Oil

Summary Introduction Regenerator:

•• High efficiency combustor
Tema Oil (TOR) has successfully The TOR refinery is located in
•• Full combustion mode
operated a residue fluid cata- Ghana, and they have been op-
lytic cracking (RFCC) unit since erating a hydroskimming refin- •• Single stage
2002, which is reflected by the ery since 1963. In 1999, a deci- •• Equipped with catalyst
fact that TOR has reached re- sion was made to invest in an cooler
cord nickel levels in the Europe/ RFCC unit to upgrade their old
Middle-East/Africa/FSU region. hydroskimming refinery and
The evolving resid FCC catalyst fulfil the rapid growth in petro- Feed nozzles:
portfolio of Grace Davison has leum products consumption in •• OPTIMIX
been successfully utilised by the region. TOR elected to build
TOR, and this article highlights a 14 KBPD UOP RFCC unit, hav-
Riser separation device:
the yield and selectivity ben- ing the following main design
efits achieved with these cata- features: •• VSS
lysts when processing heavy
feedstocks.

Catalagram European Edition May 2008 9

Figure 1: feedstocks as demonstrated by
Nickel Content in the Feedstock (Monthly Averaged Back Figures 1 and 2, which show
Calculation from E-Cat Metals) how the feed nickel and vana-
dium content have more than
doubled compared to the de-
35
sign content.
30 Figures 3 and 4 show e-cat
25
nickel and vanadium levels, re-
spectively. It can be seen that e-
20
Ni (ppm)

cat Ni levels have peaked at an

15 impressive 17,000 ppm, which
design (12.1 ppm) is a record in the Europe/Mid-
10
dle-East/Africa/FSU region. It
5 should be noted that since the
unit start up, TOR has never
0
used antimony passivator. E-
F M M J J A S J F M AM J J A O N D J F M AM J J A S O N D J F M J J A S
Month 2003-2004-2005-2006 cat vanadium levels have also
increased, and have reached
RFCC Unit History at availability of feedstocks has 1,500 ppm.
TEMA OIL been insufficient, which has
forced TOR to operate at a low- The average performance of the
The RFCC unit was successful- er throughput than design for TOR RFCC unit will now be dis-
ly started up in October 2002 most of the time. However, this cussed. Various operating pe-
processing pure straight run at- has allowed the processing of riods have been distinguished,
mospheric residue originating much poorer feedstocks than which mainly differ by the feed-
from Nigerian crudes. TOR se- originally specified. stock quality, throughput, re-
lected a catalyst from the Grace generator operating conditions,
Davison Ultima family, and the To improve the unit perfor- catalyst type and make-up rate.
results of the guarantee test mance, Grace Davison recom- Table 1 provides commercial
run exceeded the licensor fore- mended a switch from the Ul- data from the period when
cast and TOR expectations. Al- tima to the ResidMax catalyst ResidMax first replaced the
though the unit has now been in February 2004. ResidMax ULTIMA catalyst. This period
running well for 5 years, some allowed the diversification of is characterised by an increase
operating problems have been the crude sources and the pro- in throughput and feed metals.
encountered. For example, the cessing of more contaminated At a constant catalyst addition
rate the e-cat MAT increased
slightly, demonstrating the bet-
Figure 2: ter stability and metals toler-
Vanadium Content in the Feedstock (Monthly Averaged Back ance of ResidMax. Conversion
Calculation from E-Cat Metals) levels increased slightly, and
dry gas and coke selectivities
improved with ResidMax to the
4 benefit of naphtha.
As shown in Table 2, the second
3 ResidMax period was operated
with a lower throughput due to a
lack of available feed. However,
V (ppm)

2
this enabled the processing of
design (1.4 ppm)
feedstocks with much higher
1 Concarbon and metals. The
catalyst addition rate was kept
constant, and the e-cat activity
0
F M M J J A S J F M AM J J A O N D J F M AM J J A S O N D J F M J J A S dropped by approximately
Month 2003-2004-2005-2006 3 numbers, which is only a

10 www.e-catalysts.com
moderate decrease considering Figure 3:
the significant increase in Equilibrium-Catalyst Nickel Level
feed metals. It can be seen
that LPG and naphtha yields
were maintained, but bottoms
18,000
upgrading suffered slightly due
16,000
to the decrease in activity.
During the third ResidMax pe- 14,000

riod (Table 3), the unit through- 12,000

put was dropped slightly but

Ni (ppm)
10,000
feed contaminants reached 8,000
record levels, and Concarbon
6,000
reached an impressive 5.1. The
4,000
catalyst addition rate was sub-
stantially increased resulting in 2,000

a decrease in e-cat metal levels 0

and a significant increase in Sep. 2002 to Oct. 2006

MAT. Consequently, conversion

increased and bottoms upgrad-
ing clearly improved. This dem-
onstrates that sufficiently high
MAT needs to be maintained
even when processing very
heavy feedstocks.
“e-cat Ni levels have peaked at an
TOR recently decided to switch impressive 17,000 ppm, which
from ResidMax to NEKTOR to
allow for further improvement
in resid processing. NEKTOR
is a record in the Europe/Middle-
entered the unit in April 2007
and has already resulted in a East/Africa/FSU region”
clear improvement of the unit
performance, which will be
detailed in a future publication.

Conclusions

The Grace Davison resid FCC Figure 4:

catalyst portfolio has helped
Equilibrium-Catalyst Vanadium Level
TOR to successfully pro-
cess heavier crudes in their
RFCC unit. Good performance
1,600
was initially observed with
ULTIMA and the unit ran un- 1,400
constrained. The subsequent
switch to ResidMax allowed 1,200

TOR to process feedstocks with

V (ppm)

higher Concarbon and contami- 1,000

nant metals, whilst maintain-

800
ing conversion and bottoms
upgrading. Most recently, NEK-
600
TOR has been utilised resulting
in further improvement of unit 400
performance. Sep. 2002 to Oct. 2006

Catalagram European Edition May 2008 11

Table 1:
Replacing ULTIMA with ResidMax

Averaged Operating Period Feb. 03 - Feb. 04 Mar.04 - May 05

ULTIMA ResidMax
Feed Ni+V+Na wtppm 17.3 18.2
Throughput m3/hr 80.0 91.7
Fresh Cat Addition Rate mt/d 2.3 2.3
E-Cat MA wt% 65.1 66.0
C2- wt% 3.0 2.7
LPG wt% 12.0 12.2
Naphtha (90% @ 180°C) wt% 46.0 47.8
LCO (90% @332°C) wt% 18.4 17.6
MCB wt% 13.2 13.4
Coke wt% 7.5 6.4
Conversion wt% 68.4 69.0

Table 2:
The Second ResidMax Period

Averaged Operating Period Mar. 04 - May 05 Jun.05 - Feb 06

ResidMax ResidMax
Conradson Carbon wt% 3.2 4.8
Feed Ni+V+Na wtppm 18.2 40.7
Throughput m3/hr 91.7 81.2
Fresh Cat Addition Rate mt/d 2.3 2.4
E-Cat MA wt% 66.0 62.6
C2- wt% 2.7 3.0
LPG wt% 12.2 12.4
Naphtha (90% @ 180°C) wt% 47.8 47.9
LCO (90% @332°C) wt% 17.6 14.7
MCB wt% 13.4 14.0
Coke wt% 6.4 8.0
Conversion wt% 69.0 71.3

Table 3:
The Third ResidMax Period

Averaged Operating Period Jun.05 - Feb 06 May 06 - Sep. 06

ResidMax ResidMax
Conradson Carbon wt% 4.8 5.1
Feed Ni+V+Na wtppm 40.7 58.2
Throughput m3/hr 81.2 76.0
Fresh Cat Addition Rate mt/d 2.4 4.3
E-Cat MA wt% 62.6 68.3
E-Cat V/Ni wtppm 1140/13510 1040/10370
C2- wt% 3.0 3.7
LPG wt% 12.4 14.9
Naphtha (90% @180°C) wt% 47.9 48.3
LCO (90% @332°C) wt% 14.7 13.5
MCB wt% 14.0 10.6
Coke wt% 8.0 9.0
Conversion wt% 71.3 75.9

12 www.e-catalysts.com
 European Region FCC E-Cat Trends:
A Ten-Year Review
by Marilyn Moncrief, David Hunt, Kelly Stanford, Colin Baillie
Grace Davison Refining Technologies

T
housands of equilibrium
fluid cracking catalyst
(e-cat) samples are
tested each year in the Grace
Davison Refining Technologies
laboratories. These samples
provide important insights into
FCC unit operations and are
critical for unit optimisation
and troubleshooting.
The purpose of this article
is twofold. First, it will
communicate how e-cat activity,
contaminants and other
properties have shifted over the
past ten years in the European
region.1 Second, it will allow
has experienced an increase in
activity from an average value
of below 67 to current values
of ca. 69.5. The majority of the
increase was observed between
1997 and 2003, with the values
stabilising somewhat in the
period since.
Figure 1:
Average MAT Activity in the European Region 1997-2006
70
69
MAT, wt.%
Higher activity is consistent
with increases seen in e-cat rare
earth content (Figure 2) and
e-cat unit cell size (Figure 3).
In the European region average
rare earth content has climbed
more than 50% over the last
ten years, from below 1.7 to

the individual refiner to rank

68
their own FCC e-cat properties
relative to the industry in
several key categories.
67

Figure 1 identifies interesting

trends in MAT activity. In the last
66
ten years, the European region 1997 1998 1999 2000 2001 2002 2003 2004 2005 2006

Catalagram European Edition May 2008 13

Figure 2:
Average Rare Earth in the European Region 1997-2006 2.6 wt.%. This increase in rare
earth has been matched by a
similar increase in unit cell size,
2.9
from 24.28 to 24.31 Å over the
period 1997-2006.
2.7

2.5 FCC catalyst alumina content

has experienced a steady up-
RE2O3, wt.%

2.3 ward trend from 41.2 to 46.9

wt.%, as shown in Figure 4. This
2.1
increase in alumina confirms
the importance of the matrix
1.9
function for FCC catalyst per-
1.7 formance.2
Trends in e-cat contaminant
1.5 metals can be seen in Figures
1997 1998 1999 2000 2001 2002 2003 2004 2005 2006
5 to 11. Nickel has increased
steadily since 1997 by over 40%
Figure 3: from ca. 1050 to over 1500
Average Unit Cell Size in the European Region 1997-2006
ppm (Figure 5). Vanadium lev-
els have also increased in the
24.33 last ten years but to a much
24.32
lesser extent than nickel with
values increasing from ca. 1800
24.32
to 1900 ppm (Figure 6). Howev-
24.31
er, vanadium levels were actu-
24.31 ally on the decrease until 2002,
UCS, Å

24.30 at which point the levels have

24.30
steadily increased. Nickel, and
to a lesser extent vanadium,
24.29
acts as a dehydrogenation cata-
24.29
lyst that increases the yields of
24.28 the unwanted products hydro-
24.28 gen and coke.3 Vanadium is also
1997 1998 1999 2000 2001 2002 2003 2004 2005 2006
mobile under FCC regenerator
conditions and reduces catalyst
Figure 4: activity by destroying zeolite
Average Alumina in the European Region 1997-2006 framework.4

Increased e-cat activity together

48.0
with higher nickel and vanadi-
47.0 um levels suggest that today’s
catalysts have improved zeolite
46.0
and matrix design for metals
45.0 trapping.
Al2O3, wt.%

44.0
Although the average nickel and
43.0
vanadium are increasing across
the board, the e-cat database
42.0
also provides evidence for a
41.0
growing number of FCC units
processing low metals feeds in
40.0
1997 1998 1999 2000 2001 2002 2003 2004 2005 2006

14 www.e-catalysts.com
 Figure 5:
a response to the increasingly
Average Nickel in the European Region 1997-2006
stringent regulations for low-
sulphur gasoline and diesel fu-
els. Figure 7 shows the average 1800

e-cat Ni+V levels for refiners

processing low metals feeds 1600
(defined here as Ni+V < 1000
ppm). In the last five years, the
average nickel and vanadium 1400

Ni, ppm
levels have fallen from 500 to
335 ppm in this feed sector. 1200

In contrast, Figure 8 shows av-

1000
erage e-cat Ni+V levels for re-
finers processing resid feeds
(defined here as Ni+V > 3000 800
1997 1998 1999 2000 2001 2002 2003 2004 2005 2006
ppm). It is clear that in this pro-
cessing scenario the average
metals levels are increasing, Figure 6:
with an increase in over 25% Average Vanadium in the European Region 1997-2006
from ca. 4850 to 6100 ppm.
2400
Average iron levels have
dropped by 11% in the Euro- 2200
pean region from 0.535 wt.%
in 1997 to 0.476 wt.% in 2006 2000
(Figure 9). Organic-based iron
V, ppm

deposited on the catalyst dur- 1800

ing the cracking reactions can
have a serious adverse effect 1600
on activity and bottoms crack-
ing.5 1400

Calcium levels remained stable 1200

in the European region between 1997 1998 1999 2000 2001 2002 2003 2004 2005 2006

1997 and 2002 (Figure 10).

However, calcium levels have Figure 7:
doubled in the period since Average Ni+V in the European Region in the Low Metals Feed
2002, and in 2006 the aver- Sector (Ni+V < 1000 ppm) 2002-2006
age value was ca. 0.065 wt.%.
600
Calcium is often found on the
surface of the e-cat together
with iron, and may be involved
500
in the mechanism by which iron
poisons the e-cat.
Ni+V, ppm

400
Sodium has remained fairly
constant over the last decade
with an overall slight increase
300
of 7% (Figure 11). Sodium on
e-cat comes both from the raw
materials used to manufacture
200
2002 2003 2004 2005 2006

Catalagram European Edition May 2008 15


FCC catalysts, as well as salt
contamination in the feedstock.
Sodium can deactivate the cata-
lyst by poisoning the acid sites
Figure 8:
Average Ni+V in the European Region in the Resid Feed Sector
(Ni+V > 3000 ppm) 2002-2006
7000

on the matrix and zeolite, and

also by surface area sintering.6

To summarise, data presented 6000

in this article suggests that the

Ni+V, ppm
FCC industry in the European
region increasingly values high
activity catalysts. In addition, 5000

e-cat contaminant metals, such

as nickel, vanadium, calcium
and sodium, continue to in-
crease. As a result, the industry 4000
2002 2003 2004 2005 2006
will continue to demand FCC
catalysts that provide excellent
coke selectivity.

Figures 5 to 8 clearly show the

diversifying feedstock scenario
in European Region FCCU oper-
ations, with e-cat metals levels “e-cat contaminant metals, such
revealing increases in the resid
and low metals feed sectors, at
the expense of the “classical” as nickel, vanadium, calcium and
VGO feed type. In response to
this diversifying feedstock sce- sodium, continue to increase”
nario Grace Davison has de-
veloped catalyst families spe-
cifically designed for resid and
hydrotreated feed sectors.

Figure 9:
Average Iron in the European Region 1997-2006

0.60

0.58

0.56

0.54

0.52
Fe, wt.%

0.50

0.48

0.46

0.44

0.42

0.40
1997 1998 1999 2000 2001 2002 2003 2004 2005 2006

16 www.e-catalysts.com
Figure 10:
Average Calcium in the European Region 1997-2006 References

1. For a recent ten-year review of

0.10 worldwide FCC e-cat trends, see
Moncrief, Hunt and Stafford,

0.08 “Worldwide FCC Equilibrium Cata-

lyst Trends – A Ten-Year Review,”
US Catalagram No. 102, 2008,
0.06
pg.17-23.
CaO, wt.%

2. Grace has recently reported the

0.04 value of alumina-sol catalyst tech-
nologies, see Petti, Yaluris and
Hunt, “Recent Commercial Experi-
0.02
ence in Improving Refining Profit-
ability with Grace Davison Alumi-
0.00
na-Sol Catalysts,” US Catalagram
1997 1998 1999 2000 2001 2002 2003 2004 2005 2006
No. 99, 2006, pg. 2-11.
3. Petti, Tomczak, Pereira and Cheng,
“Investigation of Nickel Species on
Commercial FCC Equilibrium Cat-
alysts – Implications on Catalysts
“e-cat metals levels reveal Performance and Laboratory Eval-
uation,” Applied Catalysis General,

increases in the resid and low 169, 1998, pg. 95-109.

4. Wormsbecher, Cheng, Kim and
Harding, “Deactivation and Test-
metals feed sectors, at the ing of Hydrocarbon Processing
Catalysts,” ACS Symposium Series

expense of the “classical” VGO 634, 1996 American Chemical So-

ciety 1996, pg. 283-295.

feed type” 5. Yaluris, et al, “The Effects of Fe

Poisoning on FCC Catalysts,”
NPRA Annual Meeting 2001, New
Orleans, LA, AM 01-59.
6. Zhao and Cheng, “ Deactivation
and Testing of Hydrocarbon Pro-
Figure 11: cessing Catalysts,” ACS Sympo-
Average Sodium in the European Region 1997-2006 sium Series 634, 1996 American
Chemical Society 1996, pg. 159-
0.30 170.

0.29

0.28

0.27

0.26
Na, wt.%

0.25

0.24

0.23

0.22

0.21

0.20
1997 1998 1999 2000 2001 2002 2003 2004 2005 2006

Catalagram European Edition May 2008 17

 ENI Commercial Experience
with NEKTOR-ULCC

by Pietro Greco
Regional Technical Sales Manager
Grace Davison Refining Technologies Europe

Introduction ENI Catalyst Evaluation FCCU Operating Data

program

The main FCC unit objective at In 2006 an extensive evalua- As shown by the FCCU operat-
the ENI Sannazzaro refinery is tion of FCC catalysts was per- ing data in Table 1, the switch
to maximise atmospheric resi- formed. The reference catalyst from NEKTOR to NEKTOR-ULCC
due processed in the feed. Oth- in this screening was NEKTOR, in the Sannazzaro FCC Unit re-
er unit objectives include: used with great success in the sulted in reduced hydrogen in
ENI circuit. From the data gen- flue gas. Indeed, the hydrogen
•• Minimising dry gas yield erated with the DCR circulat- content was reduced by 33%
•• Maximising slurry conver- ing pilot plant riser at the ENI during the January to July 2007
sion at constant gasoline S. Donato Research Center in period, despite an increase in
yields Milan it was established that Ni/Sb ratio.
•• Maximising olefins ratio of NEKTOR-ULCC offered the most
C4/C3 benefits. To summarise, at con- This is further evidenced in
•• Minimising sulphur in stant conversion NEKTOR-ULCC Figure 1, which shows that
gasoline resulted in slightly higher activ- NEKTOR-ULCC resulted in low-
•• Maximising gasoline MON/ ity, lower hydrogen and coke er hydrogen in the flue gas at
RON and increased gasoline. constant nickel equivalents.

Table 1:
Reduction in Hydrogen in Flue Gas

NEKTOR NEKTOR-ULCC
Jan Feb March April May June July
H2 in F.G (%Mol) 14.5 13.5 12.6 11.1 11.5 9.8 9.5
Ni (avg ppm) 3407 3624 3383 3421 3421 3220 2948
Sb (avg ppm) 503 593 570 527 598 474 349
Ni/Sb 6.8 6.1 5.9 6.5 5.7 6.8 8.5

18 www.e-catalysts.com
 Figure 1:
Hydrogen in the Flue Gas at Constant Nickel Equivalent
Supporting E-Cat Data
25.0
The following section describes 23.0
the E-Cat trends as the catalyst 21.0

Hydrogen (mol %)
changed out from NEKTOR to 19.0
NEKTOR-ULCC. 17.0
15.0
Figure 2 demonstrates that 13.0
NEKTOR-ULCC results in a clear
11.0
reduction in the E-Cat gas fac-
9.0
tor. The reduction in the E-Cat
7.0 H2 NEKTOR
gas factor is due to the excel- H2 NEKTOR- ULCC
lent metals tolerance exhibited 5.0

00
00
00
00

00
00
by NEKTOR-ULCC.

45
35
30
20

40
25
Ni equivalents (Adjusted for Sb)
This is further demonstrated in
Figure 3, which shows how the Figure 2:
E-Cat Gas Factor is reduced de- Reduction of E-Cat Gas Factor at Constant Nickel Equivalent
spite the significant increase in
the E-Cat nickel equivalents.
4.5
NEKTOR-ULCC also resulted in a 4.0
reduction of the E-Cat coke fac-
3.5
tor as evidenced in Figure 4.
Gas Factor

In addition, E-Cat MAT also 3.0

slightly increased with values 2.5
approximately 1% higher (Fig-
2.0
ure 5).
1.5
NEKTOR NEKTOR-ULCC
E-Cat samples taken from the 1.0
Sannazzaro FCC unit at a 50% 00
00
00
00
00

00
00
00
00

change-out level were analysed

39
35
31
27
25

41
37
33
29

by ENI at S. Donato in a Single (Ni+V/4-0.4/0.33*Sb)

Receiver SCT MAT unit. To sum-
marise, NEKTOR-ULCC resulted Figure 3:
in the following trends: Reduction of E-Cat Gas Factor Despite Increasing Nickel
Equivalents
•• Higher conversion
3.5 5,000
•• Increased LPG and gasoline
yields
•• Similar LPG olefinicity 3.0 4,500
•• Improved bottoms upgrad-
Ni Equiv

ing
2.5 4,000
GF

2.0 3,500

NEKTOR NEKTOR-ULCC

1.5 3,000
Date
GF Ni Equiv.

Catalagram European Edition May 2008 19

 Figure 4:
Reduction of E-Cat Coke Factor at Constant Nickel Equivalents
Conclusions
2.0
The switch from NEKTOR to
1.8
NEKTOR-ULCC in the Sannazza-
1.6 ro FCC unit resulted in a clear
Coke Factor

1.4 reduction in hydrogen yield,

coke make and Delta Coke.
1.2 This has opened new oppor-
1.0 tunities for processing more
atmospheric residue, or in-
0.8 creasing feed rate at constant
NEKTOR NEKTOR-ULCC
0.6 residue. Further improvements
include higher conversion lev-

00
00
00

00
00
00
00

00
00

els, increased LPG and gasoline

41
35
31

39
37
33
29
25

27

(Ni+V/4-0.4/0.33*Sb) yields and improved bottoms

cracking.

“E-Cat Gas Factor is reduced

despite the significant increase
in the E-Cat nickel equivalents”

Figure 5:
E-Cat MAT

76

74

72
MAT, wt. %

70

68

66
NEKTOR NEKTOR-ULCC
64
50

00
50

00
50

00
00

50

00

72

75
67

70
62

65
55

57

60

V + Na, ppm

20 www.e-catalysts.com
Catalagram European Edition May 2008 21
 What Six Sigma Can
Do for You
by Stefan Brandt
Regional Technical Sales Manager
Grace Davison Refining Technologies Europe

G
race Davison began im-
plementing Six Sigma
several years ago in
1999. The “Six Sigma” concept
is often misunderstood, so dur-
ing the implementation phase
the following definition was
used to help clarify what was re-
ally meant.
Six Sigma is a well-defined
methodology involving
• the rigorous application of a
set of statistical tools
• by teams lead by specially
trained experts (Black Belts)
• to eliminate defects/errors
• in carefully selected proj-
ects
• which are closely aligned
with the company strategy
• and bring precisely defined
and monitored financial
contributions.
Basic to Six Sigma is the eight-
component toolbox described
in Figure 1. Clearly these tools
are in themselves neither new
nor revolutionary, so what
makes Six Sigma so special? It
is the consequent application of
these tools to process analysis The most frequently encoun-
and improvement throughout tered applications of the Six
the organisation which makes Sigma technique are to be
a Six Sigma company different. found in the manufacturing en-
Training and, in particular, com- vironment. It would be a mis-
mitment and support from Top take, however, to think that
Management are essential to Six Sigma is only applicable to
make the Six Sigma approach production processes. Design
an integral part of the organisa- for Six Sigma, DFSS, is a variant
tional culture. using advanced statistical tech-
niques in R&D, and is being
A recent further refinement, extensively used in developing
Lean Six Sigma, is now being our EnhanceR-based catalyst
deployed within Grace Davison formulations. With increased
with the objectives of increas- experience in Six Sigma and,
ing productivity and reducing / in particular, widespread train-
eliminating waste. ing through the workforce
Figure 1:
The Eight Six Sigma Tools
The Eight Six Sigma Tools:
• Process Maps
• Cause and Effect (C&E) Matrix
• Measurement Systems Analysis
• Capability Studies
• Failure Mode and Effects Analysis (FMEA)
• Multi-Vari Studies
• Design of Experiments (DOE)
• Control Plans

22 www.e-catalysts.com
regarding the Six Sigma Tool- Figure 2:
box (Black, Green, Yellow Belt The WFCC-138 Alarm Management FCC
qualifications) the Six Sigma
approach is now being suc-
700
cessfully applied to the trans-
before
actional processes operating in 600
after
administrative areas of the or-
500
ganisation.
400

Alarms
Six Sigma is also used in our
300
Technical Service, for instance
when analysing large, complex 200
data sets in connection with
100
troubleshooting customer op-
erations. Another Technical Ser- 0
Chattering Program
vice application for customer standing alarms alarms / h
alarms / h messages / h
support is the planning, perfor- before 75 274 600 120
mance and subsequent analysis after 30 70 300 60

of environmental additive trials.

There is increasing interest in
these trials as public health and
environmental concerns bring
legislation for tighter emission
limits. It is important to draw
accurate conclusions regarding
cost effectiveness of the addi-
tive from such trials, which are
often short and upset-prone.
One more application of Six
Sigma that is creating interest
amongst our customers actu-
ally derives from the Manufac-
turing environment. This proj-
ect concerned optimisation
of the Process Control System
alarm management. Figure 2
shows the significant reduc-
tions achieved in each of the
four alarm categories. FCC unit
operations certainly could also
benefit from a similar Six Sig-
ma process control system im-
provement.

Clearly Six Sigma goes beyond

the limited scope of internal
usage. Contact us to find out
more about what Six Sigma can
do for you.

Catalagram European Edition May 2008 23

 19TH WORLD PETROLEUM CONGRESS
JUNE 29th to JULY 3rd SPAIN MADRID 2008

The World Petroleum Congress is considered to be the most influential

meeting place of the global oil and gas industry, and this year it
will be celebrating 75 years of excellence in Madrid from June 29th
until July 3rd. This is where governments and oil companies, IOCs
and NOCs, industry and stakeholders from around the globe come
together to set out the way forward for the petroleum sector. Held
every three years, the World Petroleum Congress is expecting around
4000 delegates from countries all over the globe.

CEPSA have recently announced that they will be presenting a paper

during the WPC discussing the performance of the Grace Davison
Protagon-20 FCC Catalyst at the CEPSA Huelva refinery. CEPSA owns
three refineries in Spain, with an overall distillation capacity of 21
million tons of crude per year. Two of these refineries have FCC
units, both of which are using ProtAgon catalysts.

ProtAgon catalysts are designed to have an enhanced propylene

selectivity, enabling high propylene yields for FCC units running in
the petrochemical mode. These high propylene yields are achieved
without a loss of the intrinsic cracking activity.

Grace Davison is proud to be a sponsor of the World Petroleum

Congress 2008, and we look forward to meeting you there.

~
Grace Davison Refining Technologies

24 www.e-catalysts.com