Basics of Surfactants

Hans Oskarsson
Nouryon Surface Chemistry
01

Nouryon Stenungsund site

AkzoNobel Oil and Gas | Surface Chemistry
2
Agenda

Introduction to surfactants

Functions of surfactants

Classification and applications of

surfactants.

Surfactants for Oilfield

Ecolabel-taugliche Rohstoffe für Geschirrspülmittel 3

Surfactants - SURFace ACTive AgeNTS

Definition

Amphiphilic (”schizofrenic”) compounds with

the following key properties:

Adsorption at surfaces/ interfaces

Aggregation at certain concentrations

and temperatures
Some general surfactant terms

Explanation of some words:

Hydro = water
Lipo = fat/oil
Phobic = hating
Philic = loving

Hydrophobic = Lipophilic
Hydrophilic = Lipophobic
Chemical Structure – Surfactants

Water: Hydrophobic part Hydrophilic part

Oil: Lipophilic Lipophobic

The balance between the two parts decisive for

the properties of the surfactant!!
Surfactants lower the surface tension

Surface tension

Inorganic
electrolytes
g0

Organic solutes
Amphiphilic solutes
Concentration
Surfactants migrate to surfaces and aggregates
when increasing concentration

Surface active molecules

Air
orientate themselves in the
interface between two phases.
Water

When the surface is saturated

with surfactants they start to
form spherical globules in the Air
water, which are called Oil
micelles.

Interfacial tension
Water
Industrial applications

Detergent & Cleaners

Cosmetics
Pharmacy
Textile & Fibres
Leather & Furs
Paints, lacquers and plastics
Cellulose and Papers
Mining, flotation
Oil production
Metal processing
Building construction
Plant protection
Food
And others!!
2. Functions of
surfactants

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Why use surfactants?

1. Solubilization 4. Viscosity Modification

Hydrotropy Visco Elastic Surfactants (VES)
Catalysis
Cleaning

2. Interfacial tension 5. Dynamic/Reversible Systems

Foaming Delivery Systems
Emulsification
Wetting

3. Surface modification 6. Ordered Templates

Adsorption Polymerization
Dispersion Nanomaterials

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Foaming – stabilizing the interface of
liquid and air

Most surfactants stabilize foams.

The stabilization depends on
the packing at the air/water
interface.
- Stabilization by addition
of polymer, proteins and particles

- Destabilization by hydrophobic
surfactants and/or branched
hydrophobe surfactants
Surface active polym. (e.g silicons)

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Wetting:
Formation of a Liquid-Solid Interface

Bad wetting, high Good wetting, low

surface tension, big surface tension, small
contact angle contact angle

Contact angle reduction is the key!

 Substrate

• Type of material
• CST (Critical Surface Tension)

Material mN/m
Glass >73
Polystyrene 32
Polypropylene 28
Teflon 18
Water 72

To wet a surface, the surface tension of the liquid

should be below the Critical Surface Tension (CST)
Emulsification

Oil emulsified
➢Surfactants allow us to mix substances of in water
different nature

➢Very important applications:

• Food industry
• Lubricants
• Paints
• Polymerization
• Cosmetics
Repulsion forces
between the head
groups avoid
coalescence of the
droplets
Emulsions

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Dispersing

Repulsion of the head groups avoid

coalescenece and precipitations of
the particles

Surfactants adsorbing on hydrophobic particles

Surface adsorption–surface
modification

Hydrophobic surface Hydrophilic surface

Influenced by:
-Hydrophobe -Hydrophobe
-CPP -CPP
-Salt/temperature -Salt/temperature
-Specific interactions
CPP (Critical Packing Parameter) = v/l ·a
v=volume of hydrophobe
l=length of hydrophobe
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a=area of headgroup
3. Types of
surfactants

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Types of Surfactants

The Hydrophobe The Hydrophile

➢ Fatty acids ➢ Nonionic types
▪ Ethoxylates
➢ Fatty amines
▪ Glucosides
➢ (Alkyl phenols) ➢ Cationic types +
➢ Fatty alcohols ▪ Quaternary, tertiary and
➢ Etc…. primary amines
_
➢Anionic types
▪ Acids, phosphonic groups
▪ Sulphonates etc…
_
➢Amphoteric types +
▪Glycinates, propionates
▪Betaines
Some important properties of non-
ionic surfactants
100
Cloud point, oC

➢ Have inversed solubility, clouding when heated 80

60
➢ Good wetters – especially with branched
40
hydrophobes
20

➢ Good emulsifiers
0 4 8 12 16 20
Moles EO
➢ Good dispersants

➢ Salt tolerant

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 Nonionic surfactant summary

➢ Second biggest class of surfactants

➢ Compatible with most other surfactants

➢ Used extensively in detergent industry

➢ Alcohol ethoxylate is the biggest sub-class

➢ Polyol (sugars) feed-stocks more popular

➢ Ecotoxicity is good In general, except for NP-ethoxylates

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 Cationic surfactants

Cationic
+ - positive charge
Hydrocarbon chain head-group Counter ion

head-groups:

Cl-

X- X-

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 Substantivity
The Key Feature of Quats

Adsorptive properties of cationic

surfactants and related nitrogen
derivatives

Adsorption, particularly onto solid

surfaces.
Attraction between the positive
charge on the nitrogen atom –
negative charge surfaces
+
N ........... .......... ..........
........... ........... ........... Surface modification
Cationic Surfactants

Substantivity leads to the following functions:

➢Softening

➢Anti-static properties

➢Lubrication

➢Corrosion inhibition

➢Adhesion

➢Hydrophobation
Cationic Surfactants in General

➢ 3rd biggest class of surfactants

➢ Adsorbs to negatively charged surfaces – modifies surface
➢ Hydrophobizing agents
➢ Can be tuned to control rheology
➢ Biocidal properties
➢ Are in some cases more toxic to aquatic organisms
(compared to other surfactants)

Surface Chemistry - General Applications and products

Anionic Surfactants

+
Hydrocarbon chain Head-group Counter ion

Head-groups:
Sulfonate Sulphate Phosphate
O O O

R–S–O– R–O–S–O– R–O–P–O–

O O O–
The Three Workhorse Anionic
Surfactants

Linear Alkylbenzene
Sulfonate (LAS)

- +
SO3 Na
- + Alcohol Sulfate
OSO3 Na
(AS)

O O - + Alcohol Ether
O OSO3 Na
Sulfate (AES)

AES is more resistant to water hardness.

Foaming products
C12-C14 common: balance surface activity and solubility
Anionic Surfactants in General

➢Good and cheap detergents

➢Good dispersing properties
➢High foaming
➢Sensitive to hard water
➢Irritating to skin
➢Alkyl benzene sulphonates are questionable for its
environmental properties (poor anaerobic degradation)
Amphoteric Surfactants

➢True amphoterics

➢Betaines

➢Imidazoline derivatives

➢APAC (Alkyl Poly Amine Carboxylate)

Amphoteric Surfactants

Properties/Functions
➢Mild and not irritating to skin
➢Hydrotroping effect
➢Soluble in strong caustic or acid solutions
➢Adjustable foam
➢Special amphoterics have co-builder effect
➢Insensitive to water hardness
➢Corrosion inhibition
4. Examples of surfactant
Oilfield applications
Corrosion inhibition
Demulsification
Cleaning
VES

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Film forming corrosion inhibitors

Surface modification
• Corrosion inhibition (filming amines)
• Adsorption of surface active amines at low concentration
(usually below the CMC). Dosage should be
• Usually a partioning in between oil/water. Solubility in the
different phases and adsorption ability critical

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Demulsification

There are three main mechanisms of chemical

demulsification:
Flocculation
–Water droplets brought together
Coalescence
–Emulsifying film rupture
–Larger droplets have lower IFT
Solids wetting
–Organics dispersed into the hydrocarbon
–Inorganics water-wet and removed with the water

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Examples of demulsifier
chemistries
- Wetting agents Sulphonates/sulphonic acids
-
SO3 Na
-
- Droppers Polyglycols

A-B-A

]n H ]nH
- Driers, interphase control Resin alkoxylates
[ [

[ ]n

- Desalters Resin alkoxylates

X
- New chemistry; cleavable links
R1-O C O-R2
O -R
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Examples of Cleaning in oilfield

Well bore cleaning

applications Rig wash
Tank cleaning

Soil remediation – sand cleaning

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Surfactants in Cleaning

The main tasks of surface active agents for cleaning are to:
✓ reduce the surface tension of water to get
wetting properties and to release soil from surfaces.

✓ emulsify fatty material

✓ disperse solid particles

Visco Elastic Surfactants (VES)

Surf.

Conc .

Salt conc
After F.Lequeux and S.J. Candau 1994
Rheology modification

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“Living polymers”
Application as Drag reducers
Surfactants form
threadlike cylindrical
micelles.
PUMP

Although the micelles are torn

apart by shear forces within
the pump, the fragments
quickly rearrange themselves.