BASF Refining Additives

Presentation at Ecopetrol
October 2008

CONFIDENTIAL 1
Refining Additives Portfolio

 Performance additives
 Conversion enhancement: Converter®
 Olefinic LPG and gasoline octane enhancement: Maximum Olefins
Additive (MOA)
 CO promoters: USP™ - ProCat®
 Fluidization enhancer: EZ FlowTM
 Environmental additives
 Gasoline sulfur reduction: Low Sulfur Additive (LSA)
 SOx emissions reduction: SOx Reduction Additive (SRA)
 Low NOx CO Promoter: OxyCleanTM , Low NOx Promoter (LNP)
 NOx emissions reduction: CLEANOx ®

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Converter

A DMS platform additive that cost-effectively provides

value...

• Upgrades unconverted oils to higher-value products

• Reliably processes poorer-quality feedstocks

• Increase yields under unit constraints

• Faster recovery from operational upsets

• Bottom line: Improved FCC profitability

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DMS - Unique Structure Provides Unique
Benefits

 DMS matrix provides

porosity for heavy
molecule diffusion and
cracking

 Pre-cracking done with the

selective external zeolite
surface rather than an
amorphous non-selective
matrix

 The combination of the

matrix and zeolite 5,000 Å
technologies allows for a
high activity with low coke
selectivity
8/14/2006 CONFIDENTIAL 4
Summary

•Excellent approach to create additional value in the FCC

•Converter significantly improves FCC performance by upgrading
unconverted oils to gasoline and LPG
• High Activity and Excellent Coke selectivity
•Allows flexibility for processing higher feed rate, higher
conversion (upgrading FCC bottoms) or using cheaper
feedstocks/Ecat
•Operational flexibility : Ecat/Converter: Rapid increase in
ACT
• Additional benefits
Enhanced synergy with ZSM-5
• Incremental value generated : US $0.35 - $1.00/bbl of feed

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Maximum Olefins Additives

BASF has developed the next generation of ZSM-5 based

additives which provide the refinery with flexible and cost
effective options to increase LPG Olefins and Octane in the
FCC

• C3= and C4= is generated from of C6 and C9 olefins in

the gasoline fraction.
• C6 and higher olefins have lower octane. Cracking these
results in higher octane of the remaining gasoline.

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Components of all ZSM-5 based additives
are the similar but like all good food,
good ZSM-5 additive requires…..

• Excellent ingredients

• Great recipe

• Know-how

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Components of all ZSM-5 based
additives

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Not all ZSM-5 are created equal

Zeolite

Op tivit
es

ac
ion acc

tim y a
al nd
fus or
)

mi hy
dif al f

xin dro
ed ruci

g i th
pr is c

s r erm
ZSM – 5

eq
(im ure
ov

uir al st
t

Products
oli truc

e d ab
fo ility
S
te

rb
to trix

es
ze
Ma

t
Alumina •Low reactive Al results in excess P that
Phosphorus
attacks of zeolite and blocks channels
•High reactive Al will drain P and reduce
activity of zeolite

8/14/2006 CONFIDENTIAL 9
Maximum Olefins Additive Delivers
Superior Performance at Same Cost

9
8
7
Weight Percent

6
5
4
3
2
1
0
Propylene N-Butylene Isobutylene Isobutane

Base With traditional ZSM-5 With Maximum Olefins Additive

8/14/2006 CONFIDENTIAL 10
What is CO Promoter ?

CO Promoter’s main purpose is to convert/“promote” /

catalyze the reaction of carbon monoxide to carbon dioxide
in the presence of oxygen

CO + 1/2 O2 CO2

Regenerator Reactions:
C + 1/2 O2 CO (i)
CO + 1/2 O2 CO2 (ii)
C + O2 CO2 (iii)

CO Promoters are designed to increase the rate of the

reaction (ii)
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Main purpose of CO Promoter ?

•Pull the CO conversion from dilute phase into

the dense bed

•Protect the mechanical integrity (better cooling

in dense bed) of the unit

•Cleaner burning of re circulating catalyst

(lower CRC)

•Ensure reduction in CO emissions

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EZ Flow

Main purpose of additive is to improve

circulation

- Smaller APS
- Same Properties as FCC catalyst
- With & without activity
- Supports better fluidization

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Variables affecting fluidization properties
of catalyst

Density
Fluidization
Particle size distribution
Catalyst circulation
Attrition Resistance
Catalyst losses
Sphericity
Erosion
Roughness

8/14/2006 CONFIDENTIAL 14
Monitoring fluidizability of catalyst

Umb 2300 g0.126g0.523 e {0.716F45}

= Geldart
Umf dp0.8g0.934{p - g}0.934

e {0.508F45} Gulf Oil

F-Prop =
dp0.568ABD0.663

Umb 6.9
= BASF
Umf (80 - 40)^2*{[(APS+0.5*80)/100]}^3.6

8/14/2006 CONFIDENTIAL 15
Trends not absolute values are important

Umb/Umf, BASF and F-Prop

2.50 0.115
Umb/Umf BASF*10-1

0.11
2.00 0.105
0.1

F Prop
1.50 0.095
1.00 0.09
Umb/Umf Short 0.085
0.50 BASF * 10-1 0.08
F-Prop 0.075
0.00 0.07
3/17/06

4/17/06

5/17/06

6/17/06

7/17/06

8/17/06

9/17/06

10/17/06

8/14/2006 CONFIDENTIAL 11/17/06 16

Comparison of properties

Properties Fresh Catalyst Equilibrium EZ Flow

APS () 75 70-84 47

Particle Size () Wt% Wt% Wt%

0-20 2 0 11

0-40 12 1-12 38

0-80 53 40-67 85

ABD 0.7 0.8-1.03 0.8

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Low Sulfur Additive

Low Sulfur Additive (LSA) is a unique

bi functional formulation which targets gasoline
volume expansion and at the same time as
reducing sulfur compounds in the gasoline

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Reaction Scheme & Sulfur Removal With
Additives

Sulfur Compounds in Feed

Gasoline -S
Benzothiophenes Alkyl -Benzothiophenes
Mercaptans
cracking coking
Cyclization
Thiophenes Alkyl-Thiophenes
alkylation
H2S Coke-S
+olefin

+olefin

R- Tetrahydrothiophenes LCO/HCO-S

H2S
Coke

8/14/2006 CONFIDENTIAL 19
Commercial Application: LSA - 35%
Reduction in Gasoline Sulfur
3.8
3.6
3.4
3.2
CRN S carryover, as kgs/kgs

3.0
2.8
2.6
2.4
2.2
2.0
1.8
1.6
1.4
1.2
1.0
0.8
0.6
0.4
0.2
0.0
0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 1.8 2
Feed S, wt%

NO Additives LSA Period

8/14/2006 CONFIDENTIAL Time 20
Commercial Application: US
Refinery – LSA

90% Distillation Point Sulfur in light fraction Sulfur in light fraction

(NIR*) versus total sulfur versus total sulfur
gasoline : Base gasoline : With LSA
165 12.5% 10.6%

170 14.1% 11.5%

175 15.8% 12.3%

180 17.5% 13.2%

* Near Infrared Technique

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SOx Reduction Additive (SRA)

 Magnesium-based chemistry
 Optimized dual functionality
 Oxidation of SO2 to SO3
 Absorption of SO3
 Excellent performance in full and partial-burn regenerators
 Cost-effective solution to meet SOx abatement

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Sulfur Distribution

 Oxidation of sulfur compounds in coke and SOx Reduction

Additive regeneration

S + O2 SO2
Oxidation occurs in
2 SO2 +O2 2 SO3 regenerator
MgO + SO3 MgSO4

Reduction occurs
MgSO4 + 4H2 MgO + H2S + 3H20 in reactor

 Coke sulfur concentration depends on feed type

8/14/2006 CONFIDENTIAL 23
Sulfur Distribution

Typical sulfur distribution during cracking process

• H2S (40 – 50 %)
• Gasoline (5 – 15 %)
• LCO and Bottoms/Slurry (40-50%)
• Coke (5 – 10 %)
All coke sulfur is converted SOx in regenerator

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SRA Efficacy

SOx Captured (lbs)

Pick-up Factor =
Additive Used (lbs)

SOx Reduction Additive Pick-up Factor = 25 - 30

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NOx Reduction Additives

Three proven technologies

- OxyClean (2X CO Promoter)

- Low NOX Promoter (2-3 X CO Promoter)
- CLEANOx (1 – 2 % of inventory)

Reduction of NOx achieved

- OxyClean ( 30 -40% Reduction)

- LNP non platinum (40-50%)
- Up to 70% reduction

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