Catalagram

MARCH 2012 / www.grace.com

A Catalysts Technologies Publication

Rare earth price volatility is a serious issue facing the global refining industry.
Grace, with our long history of innovation and strong R&D, leads the industry
with the first line of commercially successful zero/low rare earth FCC catalysts:
the REpLaCeR® family.

Launched in the first quarter of 2011, the REpLaCeR® family includes five new
catalysts for both hydrotreated and resid feed processing with zero and low
rare earth content. The REpLaCeR® family of catalysts utilizes proprietary
zeolites and state-of-the-art stabilization methods to deliver performance similar
to current rare earth-based FCC technologies.

We’re also investing in our plants to bring these products to the refining industry
quickly and globally.

So if you’re concerned about rare earth pricing and availability, but need optimal
FCC performance, call the technical experts at Grace. We’ll customize a solution
using one of our new zero/low rare earth catalysts that delivers the yields you expect.

Grace Catalysts Technologies Europe W. R. Grace Singapore

7500 Grace Drive Grace GmbH & Co. KG PTE Ltd.
Columbia, MD 21044 USA In der Hollerhecke 1 501 Orchard Road
+1.410.531.4000 67547 Worms, Germany #07-02 Wheelock Place
+49.6241.403.00 Singapore 238880
+65.6737.5488
 The Successful Development and Commercialisation of
2 Catalagram
MARCH 2012 / www.grace.com

Zero- and Low-Rare-Earth FCC Catalysts A Catalysts Technologies Publication

By Colin Baillie and Rosann Schiller,

Grace Catalysts Technologies

Improved Product Yields and Attrition Resistance Using the

7 ResidCrackeRTM FCC Catalyst at BAYERNOIL Neustadt
By Colin Baillie and Sabeeth Srikantharajah,
Grace Catalysts Technologies,
and Bernhard Zahnbrecher,
BAYERNOIL

Development of New Catalysts for Middle Distillates European

11 Maximisation
Catalagram
By Ruben Miravalles and Tamara Galindo, Repsol
MARCH 2012
Improving Catalyst Management at the Orpic Sohar
16 Refinery Managing Editor:
Colin Baillie
By Maria Luisa Sargenti and Nathan Ergonul and Matthias Scherer,
Grace Catalysts Technologies
and Hemant Upadhyay, Robert McClung and Talal Said Al Rawahi,
Contributors:
Orpic Refinery
Colin Baillie
14th Grace FCC Technology Conference Nathan Ergonul
19 By Colin Baillie,
Tamara Galindo
Maria Luisa Sargenti
Grace Catalysts Technologies Matthias Scherer
Rosann Schiller
Editorial Sabeeth Srikantharajah

2012 is upon us, and it will be a challenging year for many refineries. Extra capacity from new refineries
Guest Contributors:
in emerging regions is expected to put increasing pressure on refineries in more established centres.
Robert McClung
Ruben Miravalles
While many companies cut research and development during difficult economic times, Grace has
Hemant Upadhyay
held R&D expenditures and increased capital budgets to support investment in new technologies. Talal Said Wasser Al Rawahi
We continue to invest heavily in R&D as we recognise the importance of building strong customer Bernhard Zahnbrecher
relationships by providing the most innovative and high-performing products available.

An example of such innovation is provided in the opening article that discusses the REpLaCeR® Please address your
comments to:
series of catalysts, which are being used in over 50 applications globally. This highlights how Grace
refining.catalysts@grace.com
leads the industry with the first commercially successful low and zero rare-earth FCC
catalysts. In addition, this edition of the European Catalagram® includes a BAYERNOIL article on Grace Catalysts
ResidCrackeRTM our latest catalyst for resid processing, as well as a Repsol article on DieseliseRTM, Technologies
In der Hollerhecke 1
a state-of-the-art technology for LCO maximisation. Our world-class technical service engineers
67547 Worms, Germany
continue to support you so that you obtain the maximum value from our commitment to the future +49.6241.403.00
of refining. As an example an article is included describing how catalyst management has been
improved at the Orpic Sohar Refinery in Oman.

Grace restates our pledge to invest in innovation to enable our customers to be successful in 2012,
and in the years to come.

Sincerely,

Colin Baillie © 2012

Marketing Manager W. R. Grace & Co.-Conn.
Grace Catalysts Technologies
2.25.12
The Successful Development and
Commercialisation of Zero- and
Low-Rare-Earth FCC Catalysts

Colin Baillie Catalysts are generally a refinery's second-highest raw material cost after crude oil. It is therefore not
Marketing Manager surprising then that due to the current cost of rare-earth metals, and the volatility of the market, refiners
are increasingly asking catalyst suppliers to relieve their cost pressures while maintaining or even im-
Grace Catalysts proving product performance. Grace Catalysts Technologies responded quickly to the issues of rare-
Technologies earth price and availability by developing the REpLaCeR® family of zero- and low-rare-earth FCC
Worms, Germany catalysts for both hydrotreated and resid feed processing.

Rosann Schiller
Senior Marketing Rare-Earth Price Volatility
Manager
The problem of rare-earth price volatility is not only limited to the refining industry. These highly sought
Grace Catalysts after metals are also key raw materials for many strategic industries with applications ranging from mili-
Technologies tary devices to electronic components. In addition, they are essential constituents in newly evolving
Columbia, MD, USA green technologies, such as hybrid cars and wind turbines. Their decreasing availability is primarily due
to the fact that the world’s supply only comes from a few sources, with China alone currently account-
ing for 95% of the world’s rare-earth metal output. During the last decade exports of rare-earth from
China have decreased significantly from approximately 57,000 MT/year in 2006 to less than
25,000 MT/year in 2010.1 In 2011, the export quotas for rare-earth were similar to 2010 levels,
however more materials fell under the quota system; therefore the total amount of rare-earth exported
was less than prior years. This reduction in export quotas caused the price of rare-earth to rapidly rise.
The key index for FCC catalysts is the cost of 99% lanthanum oxide FOB from China, which increased
dramatically from 2,300 $/MT in January 2007 to approximately 140,000 $/MT mid 2011 according to
the Asian Metals Index. Since then, rare-earth prices have subsided somewhat but lanthanum prices
remain considerably higher than the base level in early 2010. With the huge uncertainty that exists in
rare-earth prices there remains a huge importance of zero- and low-rare-earth FCC catalysts that are
capable of providing, or even increasing, the performance of their rare-earth counterparts.

2 March 2012
The Role of Rare-Earth in FCC Commercial Experience of Zero
Catalysts Rare-Earth Catalysts
Lanthanum and cerium are the two main rare-earths used in FCC Rare-earth free REsolution® catalysts are based on the Z-21 zeo-
catalysts. These metals limit the extent to which zeolite dealumi- lite and are intended for hydrotreated and VGO applications.
nation occurs (thus stabilising the structure) under the conditions Within the first year of commercialisation, the REsolution® catalyst
of the FCC unit. The aluminium atoms within the zeolite structure has been successfully used in 12 refineries in the EMEA region.
are the primary catalytic sites in FCC catalysts and therefore play The REsolution® catalyst is comparable to the rare-earth based
an important role in providing activity and selectivity. For example, NADIUSTM catalyst, which typically has rare-earth levels between
a higher amount of aluminium atoms will increase the amount of 1.8 and 2.5 wt.% and was previously Grace’s most successful cat-
hydrogen-transfer reactions that occur. Such reactions compete alyst for low-metal feed applications. Table 1 shows ACE pilot
with cracking reactions and are important for preserving mole- plant testing comparing the REsolution® and NADIUSTM catalysts
cules in the gasoline range. Therefore by restricting the loss of after CPS-3 deactivation at 600/400 ppm Ni/V levels. The NA-
aluminium atoms in the zeolite, rare-earth increases the activity DIUSTM catalyst used in the study had a rare-earth level of 2.3
and gasoline yield of FCC catalysts. Rare-earth also plays an im- wt.%. It can be seen that the catalysts provide very similar overall
portant role to prevent metals deactivation as it is a very effective yields.
vanadium trap. Therefore for resid processing in particular these
metals play an important role in maintaining stability and activity. One of the first trials of the REsolution® catalyst was at the MiRO
refinery in Germany. In February 2011 they switched from a cata-
Grace has a long history of providing innovation in the develop- lyst containing 3.1 wt.% rare-earth to the rare-earth free REsolu-
ment of FCC catalysts, including the addition of rare-earth metals tion® catalyst. Moving from such a high rare-earth based catalyst
to stabilise the zeolite Y component of the FCC catalyst, which to zero rare-earth will result in higher LPG yields at the expense of
was revolutionary for catalytic cracking. Grace also has a suc- gasoline, as recognized by the refinery. However, most users of
cessful history of developing rare-earth free FCC catalysts. We in- the REsolution® catalyst were previously using a NADIUSTM cata-
troduced new catalysts and zeolite components that enhanced lyst, and it is important to note that such a shift in product yields is
gasoline octane in the 1980’s and 1990’s, delivering activity and not observed moving from a lower rare-earth catalyst to a rare-
stability without the use of rare-earth. These rare-earth free zeo- earth free catalyst. Table 2 shows the FCC unit yields at the MiRO
lites were used in over 85% of our catalysts in North America at refinery. It can be seen that the REsolution® catalyst provided
the time. Later in the 1990’s Grace developed Z-21, a rare-earth lower dry gas, higher LPG (particularly propylene and C4 olefins)
free stabilised zeolite Y. Based on this new technology the at the expense of gasoline. Bottoms yield and coke were very sim-
NEXUS catalyst family was commercialised in 1997, as a rare-
® ilar. The REsolution® catalyst continues to perform extremely well,
earth free catalyst family for low-metal feed applications. The and the yields are in line with refinery expectations.
NEXUS® catalyst has since been used in 10 applications. Grace
has now developed the REpLaCeR® family of zero- and low-rare-
earth FCC catalysts, which are based on the existing Z-21 zeolite
technology, as well as the new Z-22 zeolite technology developed
in 2010. State-of-the-art methods are used to stabilise the rare-
earth free Z-21 and Z-22 zeolites, involving proprietary stabilizing
compounds and unique manufacturing processes. FCC catalysts
incorporating these new zeolites provide similar and even im-
proved performance compared to rare-earth containing catalysts.

The REpLaCeR® family of zero rare-earth FCC catalysts for hy-

drotreated and VGO applications includes the REsolution® cata-
lyst based on the existing Z-21 zeolite, as well as REactoRTM and
REpLaCeR® catalysts based on the newly developed Z-22 zeolite.
The development of rare-earth free catalysts for the resid feed
sector is much more challenging due to the additional demands
placed on zeolite stability. However, significant advancements
have been made by applying processing technology involving
metals resistance functionality to catalyst systems containing the
Z-21 and Z-22 zeolites. This has resulted in the rare-earth free
REduceR® catalyst, which is being blended with rare-earth based
resid FCC catalysts at levels up to 80%. The REduceR® catalyst
enables performance to be maintained or even improved in resid
processing applications whilst significantly reducing the overall
rare-earth requirement and cost.

GRACE EUROPEAN CATALAGRAM® 3

Commercial
Experience NADIUSTM REsolution®
of Low
Cat-to-Oil [-] 4.6 5.0
Rare-Earth
Catalysts for Standard Conversion (ASTM), wt.% ff 68.0 68.0
Resid Feed Gas Phase, wt.% ff 14.8 14.7
Applications Hydrogen, wt.% ff 0.11 0.07
The rare-earth free RE- Dry Gas (H2+C1-C2), wt.% ff 1.2 1.2
duceR® catalyst is based
LPG (C3-C4), wt.% ff 13.4 13.3
on Z-21 and Z-22 zeolite
LPG Olefinicity, wt.% ff 68.6 69.1
technology and can be
used as a blending compo- Coke, wt.% ff 2.0 2.0
nent with a rare-earth Coke On Catalyst wt.% ff 0.40 0.39
based resid catalyst, reduc- Standard Gasoline (ASTM), wt.% ff 51.2 51.2
ing the overall rare-earth
Standard LCO (ASTM), wt.% ff 20.1 20.1
requirement whilst main-
Standard HCO (ASTM), wt.% ff 11.9 11.9
taining performance. Figure
1 shows the activity reten- Ethane, wt.% ff 0.3 0.3

tion of REduceR catalyst

® Ethene, wt.% ff 0.4 0.4
blends with the NEKTOR- Propane, wt.% ff 0.6 0.6
ULCCTM resid catalyst
Propylene, wt.% ff 3.7 3.7
(ACE pilot plant, CPS-3 de-
i-Butane, wt.% ff 3.0 3.0
activation, 2000/3000 ppm
Ni/V), and it can be seen n-Butane, wt.% ff 0.6 0.6

that even at a blend ratio of i-Butene, wt.% ff 1.5 1.5

60% the REduceR cata- ®
C4- Olefins, wt.% ff 5.5 5.5
lyst provides very good ac-
Research Octane Number [-] 92.9 93.0
tivity retention.
Motor Octane Number [-] 81.1 81.0

The REduceR® catalyst has RON Barrels [-] 47.5 47.6

been successfully commer- MON Barrels [-] 41.5 41.5

cialised, and is currently
TABLE 1: ACE Pilot Plant Testing Comparing REsolution® and NADIUS T M
being used in 18 resid ap- Catalysts
plications at European re-
fineries. One such example
is at the BAYERNOIL
Vohburg refinery in Ger-
NEKTORTM REsolution®
many, which processes a
resid feedstock with typical Dry Gas, wt.% Base -0.11
Ecat Ni+V levels of > 7,000
Propane, wt.% Base 0.24
ppm. This refinery was pre-
Propylene, wt.% Base 1.03
viously using a NEKTORTM
catalyst that contained ca. i-Butane, wt.% Base -0.21
3.1 wt.% rare-earth, and n-Butane, wt.% Base Base
performed extremely well. i-Butylene, wt.% Base 0.17
In April 2011, BAYERNOIL
n-Butylene, wt.% Base 0.69
Vohburg began to blend
Gasoline (C5-221˚C), wt.% Base -1.92
30% of the REduceR® cata-
lyst with the NEKTORTM LCO (221-380˚C), wt.% Base -0.14
catalyst, with the simple ob- Bottoms (380˚C), wt.% Base 0.02
jective of reducing rare- Coke, wt.% Base 0.09
earth whilst maintaining
high performance. The Table 2: FCC Unit Yields at the MiRO Refinery Using the REsolution® Catalyst
FCC unit data provided in
Figure 2 shows that the
REduceR® catalyst blend
provided similar/better bot-

4 March 2012
toms upgrading than the NEKTORTM catalyst. In addition, a lower
80
delta coke was obtained, which reduced regenerator bed temper-

Interpolated Standard Conversion

79
ature by 10˚C. This allowed the refinery to increase conversion at

@ Constant C/O, wt.% FF

78
constant feed Atmospheric Residue content. 77
76

The refinery considered the performance of the REduceR® cata- 75

74
lyst to be such a success that they increased the blending ratio
73
from 30% to 50%, thus reducing the overall rare-earth content of
72
the catalyst to 1.5 wt.%. Table 3 shows the FCC unit product 71
yields obtained with the 50% REduceR® catalyst blend compared 70
0 20 40 60 80 100
with the NEKTORTM catalyst. During the REduceR® catalyst trial
REduceR® Content in Blends with Base, %
feed quality deteriorated and feed throughput decreased, there-
fore for the purpose of evaluating the actual catalyst performance FIGURE 1: Activity Retention of REduceR® Catalyst
the yields shown are calculated on the basis of constant feed Blends for Resid Applications
properties and independent operating conditions. The key objec-
tive of the refinery was to maintain conversion and bottoms up-
grading whilst reducing rare-earth content. As can be seen these
key objectives were met, and in addition conversion and bottoms
upgrading were even increased. The REduceR® catalyst provided
a similar coke yield but an improved delta coke, and allowed
regen bed temperature to be decreased by 15˚C.

Regenerator Bed Temperature Delta Coke (Non-Mass Balanced)

725 0.93

720 0.91
0.89
715
0.87
Wt.%

710 0.85
˚C

705 0.83
0.81
700
0.79
695
0.77
690 0.75
508 510 512 514 516 518 520 522 524 60 62 64 66 68 70
ROT, ˚C Apparent Conversion (non-mass balanced), wt.% FF

Apparent Conversion Slurry Yield

77 16

75 15
14
73
13
Wt.% FF

Wt.% FF

71 12

69 11
10
67
9
65 8
50 55 60 65 70 75 80 85 90 65 67 69 71 73 75 77
At Res in Feed, wt.% Conversion, wt.% FF

NEKTORTM 30% REduceR® Catalyst

Figure 2: FCCU Data of the REduceR® Catalyst Blend at 30%

GRACE EUROPEAN CATALAGRAM® 5

 50

45

40

35

30

25

20

15

10

Dec 10 Jan 11 Feb 11 Mar 11 Apr 11 May 11 Jun 11 Jul 11 Aug 11 Sep 11 Oct 11 Nov 11 Dec 11

Figure 3: Rapid Global Market Acceptance of the REpLaCeR® Family of Catalysts

The refinery were extremely satisfied with the REduceR® catalyst Conclusion
trial, and in September 2011 increased the blending ratio of the
In response to the increased cost and decreasing availability of
REduceR® catalyst to 70%, thus reducing rare-earth to 1.0 wt.%.
rare-earth Grace Catalysts Technologies has successfully com-
More recently they are using 80% of the REduceR® catalyst, with
mercialised the REpLaCeR® family of low and zero rare-earth cat-
an overall rare-earth content of 0.6 wt.%. Despite the high nickel
alysts. The REsolution® catalyst is based on the Z-21 zeolite,
and vanadium levels the refinery continue to see excellent per-
while REactoRTM and REpLaCeR® incorporate the newly devel-
formance.
oped Z-22 zeolite. Each of these catalyst families are rare-earth
free, and are intended for hydrotreated and VGO applications. For
resid applications the REduceR® catalyst has been developed,
50% NEKTORTM
NEKTOR TM which is also a rare-earth free catalyst utilising either the Z-21 or
50% REduceR®
Z-22 zeolite. The REduceR® catalyst is currently being blended at
Cat-to-Oil Base Base +0.4 30-80% levels with rare-earth based catalysts, thus providing
Conversion, wt.% Base Base +0.5 resid catalysts with rare-earth levels between 0.6 and 2.5 wt.%,

Hydrogen, wt.% Base Base +0.02 and is proving to be a highly successful solution for refiners to re-
duce catalyst cost whilst maintaining performance. As shown in
C1+C2’s, wt.% Base Base +0.2
Figure 3, the REpLaCeR® family of catalysts have received rapid
Propylene, wt.% Base Base +0.4
global market acceptance.
C4 Olefins, wt.% Base Base +0.6
LPG, wt.% Base Base +2.0 Through the development of proprietary non rare-earth stabilised

Gasoline, wt.% Base Base -1.6 Z-21 and Z-22 zeolites Grace is the only catalyst supplier that pro-
vides zero rare-earth FCC catalysts for hydrotreated and VGO
LCO, wt.% Base Base -0.2
feedstocks, as well as low rare-earth FCC catalysts for resid feeds
Slurry, wt.% Base Base -0.2
that can provide similar, or even improved, performance.
Coke, wt.% Base Base -0.1
Delta Coke, wt.% Base Base -0.09

References
CAR, MT/D Base Base
1. Rare-Earths Recycling Study, Oeko-Institut, January 2011.
Ecat Ni, ppm Base Base
Ecat V, ppm Base Base

Regen Bed Temp, ˚C Base Base -15˚C

TABLE 3: FCCU Data of the REduceR ® Catalyst

Blend at 50%

6 March 2012
Improved Product Yields
and Attrition Resistance
Using the ResidCrackeRTM
FCC Catalyst at
BAYERNOIL Neustadt

Colin Baillie High catalyst losses from the FCC unit can have considerable consequences for refineries, such as con-
Marketing Manager tamination of slurry oil, erosion of slurry circulation pumps, required cleaning of heavy oil tanks due to
catalyst build up, failure to meet atmospheric particulate emissions regulations, premature failure of flue
Sabeeth gas power recovery turbines, as well as loss of catalyst fluidity leading to lower FCC unit throughput and
Srikantharajah worsening product yields.1 There are many operational factors that can cause increased catalyst losses
Technical Service from the FCC unit, however they will not be discussed in this article. High catalyst losses can also be the
Manager result of excessive attrition of the FCC catalyst in a fluid bed, which is caused by catalyst particles collid-
ing at high velocity with other particles or solid surfaces. Therefore, one of the most fundamental fea-
Grace
tures of a successful fluid catalytic cracking (FCC) catalyst is a high attrition resistance to enable it to be
Worms, Germany
better retained within the FCC unit. Grace FCC catalysts utilise a proprietary alumina sol (Al-Sol) binder

Bernhard system, which provides excellent attrition resistance and leads the industry in unit retention. This article
Zahnbrecher will highlight how the ResidCrackeRTM catalyst has helped the BAYERNOIL Neustadt refinery to reduce
particulate emissions, whilst providing improved product yields.
BAYERNOIL Neustadt
Refinery

BAYERNOIL Neustadt Refinery Overview

The BAYERNOIL Neustadt refinery is located in the Bavaria region of southern Germany, and along with
the nearby BAYERNOIL Vohburg refinery contributes to a total capacity of 10.3 million tons per year. The
two locations contain 3 crude units, 2 vacuum towers, 2 FCC units, 1 mild hydrocracker and hydrogen
plant, 1 visbreaker, 3 reformers and 1 ether plant. The FCC unit at Neustadt is a stacked model and was
built in the 1970’s. It has a typical throughput of 150 tons per hour, operates in deep partial burn, and
processes mild hydrocracker unconverted oil and atmospheric residue. The feedstock has a concarbon
of 2.5 wt.%, and the Ecat metals levels are approximately 5000 ppm vanadium, 5000 ppm nickel, 6000
ppm Fe and 4500 ppm sodium.

GRACE EUROPEAN CATALAGRAM® 7

Reducing
Particulate FCC Neustadt Ammonia Injection and Dust Concentration After ESP
Emissions at
BAYERNOIL Dust Concentration
Neustadt

Dust Concentration After ESP

and Ammonia Injection
In addition to third-stage
cyclones the BAYERNOIL
Neustadt refinery also has
an electrostatic precipitator
(ESP) to help control partic-
ulate emissions. ESP’s
have been used for the re-
Ammonia
duction of FCC particulate
Injection
emissions since the 1940’s,
and modern ESP’s can be

07
07
07

07

07

07
07

07
07
07
6

07
6

7
0
00

00
designed to reduce particu-

20
20
20

20

20

20
20

20
20
20
20

20
.2

.2
8.
5.
1.

2.

4.

2.
9.

0.
7.
6.
2.

3.
.11

.11
late emissions to very low

.0
.0
.0

.0

.0

.1
.0

.1
.0
.0
.1

.0

18
18
18

18

18

18
18

18
18

18
18
18
18

18
levels. ESP operation con-
sists of three main steps:
Figure 1: Ammonia Effect on Particulate Emissions
particle charging, particle
collection, and particle re-
moval. The ESP at the
Neustadt refinery was in- FCC Neustadt Dust in Fluegas After ESP

stalled in the 1990’s and

was recently revamped in Catalyst System Before Grace, Grace Catalyst System,
Fluegas Dust Concentration mg/Nm3

Ammonia Injection Required to Stay Within Limits No Ammonia Injection

2008. It has 4 zones, 6 dust
Max. Allowed Dust Concentration
hoppers and an inlet tem-
perature of 220 °C. ESP
Typical Upper Dust Concentration Mechanical
performance is generally
ESP
affected by various factors. Problems
For example, a higher ESP
voltage (typically between
20 to 80 kV) is desirable,
and optimum performance
also requires proper sizing
of the precipitator (and of
the electrodes). The flue
gas nature (temperature,
01.01.2009 01.07.2009 01.01.2010 01.07.2010 01.01.2011
moisture content, composi-
tion) and the dust nature
(electrical resistivity, parti- Figure 2: FCC Catalyst Effect on Particulate Emissions
cle size, temperature) also
play a role, as does the gas ammonia injection). This is ery moved to a Grace catalyst in 2010 a dramatic reduction in
velocity. At the Neustadt highlighted by Figure 1, particulate emissions was observed even without the use of am-
refinery the key factors for which shows how ammonia monia injections. Other parameters were investigated to dis-
achieving optimum particu- injection has been used to cover whether there could be other causes for the decreased
late separation have been control particulate emis- particulate emissions, such as Ecat contaminant metals (which
identified as having the sions. The FCC catalyst could affect Ecat resistivity), carbon on regenerated catalyst, as
proper ESP design, particu- has also been identified as well as NOx concentration in the flue gas. However, none of
larly with respect to size for playing a vital role. This can these other factors were found to play a significant role in this
a certain flow rate. The be clearly seen in Figure 2, case. The improved particulate emissions achieved have subse-
high availability of all me- which shows that prior to quently been attributed to the proprietary Al-sol binder used in
chanical and electrical using a catalyst from Grace the Grace catalyst that provides improved attrition resistance.
parts of the ESP has been ammonia injection was re- This is also supported by the fact that particulate emissions
important, likewise the low quired to stay within the lim- were not affected when the Ecat in the unit (from the Grace cat-
Ecat resistivity (helped by its of particulate emissions. alyst) was replaced by external Grace Ecat during a turnaround
high metals content and However, when the refin- in Spring 2011.

8 March 2012
Improving
Previous
Product Catalyst
ResidCrackeRTM
Yields at
Standard Conversion Base Base +3.53
BAYERNOIL
Neustadt Hydrogen, wt.% Base Base

The catalyst that Hydrogen + C1-C2’s, wt.% Base Base -0.59

BAYERNOIL Neustadt Propane, wt.% Base Base +0.32
switched to in 2010 was the Propylene, wt.% Base Base +0.57
ResidCrackeRTM catalyst
n-Butane, wt.% Base Base +0.19
from Grace. ResidCrack-
i-Butane, wt.% Base Base +0.79
eRTM catalysts are designed
for resid processing, and in- i-Butene, wt.% Base Base +0.04
corporate acidity modifica- C4 Olefins, wt.% Base Base +0.63
tion, pore restructuring and LPG, wt.% Base Base +2.49
metals resistance function-
Standard Naphtha, wt.% Base Base +1.60
alities from the EnhanceRTM
Standard LCO, wt.% Base Base -0.46
Technology Platform. En-
hanceRTM based catalysts Standard Clarified Oil, wt.% Base Base -3.07

are manufactured with the Coke, wt.% Base Base -0.02

proprietary Grace Al-sol
Table 1: Improved Product Yields Using ResidCrackeR T M
binder system, which en-
sures low particulate emis-
sions due to its excellent
attrition resistance. The 3.0
ResidCrackeRTM catalyst is
2.8 Competitor
designed to give maximum
2.6 ResidCrackeRTM
intrinsic bottoms cracking
with minimal or no coke 2.4
penalty.
2.2
CF

The yield improvements 2.0

upon moving to a Grace 1.8
catalyst are shown in Table
1.6
1. The ResidCrackeRTM cat-
1.4
alyst increased conversion
by nearly 3.5 wt.%, reduced 1.2
slurry yield by approxi- 1.0
mately 3 wt.%, and in- 2,000 3,000 4,000 5,000 6,000 7,000 8,000
creased LPG and gasoline
yield by approximately 2.5 Ni + V/4 [mg/kg]
and 1.5 wt.%, respectively.
In addition, dry gas was re- Figure 3: Lower Coke Factor of the ResidCrackeR T M Catalyst
duced by over 0.5 wt.% and (no Antimony was Used)
coke yield was similar. The
improved metals tolerance
and activity retention of the
ResidCrackeRTM catalyst is
highlighted by the Ecat
evaluation graphs in Fig-
ures 3-5. Moving to the
Grace catalyst clearly pro-
vided lower coke and gas
factors, as well as a higher
stability/activity.

GRACE EUROPEAN CATALAGRAM® 9

 8.0

7.0

6.0
GF
5.0

4.0
Competitor
3.0
ResidCrackeRTM
2.0
2,000 3,000 4,000 5,000 6,000 7,000 8,000

Ni + V/4 [mg/kg]

Figure 4: Lower Gas Factor of the ResidCrackeR T M Catalyst (no Antimony was Used)

80

75
MAT (wt.%)

70

65

Competitor
60
ResidCrackeRTM
55
0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0

V+Na+Ca+Fe [wt.%]

Figure 5: Higher Stability/Activity of the ResidCrackeR T M Catalyst

To summarise, when the BAYERNOIL Neustadt refinery moved to

a Grace catalyst in 2010 a dramatic reduction in particulate emis-
sions was achieved due to the improved attrition resistance of the
proprietary Al-sol binder used in the catalyst. In addition, the
switch to the ResidCrackeRTM catalyst also considerably improved
product yields and allowed increased resid upgrading. This has
resulted in a significant increase in FCCU profitability as recog-
nised by the refinery.

References
1. P. K. Niccum, Hydrocarbon Processing, September 2010,
p 29-38.

10 March 2012
 Development of New Catalysts for
Middle Distillates Maximisation

Tamara Galindo Introduction

Increase in middle distillates consumption in Europe is a trend that began in the 1990’s and is expected
Ruben Miravalles
to continue in the future, whilst at the same time gasoline demand is decreasing. This has resulted in
an unbalance between middle distillates and gasoline demand and supply in Europe meaning that re-
Repsol
finers face an important challenge to increase the gasoil to gasoline ratio in the refinery. There are
many options by which refiners can raise production of middle distillates at the expense of gasoline. For
example, refineries can operate their FCC units in maximum distillates mode.

The Repsol Puertollano refinery is an inland refinery located in the centre of Spain. The refinery
processes heavy crudes with a deep conversion scheme, which includes a delayed coker and an FCC
and mild hydrocracker (MHC) unit. The complex also includes an ETBE and a hydrofluoric acid alkyla-
tion unit, which process the C4 fraction from the FCC unit. The FCC unit is a 40,500 bpsd Exxon Flexi-
cracker, which was started up in 1983. In 2004, an Axens mild hydrocracker unit was installed for FCC
feedstock pre-treatment, in order to adapt product quality to the more stringent regulations of maximum
sulphur in fuels. Since then, 90-95% of the feedstock processed by the FCC unit is mild hydrocracker
residue (RMHC), with the other 5-10% being a heavy feedstock, such as atmospheric residue, which is
necessary to close the unit heat balance.

The main objective at the Puertollano FCC unit is maximisation of middle distillates production. Other
unit objectives include reduction of light naphtha yield, maximum olefin content and a minimum MON
value required. To achieve these objectives, the unit operates at very low severity (low riser tempera-
ture, cat-to-oil ratio and Ecat activity), with maximum slurry recycle. Producing maximum middle distil-
lates in the Puertollano FCC unit case is a difficult challenge. The severely hydrotreated RMHC
feedstock is highly crackable with a very poor selectivity to middle distillates. In addition, the coke-mak-
ing tendency of the RMHC feed is also very low. Therefore processing this feedstock at low severity re-

GRACE EUROPEAN CATALAGRAM® 11

quires maximum slurry recycle and the simultaneous processing Two different scenarios were defined for the development of the
of a certain amount of heavy feedstock, such as atmospheric new catalyst; a high metals scenario, corresponding to atmos-
residue, in order to close the heat balance. Processing of atmos- pheric residue processing and high metals on Ecat, and a low
pheric residue in this unit has several disadvantages. For exam- metals scenario, with no atmospheric residue processed and low
ple, low sulphur atmospheric residues must be processed in the metals on Ecat. In the first phase of the project, Grace developed
FCC unit in order not to penalise the sulphur balance. Therefore several catalyst formulations and tested them at a laboratory scale
light crudes, which are not the optimum ones in the refinery in an ACE (Advanced Catalyst Evaluation) unit. A total of 19 cata-
scheme, must be distilled to feed the FCC unit. Processing of at- lysts were evaluated in the first round to select the best zeolite,
mospheric residue in the FCC also results in high metals contami- matrix and post-treatments and the 6 of the highest performing
nation on the Ecat, with a subsequent increase in catalyst catalysts were fine tuned and tested again in a second round of
consumption. trials. Upon completion the top 4 catalysts were selected for the
following phase of the project, which consisted in an evaluation in
the Repsol DCR-II pilot plant unit. Process modelling with FCC-
SIM was used to translate pilot plant results to the commercial
Grace and Repsol unit, to check unit constraints and to optimise operating conditions
Collaboration Project for the new catalysts. The catalyst that showed the best perform-
Grace has been the FCC catalyst supplier for the Puertollano FCC ance in both a high and low metals scenario, the DieseliseRTM cat-
unit for several years. Grace has continually made innovations in alyst, was manufactured by Grace at an industrial scale and the
catalyst technology, which has allowed the Puertollano FCC unit results from its commercial use in Puertollano’s refinery will now
to better adapt to the changing production scenarios. Before the be discussed.
start up of the MHC unit, the GOAL catalyst from Grace was used.
After the start up of the FCC pretreatment and in order to adapt to
the significant feed quality change and operating conditions in the
FCC unit, the GOAL catalyst was replaced by the NOMUSTM cata- Successful Commercial
lyst based on first-generation EnhanceRTM technology. Later, Application of DieseliseRTM
Grace developed the NOMUS-DMAXTM catalyst, which is a sec- Catalyst
ond-generation EnhanceRTM catalyst for increased middle distil- The DieseliseRTM catalyst trial began in September 2009. During
lates yields, and this catalyst was also successfully applied for the the catalyst turnover, the feed rate in the commercial unit was
Puertollano FCC unit operation. In order to fully optimise the chal- variable with alternating operations at minimum feed rate during
lenging Puertollano operation, Grace and Repsol decided to start the end of 2009 and early 2010 with periods of high throughput.
a joint collaboration project to develop a new generation of cata- Independently of the total feed rate, the improvement in heat bal-
lysts for middle distillates maximisation in hydrotreated feedstock ance closure achieved with the new DieseliseRTM catalyst has al-
scenarios. lowed a desired progressive reduction in the low-sulphur
atmospheric residue (AR) processing, as can be seen in Figure 1.

Feed Processing
200 30
AR Rate and Slurry Recycle, t/h

180 25
Feed Rate, t/h

160 20

140 15

120 10

100 5

80 0
31 -08

29 -08

28 -08

28 -09

27 -09

26 -09

24 -09

23 -09

23 -10

22 -10

21 -10

19 -10

18 -10
27 -08

22 -09

17 -10

18 -11

17 -11

16 -11

14 -11
11
9-
6

7
1

1
-0

-0

-0

-1

-0

-0

-0

-0

-0

-1

-0

-0

-0

-0

-0

-1

-0

-0

-0

-0

-0
01

Feed Rate AR Rate Slurry Recycle

Figure 1: Feed Rate, Atmospheric Residue Rate and Slurry Recycle

12 March 2012
 Catalyst Addition vs. V+Na on Ecat
3.0 10000

9000
2.5
Catalyst Addition t/day

V+Na Ecat, ppm

8000
2.0
7000
1.5
6000
1.0
5000
0.5
4000

0.0 3000

18 10
19 -10
21 -10
22 -10
23 -10
23 09
24 -09
26 -09
27 -09
28 -09
28 08
29 -08
31 -08

11
14 -11
16 -11
17 -11
18 -11
17 10
22 09
27 08

9-
9-
9-
9-

1-
1-
1-

7
5
3
1
7
5
3
1
7
5
3
1
7
6

-0
-0
-0
-0
-0
-1
-0
-0
-0
-0
-0
-1
-0
-0
-0
-0
-0
-1
-0
-0
-0
01

Catalyst Addition V+Na

Figure 2: Catalyst Addition vs. Vanadium and Sodium Levels on Ecat

Middle Distillates vs. Feed Rate

200
NOMUS-DMAXTM DieseliseRTM

Middle Distillates, wt.%

180
Feed Rate, t/h

160

140

120

100

80
18 10
19 -10
21 -10
22 -10
23 -10
23 09
24 -09
26 -09
27 -09
28 -09
08
08
08

11
14 -11
16 -11
17 -11
18 -11
17 10
22 09
27 08

9-
9-
9-
9-
7-
6-

1-
1-
1-

7
5
3
1
7
5
3
1
7
5
3
1

-0
-0
-0
-0
-0
-1
-0
-0
-0
-0
-0
-1
-0
-0
-0
-0
-0
-1
-0
-0
-0

28
29
31
01

Feed Rate Middle Distillates

Figure 3: Middle Distillates (140-380°C) Production

Due to the reduction in the amount of atmospheric residue needed Reduction in light naphtha production using the DieseliseRTM cata-
to close heat balance, contaminant metals on Ecat has been sig- lyst is also clear (Figure 4), although in this case the comparison
nificantly reduced, in particular deactivating ones such as vana- is not so straightforward because the level of olefins promoter in
dium and sodium. The periods of low feed rate have also the inventory has not been constant. Due to lower propylene de-
contributed to lower contaminant metals on Ecat. Consequently, mand, olefins promoter usage was stopped during the Dieselis-
catalyst addition rate has been progressively decreased until eRTM catalyst period, as can be seen in the P2O5 on Ecat (Figure
reaching the minimum technically needed to maintain levels in the 5). This factor must be taken into account because it is necessary
regenerator and stripper (Figure 2). to discount the olefins promoter effect for the comparison of the
two catalysts.
During the catalyst turnover, a continuous increase in middle distil-
lates (140-380°C) has been recorded in the unit, as can be seen
in Figure 3, thus achieving a significant improvement in the main
production objective.

GRACE EUROPEAN CATALAGRAM® 13

 Light Naphtha vs. Feed Rate
200 24
NOMUS-DMAXTM DieseliseRTM
22
180

Light Naphtha, wt.%

20
160
Feed Rate, t/h

18
140
16
120
14

100 12

80 10
31 -08

29 -08

28 -08

28 -09

27 -09

26 -09

24 -09

23 -09

23 -10

22 -10

21 -10

19 -10

18 -10
27 -08

22 -09

17 -10

18 -11

17 -11

16 -11

14 -11
11
9-
6

7
1

1
-0

-0

-0

-1

-0

-0

-0

-0

-0

-1

-0

-0

-0

-0

-0

-1

-0

-0

-0

-0

-0
01

Feed Rate Middle Distillates

Figure 4: Light Naphtha (C5-90°C) Production

Olefins Promoter Addition Rate

0.50
NOMUS-DMAXTM DieseliseRTM
0.45
0.40
0.35
P2O5 Ecat, wt.%

0.30
0.25
0.20
0.15
0.10
0.05
0.00
18 -10
31 -08

29 -08

28 -08

28 -09

27 -09

26 -09

24 -09

23 -09

23 -10

22 -10

21 -10

19 -10

17 -10

18 -11

17 -11

16 -11

14 -11
11
27 -08

22 -09

9-
9

7
6

1
1

-0

-1

-0

-0

-0

-0

-0
-0

-0

-0

-1

-0

-0

-0

-0

-0

-1

-0

-0

-0

-0
01

P2O5 Ecat

Figure 5: Olefins Promoter on Ecat (wt.% P 2 O 5 )

Shifts in commercial yields with the new catalyst are detailed in tion in olefins promoter addition rate due to lower propylene de-
Table 1. The deltas have been obtained as the difference between mand. Nevertheless, the effect of olefins promoter on the yields
average values from several test runs performed in the commer- in Table 1 has been corrected. Results show an impressive in-
cial units with the NOMUS-DMAX TM catalyst, before catalyst sub- crease of more than 3 wt.% in middle distillates, similar bottoms
stitution, and the DieseliseRTM catalyst at around 60% turnover. production and a significant reduction in light naphtha, thus
Regarding operating conditions, it can be seen that riser tempera- achieving the desired FCC product yields to better suit the mar-
ture and MAT activity have been held constant on average be- ket demand. The decrease in propylene production is not an
tween the two periods. Feed rate was slightly lower during the issue in the current situation due to the low product demand, and
DieseliseRTM catalyst period whereas slurry recycle was slightly in any case LPG production loss could be easily recovered with
higher. The main change in operating conditions was the reduc- the addition of ZSM-5 additive.

14 March 2012
 ∆Yield
Ecat Comparison in Pilot Plant
Direct comparison of both the previous and current catalyst in the Yields (wt.%): ∆
industrial unit is difficult. Firstly, feedstock quality has been vari-
Conversion @ 161˚C -3.8
able, with atmospheric residue being progressively reduced during
FUEL GAS 0.2
the catalyst turnover. Secondly, some of the operating conditions
that greatly impact yields and selectivity, such as feed rate (which C3 Total -1.18
affects residence time) and olefins promoter addition rate, have C4 Total -1.15
been varied during the DieseliseRTM catalyst turnover. For this rea- LPG -2.3
son, in order to check the good results observed during the indus-
LCN-L -2.9
trial trial, several NOMUS-DMAXTM and DieseliseRTM Ecat
LCN-M 1.1
samples collected from the commercial FCC unit were tested in
the DCR pilot plant at Repsol R&D facilities. For the pilot plant Gasoline -1.7
comparison the Ecat samples were tested at constant operating Middle Distillates 3.5
conditions, which simulates the operation in the industrial unit, Slurry 0.3
using a representative feed sample collected from the Puertollano
Coke 0.0
unit. The results of pilot plant comparison of both catalysts at con-
Operating Conditions
stant coke, which are shown in Table 2, confirmed the excellent
results observed in the commercial unit. Feed Rate, t/h -24.9
RA Rate, t/h -6.4
Slurry Recyle, m3/h 5.8

Conclusions Feed Density -0.0042

Riser Temperature 0
The development of a new generation of EnhanceRTM FCC cata-
lysts for middle distillates maximisation has resulted in a signifi- Preheat Temperature 11
cant benefit for the Puertollano refinery. The DieseliseRTM catalyst MAT Activity, wt.% 0
has achieved an improvement in the two main production objec- Olefins Promoter, % Ecat -2.5
tives, namely a significant increase in middle distillates production
in a very challenging hydrotreated scenario and a decrease in Table 1: Yields and Operating Data Comparison of
DieseliseR T M Catalyst vs. NOMUS-DMAX T M Catalyst
gasoline production, thus allowing the FCC unit product yields to
better match the refinery demand. The optimised catalyst also al-
lows the FCCU heat balance to be closed without having to ∆Yield
∆
process atmospheric residue, which provides a reduction in Ecat
Yields (wt.%):
metals and catalyst consumption, and a decrease in the sulphur
content of FCC products. Conversion @ 161˚C -4.4
H2S 0.00
Last, but not least, this project involved close collaboration be- FUEL GAS 0.1
tween Repsol and Grace, which provided a successful outcome in
C3 Total -0.47
an area of joint interest. It has been an exemplary project, cover-
C4 Total -0.50
ing all the stages from research in new catalytic technology to de-
velopment and testing, first at laboratory scale, followed by pilot LPG -1.0
plant validation and successful application to commercial produc- LCN-L -2.5
tion and operation. LCN-M -1.0
Gasoline -3.4
Middle Distillates 3.0
Slurry 1.2
Coke 0.0

Table 2. DCR Pilot Plant Comparison of Ecats at

Constant Coke

GRACE EUROPEAN CATALAGRAM® 15

Improving Catalyst
Management at the
Orpic Sohar Refinery

Maria Luisa It is known that the performance of the FCC unit will benefit from the stable and regular dosage of the
Sargenti catalyst into the unit. To be able to regularly replace fresh catalyst the best practice is to ensure a stable
Technology activity in the inventory and minimize the upsets typically caused by slug additions of fresh catalyst.
Coordination
Manager However there are other activities around the FCC unit operation where the management of the catalyst
is especially important and the risk and costs for mismanagement could be magnified if a big volume has
Nathan Ergonul to be moved every day. The Orpic Sohar refinery in Oman wanted to improve the catalyst, Ecat and ad-
Technical Sales
ditives injections, as well as find an optimum solution to their current hoppers’ configuration whilst im-
Manager
proving the current fresh catalyst unloading system, which is described in this article.

Matthias Scherer
Director Sales,
Administration &
Logistics
Orpic Sohar – Site Description
Orpic is the leading Omani producer and distributor of refined products in Oman. The Sohar refinery, lo-
Grace Catalysts cated 220 km north-east of Muscat, is the largest of the two refineries in Oman. With a production ca-
Technologies pacity of 116 kbbl/day, Sohar refinery’s main products (gasoline, propylene and diesel) are distributed
among different markets in and outside the country.
Hemant Upadhyay
The FCC unit typically process 100% atmospheric residue and approximately 2% of the total catalyst in-
Robert McClung
ventory is rejuvenated with fresh material every day by injecting between 20-30 MT/day of fresh catalyst
combined with additives and/or Ecat depending on the operational requirements.
Talal Said Wasser Al
Rawahi

Orpic Sohar Refinery

16 March 2012
Figure 1: Design Set Up of Catalyst and Additive Injection System at Orpic Sohar

Catalyst and Additive Injection

System
In the original design set up, four hoppers are used for the storage
of the FCC fresh catalyst, Ecat and the OlefinsUltra® ZSM-5 addi-
tive. During the last year, a specifically customized D.A.I.S.1
QUATTRO System has been installed to enable the refinery to op-
erate at maximum flexibility and reliability.

Due to the particular set up of the refinery, a technical visit prior to

the installation of the addition device was necessary to determine
the optimal location of the D.A.I.S. units and design the proper
connection between the hoppers. Due to the volume managed in
the daily additions, the catalyst injection is an intensive operation.
Therefore it was suggested to install two D.A.I.S. QUATTRO units
to be operated on a stand-by basis. With this solution it will be
possible to constantly maintain an uninterrupted dosage of fresh
catalyst into the FCC unit. An additional flow bin was also included
to allow separate injections of Grace’s combustion promoter if re-
quired, as shown in Figure 1.

Moving from the Unloading from Figure 2: The Super Sacks Previously Used to
Super Sacks to Using a Container Unload Fresh Catalyst at Orpic Sohar
Trailer Tipper
In the conventional operation approximately 20-30 super sacks
(1000 kg each) of fresh catalyst were unloaded every day into the However, to do this requires the necessary facilities for unloading
storage hopper (Figure 2). The handling of such a large volume of the trailer on site.
material had previously been an intensively time consuming and
environmentally unfriendly operation. Other issues were the Bulk-lined containers are the desired solution to safely and effec-
safety concerns associated with the forklift truck movements in the tively transport overseas and store large volumes of catalyst from
area, and the costs associated with it during the previous opera- the initial production site to the final user in the refinery. For the
tion. In addition, during the unloading operation, dust generation operation at Orpic Sohar a set of trailer tippers2 was supplied to
was inevitable, causing losses of catalyst and limiting the mainte- allow the refinery to change from the traditional super sacks deliv-
nance activities in the area. ery to the safer and logistically cleaner container system, whilst at
the same time providing a second back-up system. This solution
One effective way to avoid the handling of Super Sacks is to de- was successfully installed on site in a simple manner without the
liver larger volumes of catalyst and additives overseas in more need for extra engineering and construction. The frame is ad-
suitably designed containers fitted with polyethylene bulk liners. justable to variable heights of trailers, being able to manage a

GRACE EUROPEAN CATALAGRAM® 17

 Figure 3: Illustration of the Container Trailer Tipper Facility at Orpic Sohar

trailer of maximum 40 feet without the front car. The maximum ca- spent on cleaning and housekeeping. In addition, the reduced
pacity is 35 MT including the trailer per tilting chassis. The simple dust generation represents a safer and more pleasant working en-
advantage of this system is that the truck drives the container onto vironment for the operations personnel. The reduced manual han-
the frame. The truck is then removed and the whole trailer is fixed dling of catalyst, on the other hand, can be used either to free
whilst being tilted backwards. After emptying the container, the operator man hours for other duties or to reduce site costs accord-
truck then pulls away with the empty container, and leaves while ingly. For example, the number of contract personnel performing
the new supply is already arriving. the manual handling can be re-evaluated, or the personnel can be
assigned to new duties. In conclusion, using the newly imple-
During the unloading operation the trailer is locked with chains mented D.A.I.S. QUATTRO system and the custom-built container
and a safety bar over the container. The catalyst is then trans- offloading facilities at Orpic Sohar improved the operation and al-
ported into the storage hopper by a Power Pipe2 system (see Fig- lowed the refinery operate at maximum flexibility and reliability.
ure 4). This easy to use device is operated by vacuum providing Last, but not least, the unloading process for the daily consump-
the refinery with a noticeable reduction of time during the unload- tion of catalysts is considerably reduced, with approximately only
ing operation. While one trailer is being unloaded, a second can a quarter of the time needed.
already be prepared for unloading on the second tilting chassis.

References
Improved Operation and Benefits 1. D.A.I.S. Units are exclusively manufactured for Grace by
By implementing the solutions mentioned above in a holistic ap- PNEUMIX.
proach, one of the biggest benefits is the large reduction in dust
generation while handling the fresh catalyst. The reduced dust 2. Trailer Tipper and Power Pipe are solutions manufactured by
generation within the process areas could reduce man hours PNEUMIX.

Figure 4: Illustration and Picture of the Power Pipe System

18 March 2012
 14th Grace FCC Technology
Conference

Colin Baillie From September 6th–9th, Grace Catalysts Technologies Europe held the 14th FCC Technology Confer-
Marketing Manager ence in Munich, Germany. This event, occurring approximately every three years, dates back to the
1980s and has been held in various locations across Europe, including Gleneagles (Scotland), Bu-
dapest, Berlin, Athens, Dublin, Seville and, most recently, Rome. In total, 161 participants from 34 coun-
Grace Catalysts tries were present at the Munich 2011 conference. These included representatives from 51 refineries, 5
Technologies research institutes and 11 technology providers. A range of professionals attended the conference, from
young FCC process engineers up to refinery managers from Europe, the Middle East, Africa and the
FSU. They enjoyed 7 sessions of technical presentations spread over three days.

The first session was dedicated to commercial experience of low and zero rare-earth catalysts. Dr. Frank
Wetzel from the MiRO refinery in Germany, as well as Senad Bešić and Dubravko Drazenovic from the
INA Rijeka refinery in Croatia, described how the use the rare-earth free REsolution® catalyst has helped
their refineries to reduce catalyst costs whilst maintaining high performance. Dr. Wieland Wache from the
BAYERNOIL Vohburg refinery in Germany described the successful application of the rare-earth free
REduceR® catalyst, which has been used to reduce overall rare-earth requirement from 3.1 wt.% to less
than 1.0 wt.% whilst allowing the refinery to increase resid processing. In the second session Angelos
Lappas from CPERI highlighted refinery benefits from using an external FCC catalyst testing laboratory,
Matthew Thoelke from CMAI discussed the propylene market in Europe, Rahul Pillai from KBR de-
scribed the use of catalyst coolers in maximum propylene FCC operations and Ted Knowlton from PSRI
gave a presentation on the mitigation of secondary cyclone erosion using vortex stabilizers. The first so-
cial evening was held at the Augustiner-Bräu, which dating back to 1812 is one of the oldest and most
popular restaurants in Munich. The participants enjoyed traditional local food and drink, as well as a
Bavarian band, which helped to provide a thoroughly unique experience.

GRACE EUROPEAN CATALAGRAM® 19

The third session included case studies of the Grace resid cata-
lysts NEKTORTM, NEKTOR-ULCCTM and ResidCrackeRTM. For ex-
ample Bernhard Zahnbrecher from the BAYERNOIL Neustadt
refinery described how ResidCrackeRTM has provided improved
product yields and attrition resistance since it replaced a competi-
tor catalyst at the unit. Gautham Krishnaiah explained how the
RIVE company has partnered with Grace to provide breakthrough
FCC catalysts through the commercialisation of Molecular High-
wayTM technology. Finally Cyril Dollfus highlighted the benefits of
air and FCC expander products from Dresser Rand. The fourth
session focused on environmental additives and catalyst technol-
ogy for hydroprocessing. Commercial experience of SOX MCD, a
low-cerium SOx reduction additive was provided, and Juan Var-
gas from Petroplus Coryton discussed how XNOx® W additives
provided a clear reduction in NOx emissions allowing the refinery
to reinitiate the additions of antimony whilst still remaining within
the required limits of NOx emissions. ART (Advanced Refining
Technologies®) gave presentations describing progress in the de-
velopment of catalyst systems for ultra-low sulfur diesel, as well
as catalyst systems for FCC pretreating and VGO desulfurization.
Session five closed the second day of presentations with Frans
Ruigrok from Pneumix discussing automated injection systems,
and Chris Santner from Shaw Energy and Chemicals describing
how computational fluid dynamics (CFD) can be used as an effec-
tive tool for FCC design, improvement and troubleshooting. After a
full day of technical presentations the evening social event was
held at the BMW museum, which is famous for its innovative ar-
chitecture. The participants were presented with a comprehensive time performance management system to improve refinery
survey of cars, motorcycles and engines, old and new. The BMW process unit reliability, Philip Thornthwaite from Nalco described
art car collection was also on show, which includes cars that lead- how FCCU operations can be optimised and improved using
ing artists, such as Andy Warhol, have worked on since 1975. chemical treatment programs, and Dr. Martin Weng gave the final
presentation of the conference on the use of multiphase CFD for
Sessions six and seven were held on the final day. Tamara troubleshooting and optimization of cyclones in FCC unit.
Galindo showed how the Grace DieseliseR TM catalyst has helped We would very much like to thank everyone who attended the
the Repsol Puertollano FCC unit to maximise LCO yields, Pete 14th Grace FCC Technology Conference. Without the participants
Van Opdorp from UOP gave a presentation on how to maximise and presenters, it would not have been possible to host such a
FCC margins and operating stability when processing hy- successful conference. We very much hope to see everyone
drotreated feedstocks, Luciana Franco from ENI discussed a real again, as well as new people, at the next event.

20 March 2012
 Technology Support Experience

The Leading FCC Catalyst Supplier

in Europe

www.grace.com
www.e-catalysts.com
GRACE®, GRACE DAVISON®, ENRICHING LIVES, EVERYWHERE®, CATALAGRAM®, REPLACER®, REACTOR®, RESOLUTION®,
REDUCER ®, OLEFINSULTRA®, NEXUS®, are trademarks, registered in the United States and/or other countries, of
W. R. Grace & Co.-Conn. ENHANCER™, RESIDCRACKER™, DIESELISER™, NADIUS™, NOMUS™, NOMUS-DMAX™ and NEKTOR™
are trademarks of W. R. Grace & Co.-Conn. PNEUMIX® is a trademark, registered in the United States and/or other countries, of Pneumix B.V.

This publication is independent and is not affiliated with, nor has it been sponsored by Pneumix B.V., Bayernoil Neustadt Refinery, or Orpic.
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 or status.

© Copyright 2012 W. R. Grace & Co.-Conn. All rights reserved.

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.

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