Exxal™ Alcohols for SurfactantsJuly 2018
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Partial organization chart as of June 2018
Exxal™ Alcohols
6
Global oxo platform with production sites in all three regions
ExxonMobil oxo platformIntegrated, global, flexible
Propylene C3=
Butylene C4=
Ortho-Xylene
Branched higher olefinsC6= to C12=
Neo acidsC5,C10
PAN
Jayflex™plasticizer
DINPDIDPDIUPDTDP
SC, FCC
SC, FCC
Reformer oxidation
oligomerization
carbonylation
oxo esterification
Branched oxo alcohols
Exxal™ 8 Exxal™ 9 Exxal™ 10Exxal™ 11 Exxal™ 13
Integrated feedstocks Chemical intermediates Plasticizers
Exxal™ Alcohols
Adhesives Lubricants
Stabilizer packages
Plastics / Polymers
Exxal™ 8 Exxal™ 9 Exxal™ 10 Exxal™ 11 Exxal™ 13
Acrylates/ Methacrylate
Zincdithio
phosphates
Thioglycolates
Phosphites PhosphatesEsters
Non-ionic surfactants
EO,PO
Phenolic Antioxidant
Ionic surf. sulfates,
phosphates
Industrial Surfactants
Lube Additives
Branched alcohols and derivatives are performance differentiated
• Low pour points
• High steric hindrance
Surfactant derivatives based on branched molecules offer:
• Better dynamic properties
• Superior wetting performances
• Less gel phases
Exxal Alcohol Structures
Exxal 8
Theoretically 39 primary alcohol isomers possible
Exxal 9S
Theoretically 89 primary alcohol isomers possible
Exxal 10
Theoretically 211 primary alcohol isomers possible
Exxal 11
Theoretically OVER 500 primary alcohol isomers possible
Exxal 13
Theoretically OVER 3057 primary alcohol isomers possible
Exxal 8 Exxal 9S Exxal 10 Exxal 11 Exxal 13
Chemical Name Isooctanol Isononanol Isodecanol Isoundecanol Isotridecanol
Acid ValueMg KOH/g - ASTM D1045* <0.05 <0.05 <0.05 <0.10 <0.03
Boiling Range°C – ASTM D1078* 186 - 192 201 - 207 218 - 224 233 - 239 255 – 263
Carbonyl NumberMg KOH/g ISO 1843-1/ASTM E411* <0.20 <0.20 <0.20 <0.20 <0.20
ColorPt/Co – ASTM D5386 5 5 5 5 5
Density at 20°Cg/cm3 – ASTM D4052 0.831 0.834 0.838 0.841 0.846
Flash Pt.PMCC °C – ASTM D93 >70 >80 >90 >100 >100
Hydroxyl NumberMg KOH/g – ISO 1843-5 425 377 350 321 285
Pour Pt.°C – ASTM D5950* <-40 <-40 <-40 <-40 <-40
Viscosity at 20°CMm2/S – ASTM D445 12 17 21 27 48
Water contentWt% - ISO 12937 <0.1 <0.1 <0.1 <0.1 <0.1
Exxal Alcohol Typical Properties
These are not sales specifications. The data is listed here for comparative purposes only. Sales specifications for Exxal alcohols are available through the product links at www.exxonmobilchemical.com (Alcohol at a Glance Brochure)
C6 C7 C8 C9 C10 C11 C12 C13 C14+ Avg Branching(# branches/molecule)
Spec LimitsMax
Exxal 8 < 0.1 2.6 92.0 5.1 0.3 1.6C6+C10+
2.0C73.5
C92.0 – 9.0
Exxal 9S 1.9 91.5 6.5 0.1 1.8
Exxal 10 3.0 89.8 7.2 2.0
Exxal 11 0.5 8.5 84.6 6.4 2.2
Exxal 13 0.1 0.2 1.8 21.4 69.7 6.8 3.1C9+10
2.0C14+
10.0
Structural Data for Exxal Alcohols
Average Carbon Number Distribution by GC (wt%)
C2-branching estimated between 10-15%
Global supply with regional responsiveness
Baton Rouge
ShanghaiTechnology
Center
BaytownTechnology
Center
MachelenTechnology
Center
Oxo alcohol
Higher olefin
Neo Acids
Sarnia
NDG, France
Fawley
Antwerp
Rotterdam
Singapore
Regional inventory of global grades
US EU AP Brazil
Exxal 8 • • •
Exxal 9 • • • •
Exxal 10 • • • •
Exxal 11 ◦ • •
Exxal 13 • • • •
Neo Acid • • •
Manufacturing site
Technology Center
Key Integrated site
Exxal 11 vs Exxal 13
13
Exxal™ 13 Performance at a Glance
Exxal alcohols :• Better dynamic properties• Superior wetting performances• Less gel phases
Property Units Method
Surface tension lowering and
pC20
mN/m CI-TM8
Gel phase : maximum
concentration without gel
phase by viscosity
wt%
surfactant
CI-TM5
(viscosity)
Wetting time by Draves test seconds CI-TM3
(ASTM-D2281)
Foam height by Ross-Miles mm CI-TM6
(ASTM D1173)
Dynamic surface tension by
max. bubble pressure
mN/m CI-TM7
DST*
Note CI-TM refer to ExxonMobil methods
Exxal 13 vs Competitive Alcohols8 Mole EO
Exxal™ 11 vs Exxal 13 in Surfactant Applications
20
30
40
50
60
70
80
90
5 6 7 8 9 10 11
Clo
ud
po
int
in w
ate
r °C
Mole EO/mole
Exxal 11
Exxal 13
Exxal™ 11 (EO)x and Exxal 13 (EO)x+1 have comparable cloud points and HLB values
* Model curves based on internal ExxonMobil data
Cloud Point
Exxal 11-7EO Exxal13-8EO Exxal 11-8EO Exxal13-9EO
Cloud point in water (°C) 46.5 44.3 61.6 57.7
HLB 12.8 12.8 13.5 13.3
Dyn. Viscosity (mPa.s) @40°C 28.3 36.9 31.29 40.56
Kin. Viscosity (mm2/s) @40°C 28.7 37.4 31.45 40.80
Density (g/cc) @40°C 0.9879 0.9863 0.9950 0.9940
Pour Point (°C) +11.0 +14.0 +16.0 +18.0
Exxal™ 11 and Exxal 13 Ethoxylate Comparison
At similar HLB, cloud point and pour point of the corresponding ethoxylates are close while the viscosity of the Exxal 11 ethoxylate is lower
Exxal™ 11 and Exxal 13 ethoxylates are equivalent at loweringsurface tension, while the CMC of the Exxal 13 ethoxylate is much lower
26.5 27.2
376
76
0
50
100
150
200
250
300
350
400
10.0
15.0
20.0
25.0
30.0
Exxal 11-7 Exxal 13-8
CM
C (
mg
/L)
Su
rf T
en
sio
n a
t C
MC
(m
N/m
)
Min. ST (mN/m) CMC (mg/L)
Surface Tension and CMC
Wetting: Hydrophobe Comparison
Draves Test Wetting Time, 1g/L, room temp.
3.5 3.3
0.0
1.0
2.0
3.0
4.0
5.0
Exxal 11-7 Exxal 13-8
We
ttin
g t
ime
(s)
Wetting properties of Exxal™ 11 and 13 ethoxylates are comparable
15
25
35
45
55
65
75
0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
Te
mp
era
ture
(°C
)
Active Content
Exxal 13-8EO
Exxal 11-7EO
Exxal™ 11 ethoxylates have lower gel phase formation
Gel Phase Formation
Air-sparging method. Surfactant 0.1 g/L. Air flow 0.3 L/min. T=20C. Demin. water
0
20
40
60
80
100
120
0 100 200 300 400
Fo
am
He
igh
t (m
m)
Time (s)
Foam height versus time
Exxal 13-8EO 0.1g/l I
Exxal 11 7EO 0.1 g/l
83.476.378.20
41.20
0
20
40
60
80
100
Fo
am
he
igh
t (m
m)
Foam Height collapse after 180 and 300s
Exxal 13-8EO HLB 12.8 Exxal 11 7EO HLB 12.9
300s180s
Exxal™ 11 ethoxylates show slightly higher foam formation but faster collapse
Foaming Characteristics
Exxal™ 11 Ethoxylate Exxal™ 13 Ethoxylate
Pour Point - Alcohol = =
Reactivity = =
Effectiveness (lowering surface tension) = =
Efficiency (CMC) +
Wetting time = =
Gel phase +
Foam collapse Faster Slower
Biodegradability Readily biodegradable Readily biodegradable
Maximum solubility of oil per 1g of surfactant +
Interfacial Tension +
Summary/Conclusions
Exxal™ 11can be used as an effective alternative to Exxal 13 in high performance ethoxylate surfactants
Exxal 10™ vs C9-11 Alcohols
24
GC Distribution of C10 Alcohols Ethoxylated (6EO)
25
Reactivity of Exxal™ 10 is very similar to other C10 alcohols
Method: 26.2.1 (ExxonMobil)
Cloud Points (1% in Water)
26
At the same degree of ethoxylation, Exxal™ 10 ethoxylates have lower
cloud-point than linear and semi-linear alcohol ethoxylates
Method: CI-TM1 (ExxonMobil)
Surface Tension Lowering: Hydrophobe Comparison
27
Method: CI-TM8 (ExxonMobil)
Exxal™ 10 is better at lowering surface tension, but its CMC is higher
Draves Test
28
Branched hydrophobes impart shorter wetting times
Method: CI-TM3 (ExxonMobil)
Gel Phase Formation
29
Exxal™ 10 ethoxylates exhibit less gel phase formation
than linear and semi-linear alcohol ethoxylates
Method: CI-TM5 (ExxonMobil)
Maximum solubility of oil per 1g of surfactant
30
Exxal™ 10 ethoxylates solubilize oils better than
linear and semi-linear alcohol ethoxylates
* Theoretical calculations based on internal ExxonMobil data
Interfacial Tension
31
Exxal™ 10 ethoxylates show lower interfacial tension
when compared to linear and semi-linear alcohol ethoxylates
* Theoretical calculations based on internal ExxonMobil data
Summary and Conclusion
32
Exxal™ 10 ethoxylates offer performance benefits enabling high
performing surfactants vs competitive surfactants in many applications
Best PerformingEthoxylate
Reactivity
Effectiveness (lowering surface tension)
Efficiency (CMC)
Wetting time
Gel phase
Maximum solubility of oil per 1g of surfactant
Interfacial Tension
Exxal™ 10
L C10
SL C9-11
Regulatory Landscape
Historical scheme for chemical safety regulation
Safety of FacilitiesProtect workers and
immediate environment from chemicals
Safety of Chemical ProductsProtect general public &
environment from chemicalse.g. surfactant biodegradation
Timeline
Number and complexity of
Regulations
Emerging economy
Developed economy
Emerging trend for chemical safety regulation
Timeline
Number and complexity of
Regulations
Emerging economy
Developed economy
• Proliferation of Chemicals Management regulations
• China
• Korea
• Turkey
• Taiwan
• Increased complexity (EU REACH, TSCA)
• Formulator/end user requirements increasing• Walmart
• California
• Sustainability an increasing focus
• Definition varies by country and sector
Rapidly increasing global compliance requirements
0
100
200
300
400
500
600
700
800Americas minus USA & Canada
Eurasia, ME & Africa
AP Minus China
China
We can help you navigate the increasingly complex global landscape
Regulatory Growth in Emerging Economies
Exxal 8 Exxal 9 Exxal 10 Exxal 11 Exxal 13
Chemical Name Isooctanol Isononanol Isodecanol Isoundecanol Isotridecanol
CAS Number 68526-83-0 68526-84-1 68526-85-2 68551-08-6 68526-86-3
EC Number 271-231-7 271-233-5 271-234-0 271-360-6 271-235-6
CAS Definition Alcohols, C7-9-iso-, C8-rich
Alcohols, C8-10-iso-, C9-rich
Alcohols, C9-11-iso-, C10-rich
Alcohols, C9-11-branched
Alcohols, C11-14-iso-, C13-rich
REACH (EU) Full Substance Full Substance Full Substance Full Substance Full Substance
REACH Number 01-2119449923-30-0001
01-2119459285-32-0000
01-2119449807-26-0000
01-2119449922-32-0000
01-2119454259-32-0000
Registration and world-wide inventory statusExxal alcohols
TSCAENCSISHL
KECI TCSI PICCS AICS DSL IECSCEINECSELINCS
Focus on Sustainability
Source: ExxonMobil Corporate Citizenship Report, 2015
ExxonMobil is committed to addressing the challenge of sustainable development -balancing economic growth, social development and environmental protection so future generations are not compromised by actions taken today
Our Commitment to Sustainability
By designing our approach to corporate citizenship around six key focus areas, we contribute to society’s broader sustainability objectives and manage the impact of our operations on local economies, societies and the environment
Embedding sustainability into our chemical business
of
freshwater
consumption at our
operations
2016 vs. 10-yr avg*:
-14%
Managing
water use
Workforce
Lost Time Injury
2016 Performance:
0.03
Focusing
on safety
Developing
new solutions
GHG emissions
2016 vs. 10-yr avg*:
-9%
Mitigating
emissions
of
cogeneration capacity
Equivalent to the
annual energy
needed to power 2.5
million U.S. homes
5,500MW
Energy
efficiency
Source: www.exxonmobilchemical.com
*2007-2016 Average
increase in crop
yield with
polyethylene films
such as films made
from Exceed™ XP
+50%
• Responsibility throughout life cycle
• e.g., ISO 14001 certification
• Responsible Care®
• Hazards well-characterized
• Readily biodegradable – feedstock and derivatives1
• Lower pour point – easier handling2
• Lower greenhouse gas emissions vs. ‘average’ of palm kernel oil–based alcohols3
• No ‘food versus chemical’ debate – synthetic alcohols do not directly impact food prices or land use
What defines a sustainable surfactant feedstock?
1 Per OECD 301F2 Exxal 13 pour point <40°C per ASTM D59503 Shah et al. Comparison of Oleo- vs Petro-Sourcing of Fatty Alcohols via Cradle-to-Gate Life Cycle Assessment. J Surfactants Deterg. 2016; 19(6): 1333–1351.
• Hazard properties well understood through extensive toxicological dataset
• All Exxal™ alcohols meet ready biodegradable criteria per OECD 301F
• Health Information Profiles and Product Environmental Profiles summarize key data and basis for hazard conclusions
• Available upon request
Exxal™ alcohols: thoroughly studied
Enabling Sustainable Surfactants
Biodegradability testing at EMBSI: OECD 301F
• Measures “ultimate” biodegradation
• Uses manometric respirometer
• Monitors oxygen consumption
continually
• Conducted with non-acclimated
inoculum
• Requires 60% “pass” level
Branched alcohols and their ethoxylates biodegradability
0
10
20
30
40
50
60
70
80
90
100
0 2 4 6 8 10 12 14 16 18 20 22 24 26 28
% B
iod
eg
rad
ati
on
Days
Exxal™ 10
Exxal™ 10-6EO
Per OECD 301F
ExxonMobil data
Exxal™ 8 – 4EO
Exxal™ 8 – 6EO
Exxal™ 8 – 8EO
Exxal™ 8 – 10EO
Exxal™ 9 – 1EO
Exxal™ 9 – 3EO
Exxal™ 9 – 5 EO
Exxal™ 9S – 7EO
Exxal™ 9 – 8EO
Exxal™ 9 – 20EO
Exxal™ 10 – 3EO
Exxal™ 10 – 6EO
Exxal™ 10 – 7EO
Exxal™ 11 – 7EO
Exxal™ 13 – 3EO
Exxal™ 13 – 5EO
Exxal™ 13 – 7EO
Exxal™ 13 – 8EO
Exxal™ 13 – 9EO
ExxonMobil has a diverse alcohol grade slate that meets the standards…
Branched alcohol
Exxal™ 8
Exxal™ 9
Exxal™ 9S
Exxal™ 10
Exxal™ 11
Exxal™ 13
Branched alcohol ethoxylate
Exxal™ alcohols and ethoxylates are readily biodegradable
Readily biodegradable (>60%) per OECD 301F Within 10-day window
0.1
1
10
100
Exxal 12*-7EO Exxal 13-7EO Semi-linear C13-15-7EO
Semi-linear C12-15-7EO
LC/EC 50 (mg/L)
Branched alcohol ethoxylates have lower labelling requirements
Less Toxic
More Toxic
algae
Daphnia
rainbow trout
fathead minnow
Acute aquatic toxicity of 7-mole EO surfactants
Any result below 1 mg/L would lead to classification as acute category 1 under GHS
ExxonMobil data
Exxal™ Alcohols for Sustainable Surfactants
Sustainability in Raw Material Selection
Sustainability in Manufacturing
• Fast wetting times could lead to reduced water consumption and faster processing
• Less gel phases could help with energy efficiency
• Exxal alcohols and their ethoxylate derivatives are readily biodegradable per OECD 301F
• Aquatic toxicity testing to date indicates no GHS Category 1 label required for Exxal ethoxylates
• Publication of biodegradability and toxicity testing coming in late 2018
• 3rd party LCA indicates minimal differences between Oleo and Petro based alcohols
• ExxonMobil Chemical relentlessly focuses on mitigating emissions, managing water usages, and reducing energy consumption
• All Exxal alcohols have a pour point < -40⁰ F• Low pour point Exxal alcohols could increase
energy efficiency with ease of transportation and handlingSustainability in Use
Sustainability in Disposal
ExxonMobil Vision to 2030
49
30
60
90
'00 '04 '08 '12 '16
Index
Energy 2.0%
GDP 2.7%
Chemicals 4.2%
Demand growth
Leverage our unique position for advantaged
growth
Establish ourselves as a visible industry leader in
sustainability
Grow Lead
Continue to strengthen major integrated
complexes
Strengthen
Our vision for ExxonMobil Chemical
Oxo business strategy aligned with EMCC strategy
Propylene C3=
Butylene C4=
Ortho-Xylene
Branched higher olefinsC6= to C12=
Neo acidsC5,C10
PAN Jayflex™plasticizer
Exxal™ 8 Exxal™ 9 Exxal™ 10 Exxal™ 11 Exxal™ 13
Focus on New Applications and New Products
Lower CN
Higher CN
Ethylene C2=Linear alpha olefinsC4= to C24= Coatings
Adhesives
Lube/Fuel Additives
Polymer Additives
Surfactants
Others
Customer Derivatives
www.surfactantswhycompromise.com
Performance and SustainabilityExxal Alcohols for Surfactants
Optimized and expanded production
Strong surfactant
growth
Focus on specialty products
Meeting Sustainability
goals
Performance differentiation
Back-up
Surfactant Basics
56
Surfactants Surfactants = Surface Active Agents
Small quantities of surfactants change the properties of systems by acting at interfaces (e.g. air-water, air-oil,etc)
Surfactants – End Use Applications
Some examples of areas of surfactant use are in hard surface cleaning, laundry, dishwashing, personal care, agrochemicals, paints & coatings, textile processing, etc.
What do surfactants do?
They help un-like things go together (usually water and oil)
• Create stable emulsions in creams, lotions, etc
• Lifting oily dirt from clothes, skin or hair
• Helping formulations fluids stay together
(such as metalworking fluids, paints & coatings…)
• Keeps pesticides dispersed in agricultural sprays and wets
hydrophobic surfacesDispersions
Emulsions
• Two different groups in one molecule
Tail or hydrophobe: Branched (e.g. Exxal alcohols) or linear alkyl, Alkylaryl
(nonylphenyl, alkylphenyl)
• Anionic : SO3-, COO-, (CH2CH2O)nSO3
- (sulfates, sulfonates, etc)
• Nonionic : (CH2CH2O)n-H (or EO/PO)
• Cationics : NH2, CONH2, NH4+ (Amines, etc)
• Zwitterionic or Amphoteric : RN+H2CH2COO-
(sultaines, betaines, etc)
(Water-liking)
Surfactants are Amphiphilic molecules
Hydrophobicmoiety (oil-liking)
Commercial Alcohol Ethoxylation with KOH Catalyst
Sources of Water in Ethoxylation Process
• Water from the alcohol
• Water from 45% KOH catalyst
• Water from alkoxide formation
Polyethylene Glycol (PEG) Formation in Commercial Alcohol Ethoxylation
0.0
1.0
2.0
3.0
4.0
5.0
6.0
7.0
8.0
9.0
10.0
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20
Wt
%
Mole EO/mole
Exxal 11 Alcohol Ethoxylate (7EO)
Exxal 11
EO distributions
By gas chromatography
Alcohol Ethoxylates Characterization and Analysis
AE Characteristics AE Specifications
Weight % EO Level Hydroxyl Number
Average Moles EO Color, APHA (or Hazen)
Ave. MW AE pH
HLB Moisture, ppm
EO Adduct Distribution Residual EO, ppm
Weight % Free Alcohol Cloud Point *
Residual Metal Ions Weight % PEG Level *
Effect of Degree of Ethoxylation on Key Properties of Alcohol Ethoxylates
• Detergency• Increases as the number of moles of EO increases for most alcohols (with slight variation that is
dependent on alcohol chain length)
• Foam Height• Increases as the number of moles of EO increases
• Water Solubility• Increases as the number of moles of EO increases
• Viscosity• Increases as the number of moles of EO increases
Hydrogen bonding of AE to water
Typical Surfactant Specifications & Properties
• Density• Cloud point• Pour point• Flash point• HLB number• Surface tension• Interfacial tension• Viscosity• Foaming• Wetting
Industry ApplicationST / IFT* decrease
Fast Wetting
EmulsificationCaustic Stability
Phase Behavior
Low Foaming
Textiles
Pretreat X X X X
Bleaching X X
Dyeing X
Ag ChemAdjuvants X X X X
Suspension Concentrates X X X X
Emulsion Polymerization X
I&I CleaningWetting agents X X X X
Detergents X X X X X
Leather Wetting, degreasing X X X
Oil & Gas
EOR X X X
Emulsion breakers X
Dispersants X X
Mining Frothers, flotation X X
Household
Laundry X X X X
Hard Surface X X X X
Dishwashing X
Personal Care Shampoo X
Matching Performance to Application
67
Property Units Method
Cloud point in water °C CI-TM1
Surface tension mN/m CI-TM8
Gel phase (by rheometry)Temp / wt %
surfactant curvesCI-TM5
CMC critical micelle concentration (20°C)
mg/L mmole/L
Derived from surface tension curves (CI-TM8)
Wetting time in water seconds CI-TM3 (Draves test)
Wetting time in 1% NaOH seconds CI-TM3 A (Draves test)
Foam height mm CI-TM6
Dynamic surface tension msCI-TM7 (Maximum bubble
pressure)
Pour point °C ASTM D5950
Ethoxylate distributions GC 26.2.1 (ExxonMobil)
CI-TM refer to ExxonMobil methods
Methods used