Alcohol Ethoxylates

As Replacements for
Alkylphenol Ethoxylates

Bryan White and Elizabeth Endler

Shell Global Solutions

Westhollow Technology Center
Houston, TX USA

19 May 2008
AOCS Meeting, Seattle, WA
Outline

▪ Background

▪ Key Properties

▪ Comparison of Ethoxylates
– Physical properties
– Handling
– Performance
– Biodegradation

▪ Summary and Conclusions

Background:
Alkylphenol and Alcohol Ethoxylates

▪ APEs historically used for performance and cost-benefit profiles

– Unique structure can provide benefits to the formulator
– NPEs used in hard surface cleaning, textile applications
– OPEs used in industrial applications

▪ Alcohol ethoxylates
– Used extensively in consumer applications
– Suitable for large-volume applications
• Biodegradation profile
• Performance needs to be acceptable, equivalent or improved as
compared to the original surfactant in a formulation
Key Properties for Formulating with
Nonionic Surfactants

Structure and branching

▪ General Properties influence chemical and
– Storage and Handling
– Emulsification
physical properties, such as…
– Wetting ❑Solubility
– Moderate foaming ❑Viscosity
❑Pour Point
❑Cloud Point
▪ Hard surface cleaning ❑Cleaning Performance
– Fast wetting
– Soil removal

▪ Textile processing
– Fast wetting
– Stability under a wide range of processing conditions
– Handling
Structure: Alkylphenol Ethoxylate Examples

Nonylphenol Ethoxylates (many isomers possible)

O CH2CH2O H
n

Octylphenol Ethoxylates

CH3 CH3
CH3 C CH2 C O CH2CH2O H
n
CH3 CH3
Structure: Alcohol Ethoxylate Examples

~80 % Linear
Name Hydrophobe Avg
~20 % Branched at 2-alkyl position (as shown)
EO
Length
O
O H AE 91-8 C9,C10,C11 8
m
R AE 1-9 C11 9
R = Methyl, Ethyl, Propyl, etc m = 0-9 EO units AE 25-7 C12,C13,C14,C15 7

>99 % Linear

O OH
m
Physical Properties of NPE and Alcohol Ethoxylates:
Performance and Handling Guides

HLB Pour Point

•Based on EO content
•Provides application direction
Provides a good measure of
HLB Application ease of handling and storage
4-6 W/O emulsifier (e.g. below ambient
7-15 Wetting agent temperature)
8-18 O/W emulsifer
10-15 Detergent

AE AE AE AE AE
NPE-9
91-6 91-8 1-9 25-7 25-9

HLB 13.0 12.5 13.7 13.9 12.2 13.2

Pour Point (C) -1 6 16 18 20 25

Selected Alcohol Ethoxylates are Less Viscous than
NPE-9 At Concentrations Under 40%

Viscosity (cp) of Aqueous Ethoxylate Solutions at 22 C

Surfactant 10% 20% 30% 40% 50% 60% 80%
(wt%)
AE 91-6 3 13 63 173 187 144 80
AE 91-8 2 6 29 138 Gel Gel 120
AE 1-9 2 6 26 245 Gel Gel 104
NPE-9 290 Gel Gel 3020 1080

✓ Alcohol ethoxylates based on light alcohols offer

good formulation capability at up to 40 wt% of
surfactant in solution.
✓ AE 91-6 is readily diluted in water over the entire
concentration range (10-80 wt%).
Gel Regions Are Similar or Improved for
Alcohol Ethoxylates of Light Alcohols

60

50 AE 1-9
Temperature (°C)

Gel NPE 9
40
Room
30 Temperatur
Gel
e
20

10 Liquid
Gel
AE 91-6
0

-10
0 20 40 60 80 100
Surfactant Concentration (wt%)
Cloud Points of Nonionic Surfactants Are
Affected by Presence of Electrolytes

100
Cloud Point (°C)

90 NPE-9 AE 91-6 AE 91-8

80
70
60
50
40
30
20
10
0
Water Na2SO4 Na2SiO3 NaOH Na2CO3 H2SO4 HCl

To maximize wetting and scouring at various

temperature ranges, the effects of electrolytes
should be considered when formulating with
nonionic surfactants
1 wt% Ethoxylate, 5 wt% Electrolyte, Distilled Water
Draves Wetting Times Are Comparable or
Improved with Alcohol Ethoxylates
Wetting Times (sec) at 25°C

20

15

10

0
AE 91-6 AE 91-8 AE 1-9 AE 25-7 NPE-9

Shorter wetting times can improve cleaning

efficiency and effectiveness.
Foam Stability:
Nonionic Surfactants Are Comparable
Foam Performance Rating

100

95

90

85

80

75
NPE-9EO N91-8 N1-9

All 3 nonionic surfactants slightly reduce foam formation

relative to a high-foam standard formulation
Ultimate Biodegradation Comparison
of Nonionic Surfactants:
Alcohol Ethoxylates Show Increased CO2 Evolution
% of Theoretical CO2 Evolution

100%
90%
80%
70%
60%
50%
40%
30% NPE-9
20%
10%
0%
0 5 10 15 20 25 30
Time (Days)
Summary

✓ APEs, in particular NPEs, have a long history of wide uses as

effective cleaners and emulsifiers
✓ Alcohol ethoxylates can serve as excellent replacements for
NPE in a variety of applications, including hard surface cleaning
and textile wetting
✓ Replacement options are dependent upon the specific
application and properties required
✓ As a start, products with comparable HLB values can be selected

✓ Alcohol ethoxylates can offer comparable or improved

formulation ease and performance compared to NPE
Acknowledgement

▪ Higher Olefins and Derivatives Research and

Technical Support Team, Westhollow Technology
Center
Thank you!

Questions?