Chemical Family / Active Main Polarity (RSN

Primary Function
Type Range)

Phenol–Formaldehyde Water dropper & film

8–11 (oil-soluble)
Resins (Acid Catalyzed) softener

Phenol–Formaldehyde 10–13 (slightly more

Coalescer / cleaner
Resins (Base Catalyzed) hydrophilic)

Epoxy Resins (Di-Epoxides) 9–12 Oil cleaner & coalescer

Polyamines / Ethoxylated Coalescer / charge

10–14
Amines neutralizer

Polyols (e.g., polymerized

6–9 (very oil-soluble) Penetrator / wetting agent
glycerols)

Polyol Esters 7–10 Fast water dropper

Interface cleaner / wetting

Resin Esters 9–12
agent

11–14 (adjustable by
EO/PO Block Copolymers Flocculant / Treater
EO/PO ratio)

Polyalkylene Glycols Wetter / dispersant /

10–15
(PAGs) synergist

Sulfonates (Petroleum or Wetting & solids

12–16
Synthetic) displacement

Polyethyleneimines (PEI) Charge neutralizer /

10–14
Alkoxylates coalescer

Alkylphenol–
Formaldehyde–Amine 9–13 Hybrid dropper + treater
Hybrids
Polyacrylates /
Stabilizer / performance
Methacrylates 11–15
enhancer
(copolymers)

Sulfonated Oils / Amine Wetting & oil phase

12–15
Sulfonates detergent

Wetting Agents (Amine

Variable Solid displacer
Ethoxylates, Sulfonates)
Solvent Carriers (Aromatic
— Transport medium
or Heavy Naphtha)

Hybrid Systems (Resin +

8–13 Balanced performer
Polyol + Amine)

Desalters (Cationic / Water coalescence + salt

10–13
Nonionic blends) removal

Example R&D Blend

Component RSN Weight %

Polyol ester 8 25%

Phenol–
10.5 35%
formaldehyde resin
Polyamine
12 25%
ethoxylate
Resin ester /
13.5 15%
sulfonate
Total blend RSN 10.5-11 balanced for mixed crudes, wide temperature tolerance, and s
separation.
 Interface Mechanism / Film Target Operational Role (Bottle Test / Field)

Disrupts elastic asphaltene–resin films; Improves top oil brightness, reduces

displaces natural surfactants interfacial tension locally

Promotes coalescence by lowering film Enhances interface quality, removes rag

elasticity layer

Penetrates through oil phase; dissolves

Improves water clarity, reduces BS&W
wax/asphaltene bridges

Reduces electrostatic repulsion; helps Promotes clean water cut, better

droplet collision interface

Rapidly diffuses through oil, plasticizes Accelerates initial water drop, dark-to-
film bright transition

Weakens wax–resin film; reduces droplet Improves speed of separation, minimizes

rigidity rag

Re-wets solids and removes adsorbed Cleans interface zone, improves

surfactants desalting

Flocculates submicron droplets; bridges Improves top oil clarity, accelerates

water clusters coalescence

Lowers IFT; redistributes fine solids Cleans interface solids, reduces haze

Improves interface quality, reduces

Re-wets FeS, clays; disperses tank sludge
sludging

Improves coalescence under

Reduces zeta potential of water droplets
electrostatic fields

Produces clean interface, broad crude

Balances water drop and oil dryness
compatibility

Improves wetting and film disintegration Enhances repeatability, reduces

consistency overdosing risk

Cleans solids/wax from interface Improves interface color, reduces sludge

Converts oil-wet solids to water-wet Clears rag layer, stabilizes operation

 Ensures diffusion through oil; reduces
Allows active migration to interface
viscosity barrier

Sequential mechanism: penetrate → Stable performance across variable

displace → coalesce conditions

Enhances conductivity, aids electrostatic

Improves final dehydration and salt spec
grids

lend

Purpose

Penetration & fast drop

Film softening

Coalescence

Interface cleanup

s, wide temperature tolerance, and stable

 Notes / R&D Comments

Best for heavy crude with tight film;

slower but clean separation

Useful in blends for desalting stages

High performance on waxy crude; use in

blends (with polyamine)

Needs good mixing and longer contact

time

Excellent for heavy viscous crudes; often

needs co-actives

Stable on low-salinity or freshwater

emulsions

Works synergistically with EO/PO blocks

Critical for mid-viscosity crudes; temp-

sensitive

Ideal co-agent for resin-based

demulsifiers

Common in slop oil treatments

Very effective in desalters

Cost-effective substitute for multi-

component blends

Used for difficult high TDS emulsions

Additive for tank-bottom cleanout

Key in solids-contaminated systems

Controls contact kinetics, especially at
low T

R&D ideal: single-dose field resilience

Works downstream after primary

dehydration
 Component Type Chemical Families
Penetrator / Treater EO/PO block copolymers, Polyols

Film Displacer / Coalescer Alkylphenol–formaldehyde resins, Di-epoxides

Wetting Agent / Interface Cleaner Sulfonates, amine ethoxylates, resin esters

Booster / Additive Polyamines, resin esters, polyol esters

Solvent System Aromatic, naphthenic, or light paraffinic solvents

 Primary Function
Rapid diffusion through crude; reach interface quickly

Replace asphaltenic/resinic film, reduce elasticity

Remove solids, wax, FeS from interface

Adjust drainage rate and film tension

Carrier phase controlling diffusion rate

 Field Impact
Improves response time and kinetics

Breaks tight emulsions; lowers BS&W

Improves clarity and water quality

Enables clean separation in high solids crude

Balances oil solubility and dispersibility

 Type Example Function

Form rigid, viscoelastic interfacial

Asphaltenes Polar, aromatic sheets
films

Resins Amphiphilic molecules Stabilize asphaltene aggregates

Form soaps that anchor at

Naphthenic acids Acidic surfactants
interfaces
Reinforce interfacial films
Fines (clays, FeS) Solids
physically

What Demulsifiers Actually Do

Demulsifiers are amphiphilic molecules engineered to:
1. Displace natural emulsifiers from the interface
2. Reduce interfacial film rigidity and interfacial tension (IFT)
3. Promote coalescence of dispersed water droplets
4. Accelerate water separation and dehydration
They don’t “break” emulsions by destroying the emulsion directly — they restructure the interface.

Oil-soluble demulsifiers act first (diffuse through crude).

💡 Water-soluble demulsifiers act later (in high water cut or produced water re-emulsions).
4. Mechanism of Action (Step-by-Step)
1. Diffusion: Demulsifier migrates to the oil–water interface.
2. Adsorption: Competes with natural surfactants for surface sites.
3. Film Weakening: Replaces rigid asphaltenic/naphthenic films with flexible polymeric layers.
4. Drainage: Water droplets coalesce and settle due to gravity.
5. Separation: Clear oil–water interface forms; BS&W drops.
5. Formulation Logic
A well-engineered demulsifier blend combines:
Fast-acting oil-soluble component → Break film, reduce IFT
Slow-acting water-soluble component → Enhance coalescence, clean interface
Carrier solvent (e.g., xylene, heavy aromatics, or alcohols) → Improve miscibility & delivery
Modifiers → pH stabilizers, corrosion inhibitors, anti-foamers if needed
Typical blend ratios:
Oil-soluble : Water-soluble → 70:30 or 80:20
Active ingredient → 50–70% depending on crude severity
 Type Solubility Typical Chemistry

Polyether / Ethylene oxide–propylene oxide

Oil-soluble
Polyol copolymers
Epoxy resins Alkylphenol–formaldehyde–
Oil-soluble
(diepoxides) epoxy
Ethoxylated Oil- or water- Phenol-formaldehyde + EO
phenolic resins soluble chains

Block copolymers Oil-soluble EO/PO triblocks

Modified
Water-soluble Amine–polyol hybrids
polyamines

e the interface.
 Mechanism

Displace asphaltene films, lower

IFT
Crosslink or disrupt resin
networks
Penetrate interface, displace
acids/resins
Rapid coalescence via controlled
polarity
Neutralize acidic soaps; work in
high salinity systems
 Variable Impact
Crude type
(paraffinic vs Defines polarity and interfacial structure
asphaltic)
Affects droplet crowding and film
Water cut
stability
Enhances diffusion and coalescence
Temperature
kinetics
Increases droplet size uniformity (harder
Shear history
to break)

pH and salinity Alters natural surfactant ionization

Solids (FeS, Reinforce emulsion film; require pre-

clays) flocculant or wetting aid
 Before selecting any chemistry, you must know what’s stabilizing the emulsion.

Emulsion Type Typical Stabilizer

Asphaltene-stabilized Polar aromatics, resins

Acidic / Soap-stabilized Naphthenic acids, carboxylates

Solid-stabilized Clays, FeS, Fe(OH)₃

Fine-oil emulsion (O/W) Natural surfactants + shear

Synthetic-additive
Residual polymers, inhibitors
interference

Define the Crude Character

Property Diagnostic Tool

API gravity ASTM D5002

Viscosity Rheometer
BS&W content Centrifuge
TAN Titration (ASTM D664)
Solids Filter analysis / microscopy

Salt content Conductivity / chloride test

Match Chemistry to Emulsion Mechanism

Emulsion Mechanism Preferred Chemistry

EO-PO block copolymers + phenolic

Asphaltenic (rigid film)
resin blends
Modified polyamines or
Acidic / naphthenic
ethoxylated amines
Resin + surfactant blend + wetting
Solid-rich systems
agent
High-salinity brine (>150 Water-soluble demulsifiers
000 ppm TDS) (ethoxylated amines)
Foaming / polymer
Non-ionic, low-HLB demulsifiers
interference

Solubility & HLB (Hydrophilic–Lipophilic Balance)

Low HLB (5–8): Oil-soluble → Fast action in heavy crudes.
Medium HLB (8–12): Balanced → Mixed polarity emulsions.
High HLB (12–16): Water-soluble → High-water-cut systems or polishing stages.
Tip: In bottle tests, if separation is incomplete but starts fast → need higher HLB component.
If separation is slow but clean → increase low-HLB oil-soluble portion.

Carrier & Solvent Strategy

Carrier Function
Xylene / Heavy Aromatic
Solubilizes oil-soluble actives
Naphtha
Isopropanol / Methanol Boost diffusion into water phase

Glycol ethers Temperature-stable, reduce flash

Diesel / Condensate Low-cost diluent

The carrier determines delivery efficiency at the injection point. wrong solvent = poor contact = wasted active.
stry, you must know what’s stabilizing the emulsion.

Key Sign Example Crude

Dark brown, viscous, strong film Heavy asphaltic oils

Sensitive to pH, forms under high TAN Naphthenic crudes

Interface scum, slow coalescence Corroded systems

Stable produced water Post-separator water

Foaming, delayed break Chemical flooding

rude Character
Influence

Low API = more asphaltenes → stronger

films
High viscosity slows coalescence
Defines water load for dosage
High TAN = more acid soaps
Affects film rigidity
Indicates brine composition and ion
strength

Emulsion Mechanism

Reasoning

Good oil solubility, strong film

displacement

Neutralize soaps, act at W/O interface

Weakens solid–interface bond

Resist salting-out effects

Avoid surface activity that traps gas

systems or polishing stages.

rts fast → need higher HLB component.
soluble portion.

lvent Strategy
Selection Logic

High-viscosity, asphaltic crudes

High-water-cut, low-temp systems

Offshore or high-flash-point specs

Only when compatibility proven

tion point. wrong solvent = poor contact = wasted active.
 Demulsifier Intermediates Library (Field-Proven Families)
Family Ionic Type Solubility

Ethoxylated Nonylphenol Resins Nonionic Oil-soluble

EO–PO Block Copolymers Nonionic Oil-soluble to balanced

Ethoxylated Polyamines Cationic Water-soluble

Phenol–Formaldehyde Resins Weakly anionic Oil-soluble

Polyethyleneimines (PEI) Cationic Water-soluble

Sulfonated or Carboxylated
Anionic Water-soluble
Surfactants

Modified Polyols / Glycidol Resins Nonionic Balanced

Application Target HLB Solubility Strategy

Heavy asphaltic crude 6–9 Oil-soluble actives (resins, EO–PO)

Light sweet crude 9–12 Mixed polarity blend

High-water-cut crude 12–16 Water-soluble, fast diffusion

Offshore low-temp 10–14 Add glycol ether or alcohol carrier

Acidic/naphthenic crude 8–11 Include cationic neutralizer (amine-based)

Rule: Start from the polarity opposite to the emulsion type.

W/O emulsions → add more hydrophilic demulsifier.
O/W emulsions → add more lipophilic demulsifier.

The R&D Blending Matrix (Core Framework)

a. Binary Blend Design
Start with 2 actives from different polarity ranges.
Example:
Resin (HLB 6) + EO–PO copolymer (HLB 12)
Blend ratio 70:30 → observe kinetics
Adjust until: clean interface + <0.3% BS&W @ 30 min
b. Ternary Blend (Fine-Tuned R&D System)
Add a wetting or bridging component, typically:
 Low MW ethoxylated alcohol
Glycol ether
Polyol resin fragment
It improves droplet coalescence and solids detachment.
s Library (Field-Proven Families)
Function Notes

Film displacement Base active in heavy crudes

Reduce IFT, aid coalescence High-Temp crudes

Charge neutralization High-TAN or basic systems

Strong film disruptor Good at high asphaltenes

Destabilize acidic emulsions Excellent in O/W stages

Counter cationic species Often used in brine polishing

Interface flexibility Stable in high TDS brines

Solubility Strategy

l-soluble actives (resins, EO–PO)

Mixed polarity blend

Water-soluble, fast diffusion

dd glycol ether or alcohol carrier

e cationic neutralizer (amine-based)

 Family Ionic / Non-ionic / Amphoteric

Non-ionic or weakly anionic;

Resin alkoxylates / Phenolic &
sometimes blended with EO/PO
Alkyl-phenolic resins
tails

EO-PO Block / Copolymer Non-ionic (or very mild charge

nonionics influence via ends)

Polyol / Modified Polyol families

Non-ionic / weak-hydrophilic
(polyoxyalkylene polyols)

Amine / Polyamine / Ethoxylated Cationic or amphoteric depending

Amine families on pH

Sulfonates / Ether-sulfonates Anionic

 Solubility Behavior Typical RSN or RSN Range*

Usually oil-soluble; some water-soluble if high EO

High RSN when more hydrophilic; approx 12-22 for strong resin-EO types in
content

Balanced solubility depending on EO/PO ratio;

often oil soluble but can work up to moderate RSN ≈ 6-15 depending on EO/PO / molecular weight (Scribd)
water cut

Water- or mixed-soluble; often used as coalescers

RSN tends to be lower (≈7-12) in many blends for polishing effects (Scribd)
/ modifiers

Often water-soluble or mixed; help neutralize

RSN lower (≈6-10) for many amine-alkoxylates used in Saudi crude blends (
acidic soaps / naphthenic acids

Water soluble or mixed; often used for wetting /

RSN can be high (more hydrophilic) or moderate depending on chain length
interface assistance
 Strength / Weakness

Strong film disruptors; good displacement of

asphaltenes; risk: precipitation or slow drainage if
too hydrophobic

Good interfacial tension reduction; fast break;

need correct EO/PO mix; too much EO can lead to
water-retention / foaming

Polishing / clean interface; slow droplet

coalescence; used in blends rather than sole base
in harsh W/O emulsions

Very useful if TAN or acids present; sensitive to

salinity and dosing; sometimes adverse
interaction with resin if not compatible

Good wetting; helps solids; risk: over-treatment,

foaming, or interference with other surfactants
 Blend Name / Case Components (Families)

Blend “Resin + EO-PO Resin alkoxylate + EO-PO block

copolymer” (two-base) copolymer

Amine alkoxylate + Resin

Blend “Amine-Resin” (two-base)
alkoxylate

Three-base Energetic Blend Resin alkoxylate + EO-PO block +

“Resin / EO-PO / Amine” Amine alkoxylate

Three-base Blend “Resin / Resin alkoxylate + Polyol

Polyol modifier / Amine” modifier + Amine alkoxylate

Three-base Blend “Resin / EO-

Resin + EO-PO + Polyol
PO / Polyol”
 RSNs Approx & Why Favored

RSN mix ~ (Resin heavy ~18-20 + EO-PO ~8-12) → blended RSN

~12-15; balanced

RSN ~ (amine ~6-10 + resin ~18-20) → blended RSN ~10-14

RSN approximate ~ (18 resin, ~10 EO-PO, ~7 amine) giving

overall ~12-14 effective RSN for balancing oil/water layers

RSN ~ (Resin 18-20, Polyol ~8-12, Amine ~6-10) → effective

mid-RSN, with good water phase aid

RSN ~blend ~ (18 + ~10 + ~9) = ~12-14

 What Makes Them Energetic (Why They Perform)

The resin displaces asphaltenic film; EO-PO improves

coalescence and speeds up separation. Excellent for medium
crude / moderate salinity.

Good if TAN or acidic components in crude. Amine neutralizes

acid soaps; resin handles film rigidity.

Very good kinetic break; good interface, works across

temperature variation; acid tolerance; helps in emulsions with
acids + asphaltenes.

Clean interface from polyol; faster droplet coalescence; amine

helps acid or soap effects; good at moderate water cut.

Good for W/O emulsions where water content is moderate,

acid low; gives fast break + good rinse of water phase (clean
water)
 Blend ID Component A

Blend 1 (two-base) Resin alkoxylate 70%

Blend 2 (two-base) Resin alkoxylate 60%

Blend 3 (three-base) Resin alkoxylate 50%

Blend 4 (three-base) Resin alkoxylate 60%

Blend 5 (three-base) Resin alkoxylate 55%

 Component B Component C (optional) Relative % Actives (before carrier)

100% active mix (carrier adds

EO-PO block copolymer 30% –
dilution)

Amine alkoxylate 40% – 100%

EO-PO block copolymer 30% Amine alkoxylate 20% 100%

Polyol modifier 25% Amine alkoxylate 15% 100%

EO-PO block copolymer 25% Polyol modifier 20% 100%

 Non-ionic or weakly anionic;
Resin alkoxylates / Phenolic & Usually oil-soluble; some water-
sometimes blended with EO/PO
Alkyl-phenolic resins soluble if high EO content
tails

Balanced solubility depending on

EO-PO Block / Copolymer Non-ionic (or very mild charge EO/PO ratio; often oil soluble but
nonionics influence via ends) can work up to moderate water
cut

Polyol / Modified Polyol families Water- or mixed-soluble; often

Non-ionic / weak-hydrophilic
(polyoxyalkylene polyols) used as coalescers / modifiers

Often water-soluble or mixed;

Amine / Polyamine / Cationic or amphoteric
help neutralize acidic soaps /
Ethoxylated Amine families depending on pH
naphthenic acids

Water soluble or mixed; often

Sulfonates / Ether-sulfonates Anionic used for wetting / interface
assistance
Strong film disruptors; good displacement of asphaltenes;
High RSN when more hydrophilic; approx 12-22 for strong resin-EO
risk: precipitation or slow drainage if too hydrophobic

Good interfacial tension reduction; fast break; need

correct EO/PO mix; too much EO can lead to water- RSN ≈ 6-15 depending on EO/PO / molecular weight (Scribd)
retention / foaming

Polishing / clean interface; slow droplet coalescence; used

RSN tends to be lower (≈7-12) in many blends for polishing effects
in blends rather than sole base in harsh W/O emulsions

Very useful if TAN or acids present; sensitive to salinity

and dosing; sometimes adverse interaction with resin if RSN lower (≈6-10) for many amine-alkoxylates used in Saudi crude
not compatible

Good wetting; helps solids; risk: over-treatment, foaming,

RSN can be high (more hydrophilic) or moderate depending on cha
or interference with other surfactants