Formation Damage Prevention and

Well Stimulation
Acid Additives

Introduction

Treatment may be a failure if proper additives are not used

Additives in treating fluid used to

Prevent excessive corrosion
Prevent sludging and emulsions
Prevent iron precipitation
Prevent precipitation of reaction products
Improve cleanup
Improve coverage of zones

Additives in preflushes & postflushes used to

Stabilize clays
Disperse parafins & asphaltenes
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Corrosion Inhibitors

Most important
Slows attack of corrosion on drillpipe, tubing or any other metal
Effectiveness depends on the metal
Wide range of responses observed, hence must match properly
Could still get pitting of metal surfaces as a result of
Inhibitor breakdown
Insufficient inhibitor
Metal impurities

Types of Corrosion Inhibitors

Two basic types:

Organic corrosion inhibitors

Composed of polar organic compounds with one or more polar groups
made of sulfur, oxygen or nitrogen
Do not poison refinery catalysts
Work effectively in all acid concentrations
Chemically degrade with time and do not readily provide long-term
protection at temperatures above 200 oF
Expensive
May have inhibitor aids such as potassium iodide, cuprous iodide,
cuprous chloride, and formic acid to increase effectiveness of inhibitor

Types of Corrosion Inhibitors

Two basic types:
Inorganic corrosion inhibitors
Salts of zinc, nickel, copper, arsenic, antimony, and
various other metals
Work effectively at high temperatures for long contact time
Cheap
Tend to lose effectiveness in acids stronger than about
17% HCl
Poison refinery catalysts
May liberate toxic arsine gas
Difficult to mix and unsafe to handle
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Comparison of Corrosion Inhibitor Types

Effectiveness of Corrosion Inhibitors at High

Temperatures in 15% HCl

Corrosion Inhibitors Application

Some other additives reduce effectiveness of inhibitors by altering the

tendency of inhibitor to adsorb
Should properly test with representative metal samples using the
precise acid formulation at most adverse conditions of temperature
and pressure
Could reduce tendency for corrosion by:
Precooling tubing by injecting water preflush
Using formic acid rather than HCl
Minimizing contact time

Surfactants
Used to break undesirable emulsions, reduce surface or interfacial
tension, alter wettability, speed cleanup, disperse additives and
prevent sludge formation
Requires selection of appropriate molecule
Owe their properties to their dipolar composition

Types of Surfactants
Classified into 5 groups according to ionic charge carried by water-soluble
group:
Anionic: used primarily as nonemulsifying agents, retarding agents,
and cleaning agents
Cationic: consist of long-chain primary, secondary, and tertiary amines
or are quaternary ammonium compounds
Nonionic: used as nonemulsifiers and foaming agents
Amphoteric: have hydrophilic group that changes from cationic to
nonionic to anionic with increasing pH
Fluorocarbons: lower surface tension of solutions to much greater
extent than hydrocarbon surfactants

Properties of Surfactants
Main properties of fluids or minerals affected by surfactants are:
Surface tension: adsorbs to surfaces and changes surface tension
Emulsification tendency: can lead to development of emulsions
Wettability: adsorb at interfaces between solids and liquids and alters
wettability of solids
Micelle formation: form micelles in liquids when present above a
specific concentration for each molecule, solvent, and temperature
Dispersibility: wets the dispersed phase with the liquid phase which
greatly improves dispersibility

Some Types of Surfactants

Silicate Particle Wettability

Characteristics

Examples of Surfactant Micelles

Application of Surfactants

De-emulsifiers:
Break oil-water emulsions
Action depends on how quickly can concentrate at oil/water interface
Usually are oil-soluble
Nonemulsifiers:
Prevent formation of emulsions with reservoir fluids
Mixtures of surfactants and solvents blended to obtain a final
composition with broader applications
Emulsifiers:
Ability to isolate internal phase so that is not as reactive
Common example is emulsified acid
Can also act as efficient scale removal systems

Application of Surfactants

Bactericides:
Eliminate contaminating bacteria
Mostly cationic surfactants with biocidal property, used in conjunction
with other wetting surfactants
Clay Treaters:
Reduce swelling of clays by cation-exchange process
Inhibit flocculation of clays by dispersing clays
Foaming Agents:
Generate a stable foam
Can improve foam stability by gelling the liquid

Clay Stabilizers

Stabilize clays by adsorbing through electrostatic attraction or ion exchange on clays

Common types:
1) Highly charged cations:
Inexpensive
Treat for both migration and swelling damage & treat large area of rock
2) Quaternary surfactants:
Used widely for dry gas wells
Neutralizes charges, hence reduces ion-exchange capacity of clays
3) Polyamines:
Promote water-wetting of silicates & also polymeric bridging between silicate
particles
4) Polyquaternary amines
Stabilized by charge neutralization, water-wetting, and polymeric bridging
Can be used in any water-base fluid
5) Organosilane
Well suited for formations containing nonclay fines as well as clay fines

Mutual Solvents
Soluble in both hydrocarbons and water
Examples: glycol ethers, reaction product of alcohols, and ethylene oxide
Applications:

Reduce water saturation by lowering surface tension of water to prevent water

blocks
Solubilize a portion of water into a hydrocarbon phase to reduce water saturation
Maintain a water-wet formation as is to keep best relative permeability to oil
Prevent insoluble fines from becoming oil-wet
Maintain concentration of surfactants and inhibitors by reducing adsorption of
materials
Dissolve both adsorbed inhibitor and acid-insoluble residue
Dissolve any oil on the formation pore surface
Serves as de-emulsifier
Improves cleanup of spent acid

Iron Control Additives

Sources of Iron:

Corrosion products found on walls of tubulars

Mill scale
Precipitation from iron-bearing minerals

Iron control methods:

pH Control:
Add weak acid that is slow to react to keep low pH to prevent secondary
precipitation
Example: acetic acid

Sequestering Agents:
sequester iron to hold it in solution
Examples: citric acid, ethylenediaminetetraacetic acid (EDTA), and nitrilotriacetic
acid (NTA)

Reducing Agents:
Convert ferric (Fe3+) to ferrous (Fe2+) iron which does not precipitate until pH is
above 7
Examples: erythorbic acid and sodium erythorbate

Comparison of Various Iron Control Agents

Alcohols

Applications:

Remove water blocks

Enhance fluid recovery
Decrease water content
Most common types: isopropanol and methanol
Major disadvantages:

Require large concentration

Costly
Low flash point
Increases corrosiveness
Adverse reactions & side reactions
Incompatibility with crude oils

Alcohols Limitations

Effect of Various Concentrations of Methanol

on Acid Strength at Increasing Temperatures

Organic Solvents
Remove water blocks and solids like damaging particles and organic
deposits
Examples: alcohols, xylene, toluene, and diesel
Used alone or in combination with acid
For inorganic scales with asphaltenes and paraffins: combine organic
solvent with acid
For mixed deposits: an oil-external emulsion with acid as the internal
phase is best

Summary Additives to be Used