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Production Chemistry & Corrosion Control

Course Reference P142 : Surface Operations

Trainers: Alan Foster & Kevin McLaughlin

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Oil Treatment
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Oil Treatment

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Emulsions and Crude Oil Dehydration

Introduction to Paraffins and Related Problems

Asphaltene Chemistry and its Application to Crude Oil Production

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Crude Oil Dehydration Topics

Emulsion Theory Resolving Emulsions (Demulsification) Dehydration Process Equipment Chemical Selection

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Why Remove Water?

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Wet Oil has Little Value Refineries usually specify <0.5% water The presence of water can lead to corrosion In shipping lines and process equipment In Refinery process systems System Designs Most oil production systems are sized for oil Transport Costs Transporting a by-product with no value is wasteful

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Environmental Considerations

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Removing water from oil (Deoiling), although desirable, creates potential problems:

Disposal of oily separated water

Standards from as high as 40ppm hydrocarbon (offshore)

to as low as 5ppm hydrocarbon (onshore)

Standards often exceeded due to operational problems

Solids build up in production systems

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Emulsion Theory

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Definitions Types of Emulsion Emulsion Formation Emulsion Stability Breaking Emulsions

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What is an Emulsion?

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Definition:

A mixture of two immiscible liquids, one of which is dispersed as droplets in the other, this dispersion being stabilised by an emulsifying agent.

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Types of Emulsion

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Water in Oil Emulsions (W/O)

Normal Emulsion Continuous phase - Oil Dispersed phase - Water Reverse Emulsion Continuous phase - Water Dispersed phase - Oil

Oil in Water Emulsions (O/W)

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Normal Emulsion Photomicrograph

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What is Required For Emulsion Formation?

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Two Immiscible Liquids

Oil and Water

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Source of Oil and Water

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Oil

Formation water

Water Coning in a Waterdrive Reservoir

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What is Required For Emulsion Formation?

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Two Immiscible Liquids

Oil and Water Well Bore, Pumps, Choke, Valves, Bends in Pipework, Flow Regime (Turbulent Flow)

A Source of Mixing Energy / Shear

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Potential Shear Sources

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Flow Regime
Bends in pipework

Chokes/Valves

Pumps

Well bore area perforations

Oil Bearing Formation

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What is Required For Emulsion Formation?

Two Immiscible Liquids

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Oil and Water Well Bore, Pumps, Choke, Valves, Bends in Pipework, Flow Regime (Turbulent Flow) Solids e.g.Formation Fines, Corrosion Products, Scale Treatment Chemicals - Production and Drilling

A Source of Mixing Energy / Shear

An Emulsifying Agent(s)

Natural Surfactants - e.g. Paraffins, Naphthenic Acid Salts

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Emulsifying Agent Surfactant

Simplified Head and Tail Diagram

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Water soluble surfactant head

Oil soluble surfactant tail

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Emulsifying Agent Surfactant

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Head has affinity for water phase Water - Oil Interface

Tail has affinity for oil phase

Note: Emulsifying agents exhibit limited solubility in both the oil and water phases
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Emulsion Ageing

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Increase in time

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Major Factors Affecting Baker Petrolite Normal Emulsion Stability Type and Amount of Emulsifying Agent(s) Degree of Agitation (mixing) Viscosity of Continuous Phase - Stokes Law Density Differential of Produced Fluids - Stokes Law Disperse Phase Content (Water)

as water content increases emulsion stability decreases (generally)

Emulsion Age

emulsion stability generally increases with time

affects other variables emulsion stability decreases with increase in temperature

Temperature

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Stokes Law
V = g(dw - do)r2
18u Where, V = Velocity of water droplet

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r = Radius of water droplet

dw = Density of water do = Density of oil u = Viscosity of oil g = Constant

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General Aim

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Water droplet radius is a squared function in Stokes Law Therefore, water droplet settling velocity is most easily increased by increasing the radius of the droplets Hence, any means of coalescing the water droplets will increase settling velocity and reduce the settling time needed for water separation.

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Resolving Normal Emulsions

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Demulsification

Defined as:The resolution of crude oil emulsions and the

subsequent removal of the separated water phase

(dehydration)

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The Mechanism of Demulsifiers

To Break (or destabilise) a Normal Emulsion a Demulsifier Must Achieve the Following:

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Rapid Migration to the oil/water interface Flocculation Coalescence Solids Wetting

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Factors In Demulsification
Oil Phase Oil Phase

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Water Droplet

Water Droplet

Water Droplet

Water Droplet

Demulsifier Chemicals
Without Demulsifier Treatment the Pliable Film Around the Water Droplet Remains Intact when a Collision Occurs
With Demulsifier Treatment the Film Becomes Brittle and Ruptures when a Collision Occurs

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The Process of Flocculation and Coalescence

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Droplets have strong attraction for each other

Barrier is broken COALESCENCE takes place Contact is made FLOCCULATION

Resultant larger water drop

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Solids Removal

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Removal of solids from the interface may completely resolve some emulsions Types of Solids: Inorganic

FeS, mineral scale (e.g. CaCO3), silt, clay, drilling muds Paraffin, asphaltenes

Organic

Solids removal can be achieved by: Oil wetting (dispersion in oil) Water wetting (dispersion in water)

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Solids Removal

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Advantages of Water Wetting: Removal of solid contaminant Prevents accumulation in downstream vessels easier refining Disadvantages of Water Wetting: Silting of treatment vessels Oily water problems Disposal problems Erosion of valves, pumps, hydrocyclones

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Free Water Knockout Vessel

Gas Outlet

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GAS OIL

WATER Water Outlet

Free Water Knockout

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Gun Barrel (Wash Tank)

Gas Outlet

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Gas Equalising Line Oil Inlet

GAS
Siphon

Oil Outlet

OIL
Water Outlet

WATER

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Horizontal 3-Phase Separator

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Gas Outlet

Produced Fluids

GAS

OIL
OIL+ WATER

WATER

Water Outlet
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Oil Outlet

Horizontal 3-Phase Separator

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Factors Affecting Three Phase Separator Performance

Production Rate Solids Sedimentation

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Oil Level Separator Performance Demulsifier Injection Rate

Temperature

Water Level

Foaming

Separator Design

Interface Level

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Bielectric Dehydrator
Oil Outlet Transformer

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OIL

Electrode Grid

WATER

Distributor Header Oil Inlet

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Water Outlet

Basic Theory of Electrostatic Separation

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When a water in oil mixture is subjected to an AC electrostatic field the following things happen:

Collisions occur between the relatively conductive brine droplets

Coalescence occurs
Separation according to Stokes Law

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Basic Theory of Electrostatic Separation

Brine Droplet Suspended in Oil Phase

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Brine Droplet in an AC Field (Induced Dipole)

+ + + + +

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Basic Theory of Electrostatic Separation

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A d j a c e n t D r o p l e t s i n a n A C F i e l d ( D i p o l e A t t r a c t i o n )

+ + + + + -

+ + + + + -

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Basic Theory of Electrostatic Dehydration

Emulsified Drops

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Elongated Drops

Coalescing Drops
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Important Factors for Electrostatic Coalescence

Population Density

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Voltage Gradient (Electric Field Strength)

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Population Density

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1 %

1 0 %

5 %
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Critical Voltage Gradient (Electric Field Strength)

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Lower Limit Minimum field strength to overcome resistance of stabilising films Upper Limit Maximum field strength, above which droplets are redistributed

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Crude Oil Desalting

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Differs From Electrostatic Dehydration in 3 ways:

Essentially refinery based (some exceptions)

Lower water content of crude feed

wash water added

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Desalter Performance

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Typical Desalter Performance

Salt removal Salt in Salt out Solids removal BS&W out Oil in effluent water Wash water rate 95% (single stage) 98% (two stage) 100lb/1000bbl oil max. 0.2 - 2.0lb/1000bbl oil. 50% - 80% 0.1% - 1.0% 100ppm - 1.0% 3% min. - 8% of volume of crude feed

Operating temperature

100 -150oC / 212 - 301F

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Selecting Demulsifiers

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The Bottle Test Comparative Test Essentially a Field Test Individual Test Designed to Mimic Production System

Production rates Demulsifier dose rate System temperatures Chemical injection points and sampling points Vessel residence times System specifications and problems

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The Bottle Test

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Chemicals Usually Designed for Specific System Looking For

Dry top oil Fast water drop (short residence/high water-cut systems) Low levels of residual emulsion Good interface quality Good separated water quality Low salt content Cost effective treatment levels

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Reverse Emulsions
Oil in Water Problems

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Deoiling Separated Water Why?

To recover oil (otherwise, it is lost revenue)

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To avoid environmental problems re the discharged water To prevent formation blockage re water use in secondary recovery

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Types of oil in water mixtures

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Free oil produced oil that automatically separates due to gravity

Dispersion tiny droplets of oil, emusified, or that separate slowly without agitation

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Definition of an emulsion

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Oil in water emulsion (reverse) emulsion Water is external phase Oil is dispersed phase

External (Water) Phase Dispersed (oil) Phase

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Factors involved in Reverse Emulsion stability

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Charge Particle size and density pH and ionic strength Temperature

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Particle Charge

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Oil particles are generally negatively charged

OIL PARTICLE

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Particle Charge - 2

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Negative oil particles attract layer of positive ions, this is the stern layer
STERN LAYER
+ + +

+
+ +

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Particle Charge - 3

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Third layer of positive / negative ions forms

Diffuse Layer of co and counter ions
+ + + + + + +

+ + + + + + + +

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Particle Charge - 4

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Solids and oil generally carry a nett negative charge

+ + + + + + + + + +

+
+ + + + +

Nett negative charge

Red circle represents surface nett negative charge

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Particle Charge - 5

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Overall negative charge of outer layer

Long range repulsion exists between particles

+ + + +

+ +

+ + +

LONG RANGE REPULSION

+ ++ +

+ ++ +

+ + + + +

+ + + + +

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Particle size and density

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Larger oil droplets will separate faster

Larger density difference between particles and water - faster separation

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pH and ionic strength

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pH change alters particle charge hence stability of emulsion

Increased ionic strength will destabilise emulsion

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Temperature

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Affects all other variables

Emulsion stability generally decreases as temperature increases

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Water clarification processes

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To remove oil present in water

API separators(onshore) TPI/CPI separators (offshore) Flotation units Hydrocyclones

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API Separator

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Vertical Baffle

Wood Flight Scraper

Oil Retention Baffle

Inlet Box
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Sludge Hopper Flow

PPI (Parallel Plate Interceptor) Separator

Oil Skimmer

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Outlet Weir

Inlet Weir

Outlet Parallel Plates

Inlet

Sludge Pit
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CPI Separator (Corrugated Plate Interceptor)

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Adjustable Outlet Weir

Oil Skimmer

Oil Layer

Outlet

Oil Globules

Inlet

Clean Water Outlet Channel

Sediment Trap

Sludge Pit
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Flotation Units

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By attaching gas particles (approximately 20100microns in diameter) to each particle, the apparent density of the particle becomes less than that of the surrounding liquid.

Because of this the oil and particulate matter rises in relation to the water.

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Induced Gas Flotation Cell

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Oil Solids

Air or natural gas intake

Gas disperser

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Induced gas flotation cell

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Oil Solids Gas bubbles

Air or natural gas intake

Gas bubbles lift oil and solids to the surface

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Induced air flotation cell

Air or natural gas intake

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Oil Solids Gas bubbles

Froth of removed particles

Gas bubbles lift oil and solids to the surface

Removed particles discharge Clarified water

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Cross section of a hydrocyclone showing vortex flow

Reject oil stream outlet

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Oil/water inlet

Oil/water inlet

Vortex Oil core

Water outlet
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