We create
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that makes
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refiners love
fueling the
world.
Advances in FCC Catalyst
Technology and Services
Jeremy Mayol, Vasilis Komvokis, and Carl Keeley
11th May, 2015
19.12.2014
INTERN
1
Agenda
1. Resid FCC Catalyst
2. ZSM-5 Additive for Propylene
 Resid to Propylene
3. Technical Services
R
R
to
P
2
P
FCC
Catalyst
3
 Nickel
Dehydrogenation activity
leading to increased H2 and
coke
ACE H2/C1 Ratio
Benchmark: Impact of Contaminant
Metals on FCC Unit Operation
6
5
4
3
2
1
0
0
Catalyst deactivation, with
some dehydrogenation
activity
5,000
6,000
80
75
70
65
60
0
4
2,000 3,000 4,000
Nickel, ppm
85
FACT, wt%
 Vanadium
1,000
5,000
10,000
V+Na, ppm
15,000
R&D: Analysis of Resid FCC Catalyst
Electron micro-probing
Scanning Electron Microscopy (SEM)
Nickel
 Vanadium is located throughout particle
 Nickel is concentrated in the outer-layer of catalyst (5-10 micron)
5
Innovation: Breakthrough Multi-stage
Reaction Catalyst (MSRC)
 Can we improve upon the DMS based Flex-Tec by distributing the
specialty alumina where nickel is predominantly located?
Alumina
Flex-Tec
Fortress Catalyst
 Yes: By using a technology with increased alumina content in the
outer-stage
 MSRC combines two or more FCC catalyst functionalities within a
single catalyst particle
6
Case Study: Innovative Resid Cracking
Catalysts Improve R2R Unit Profitability
 Tamoil’s Collombey refinery:
 R2R FCC Unit with 100% atmospheric residue feed
 CCR up to 7 wt% and Ni+V up to 10,000 ppm
 Two trials:
 Aegis: Outperformed the resid catalyst with the largest market
share in EMEA. Improved LPG selectivity, outstanding benefit
on bottoms cracking and improved conversion.
 Fortress: Further improved flexibility to upgrade heavy resid
feedstock with increased metals content.
Y.A. Jollien et al., Use an innovative cracking catalyst to upgrade residue feedstock, Hydrocarbon Processing, Feb 2013
Y.A. Jollien et al., Multi-Stage Reaction Catalyst with Advanced Metals Tolerance, PTQ Q4 2013
Case Study: Record Conversion at IsoCAR and Contaminant Metals Level
 +3-4% conversion increased, at iso-catalyst addition rate
Y.A. Jollien et al., Multi-Stage Reaction Catalyst with Advanced Metals Tolerance, PTQ Q4 2013
8
Case Study: Record Bottoms Upgrading
at Iso-Conversion
 Bottoms upgrading increased: increase in the LCO/slurry ratio, at
higher conversion, was +12-15%
Y.A. Jollien et al., Multi-Stage Reaction Catalyst with Advanced Metals Tolerance, PTQ Q4 2013
9
Case Study: Innovative Resid Cracking
Catalysts Improve R2R Unit Profitability
 Aegis:
 Improved LPG selectivity, outstanding benefit on bottoms cracking and
improved conversion.
 +0.40 $/bbl compared with resid catalyst with the largest market share
in EMEA
 Fortress:
 Further improved flexibility to upgrade heavy resid feedstock with
increased metals content.
 +0.30 $/bbl compared to lower contaminant metal operating period
FCC Products + Technical Services = Success!
Y.A. Jollien et al., Use an innovative cracking catalyst to upgrade residue feedstock, Hydrocarbon Processing, Feb 2013
Y.A. Jollien et al., Multi-Stage Reaction Catalyst with Advanced Metals Tolerance, PTQ Q4 2013
ZIP Olefins
Additive
11
Resid to Propylene is a Combination of
Technologies (Catalyst and Additive)
FCC Catalyst
RE-Y Zeolite
Feed
ZSM-5
Linear and
near-linear
C6-C9 olefins
Pore Diameter of 7.4 Å
C3 and C4 Olefins
↑ Gasoline Octane
Pore Diameter of 5.1 to 5.6 Å
7.4 Å
 Higher ZSM-5 usage:
 Increases LPG yield, more light olefins are produced
 Gasoline yield declines, but its octane improves
C. KEELEY, V. KOMVOKIS, M. MIRANDA, et. al., ZSM-5 Additive Maximises Propylene, PTQ Catalysis 2015
R&D: Diminishing Returns with
Increasing ZSM-5 Loading
90%
of incremental
propylene from
first 20% ZSM-5
*40% crystal
Opportunity for improvement
 Partly limited by the
availability of C6-C9 olefins
 Develop new ZSM-5 additive
to increase propylene yield at
the same zeolite content
C. KEELEY, V. KOMVOKIS, M. MIRANDA, et. al., ZSM-5 Additive Maximises Propylene, PTQ Catalysis 2015
Innovation: ZIP Olefins Additive –
Multi-stage Phosphorus treatment
Phosphorus
ZSM-5
Treatment
Pretreated
ZSM-5
Other
Raws
Phosphorus
Source
Binding
Additional Zeolite stability
Acid site strength/
Zeolite stability
Spray dry
Calcine
Multi-stage phosphorus treatment to target all three functions
C. KEELEY, V. KOMVOKIS, M. MIRANDA, et. al., ZSM-5 Additive Maximises Propylene, PTQ Catalysis 2015
Case Study: Maximum Propylene
Solution Catalyst Commercial Trial
Cepsa implemented
advanced Max Propylene
Solution (MPS Catalyst)
based on MOA (ZSM-5
based additive)
 FCC increased propylene
yield and processed
higher amounts of heavy
feed
 FCC profit increased by
$2.50/bbl
J.M. Llanes et al., New Catalyst Increase FCC olefin Yields, Hydrocarbon Processing, pgs. 63-66, April 2014
Case Study: Successful ZIP Olefins
Additive Commercial Trial
Propylene Yield (wt%)
Model Developed on “Base” MOA Case
 Statistical model built
to predict Propylene
yield for a range of
operating conditions
 MOA was replaced in
the MPS catalyst with
ZIP
Actual propylene
Estimated propylene
29-Jan
 Cepsa La Rábida
decided to trial new
ZIP Olefins Additive
26-Feb
26-Mar
23-Apr
21-May
C. KEELEY, V. KOMVOKIS, M. MIRANDA, et. al., ZSM-5 Additive Maximises Propylene, PTQ Catalysis 2015
16
Case Study: Successful ZIP Olefins
Additive Commercial Trial
Propylene Yield (wt%)
ZIP Trial Measured Against Model Predictions
 Similar Propylene for
typical feed quality,
using less additive
 This translates into a
20% reduction in
additive consumption
Actual propylene
Estimated propylene
19-Apr
17-May
14-Jun
12-Jul
17
C. KEELEY, V. KOMVOKIS, M. MIRANDA, et. al., ZSM-5 Additive Maximises Propylene, PTQ Catalysis 2015
Case Study: Improved Flexibility to
Process Heavier Feeds
C. KEELEY, V. KOMVOKIS, M. MIRANDA, et. al., ZSM-5 Additive Maximises Propylene, PTQ Catalysis 2015
18
Benchmark: Propylene
Source: BASF ECat benchmark database
 BASF Maximum Propylene Solution delivers highest Propylene yield
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Technical
Services
20
BASF is Committed to Being an
Innovative Service Provider –
Customer Success is our Goal

Delivery of our product is just the beginning of our
offerings

BASF stands behind its products and through our
technical service ensure our products perform and
deliver value

We work closely with each refinery in evaluating the
FCC unit’s performance, operation limitations, and
goals

This relationship allows BASF to help our customers
continuously optimize to meet their operating objectives

Our team has a vast experience including process
design, operational expertise, catalyst chemistry,
economics, and troubleshooting
21
Innovation: Tools for Unit Optimization
FCCU Modeling
Benchmarking
Gasoline Yield vs. Conversion
Gasoline Yield, wt%
75
70
65
60
55
50
45
40
60
65
70
75
80
85
90
95
Conversion, wt%
Pick up Factor is higher for new SOx reduction additive
800
Measured
Statistical Model
700
Pick-up factor for improved
SOx reduction additive can be
calculated in real-time
600
Statistical
Modeling
500
400
300
Base Case
Start of new SOx
reduction additive trial
200
Model= Function of feed S, flue gas O2, feed concarbon, feed rate, stripper steam rate and feed TBP dist.
N.V. Karpov, C. Keeley, J. Mayol, et al., Case history: Optimization of FCCU with multivariate statistical modelling, Hydrocarbon Processing September 2013
22
New ECat Lab at hte GmbH in Germany –
Quality Results with the Fastest
Turnaround in the World!

On December 2, 2014, BASF launched a new
FCC catalyst testing and research laboratory at
the hte GmbH (hte) site in Heidelberg,
Germany

hte is a wholly owned subsidiary of BASF SE
and a leading provider of high throughput
technology and services for enhancing
research and development productivity

Europe based laboratory significantly reduced
ECat sample transit times, leading to faster
service and also delivered a global flexibility by
doubling BASF’s capability to enable the
success of FCC units across all regions

80% of ECat results available within 20 hrs

100% of ECat results available within 30 hrs
BASF Catalyst Management Services
Operating experience

Specialists handpicked from licensors, design companies and oil refineries
Catalyst and additives

Strong supplier to provide innovative solutions and technologies
Technical Service

Specialists for start-up, monitoring, troubleshooting, optimisation, training, etc.
Logistic solution

Strong supplier with global expertise able to provide a local solution
Spent catalyst

Strong supplier already working with cement companies, steel industry, etc.
We are committed to Deliver Innovative
Products to Improve FCC unit Profitability
 Multi-Stage Reaction Catalyst combines two or more FCC
catalyst functionalities within a single catalyst particle
 The outer-stage of Fortress is enriched with specialty alumina to
make it more effective at nickel passivation
 Fortress™ Resid FCC catalyst is commercially proven at eight
refineries with similar results observed at all locations
 Novel ZIP Olefins Additive boosts Propylene production using
less additive in CEPSA trial
 BASF Technical Service ensure our products perform and
deliver value
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