Carbonate Acidizing Design

Acid Additives
By: Dr. M. Pournik

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

Main Additive Types

H2S scavengers
Chelating agents
Corrosion inhibitors
Scale inhibitors
Drag reducers
Anti-sludge agents
surfactants
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Additives Requirements

Stable @ BHT
Compatible with other additives
Minimum impact on acid reaction
Do not adversely affect the performance
of other additives
Minimum impact of wettability

Additives Recommendations
Dont over use
Amount can be determined from
stoichmetry
Expensive
They can cause damage

Acid Additive Types

Family

Surfactants
Mutual solvents

Function/Examples

Water wet formation

Nonionic//fluorocarbon
Cationic
Remove oil, accelerate cleanup
EGMBE
Complex surfactants

Acid Additive Types

Family

Function/Examples

Antisludge/emulsion
agent

Prevent emulsions and sludge

Anionics
SDS

Iron control
additives

Prevent ppt of Fe(OH)3

EDTA
Citric acid
NTA
Reducing agents
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Acid Additive Types

Family

Corrosion Inhibitors
Sulfide suppressors

Function/Examples

Control acid corrosion

Aromatic quats
Unsaturated oxygen
Prevent sulfide reactions
Aldehydes
Chelants/reducing agents

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:
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

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

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Comparison of Corrosion Inhibitor

Types
Effectiveness of Corrosion Inhibitors at High
Temperatures in 15% HCl

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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

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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

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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
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Properties of Surfactants
Main properties of fluid or mineral 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

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Some Types of Surfactants

Silicate Particle Wettability
Characteristics

Examples of Surfactant Micelles

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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
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Application of Surfactants

Silt-suspending Agents:
Remove acid-insoluble clay and silt by adsorbing
onto them and keeping them suspended by
electrostatic repulsion
Antisludge Agents:
Adsorb and provide a continuous layer of protection
at acid/oil interface to prevent sludge formation from
acid/oil contact
Surface Tension Reducers:
Lower surface tension of treating fluids which
reduces capillary pressure, aiding in cleanup of wells
Corrosion Inhibitors:
Quarternary amines and acetylenic nonionics
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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

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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
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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

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Precipitation of Iron Compounds

- Iron, ferric, is introduced during acid
treatments

- It is also present in the reservoir rocks

- It will ppt in spent acids as Fe(OH)3 or FeS
(H2S)

- Both can cause damage

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Iron Contamination
Phase separation

Phase separation

Phase separation

Acid C
Acid A
Acid B
(1 wt%
(1 wt% FeCl3)
(1 wt% FeCl3)
FeCl3)
In the field, it is a must to minimize the iron contamination in
live acids by

Cleaning the mixing tank

Pickling well tubulars or coiled tubing before pumping the
acid.
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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:
Bond to iron and 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
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Iron Control Agents

-

Added to acids to keep iron in solution

Limited solubility
Not environmentally safe
Don't work if there is H2S
What is the solution?

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Iron Control

Main source of iron is tubing

Ferric is more damaging than ferrous
Minimize iron in live acids
One acid contains Fe(III)
Use ICA, but

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Iron Control (2)

ICA include NTA, EDTA, lactic acid, citric
acid, ..etc
EDTA has limited solubility in 15 wt% HCl
Hydroxy EDTA has better solubility
Dont use in sour environment
Watch for Na or K salts with HF

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Chelates Used in Stimulation

COOH
HOOC

COOH

HOOC

COOH
HO

HOOC

EDTA

HOOC

COOH

HEDTA

COOH

HO

COOH

NTA

COOH
COOH

EDG
(HEIDA)

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Comparison of Various Iron Control

Agents

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Alcohols
Applications:
Remove water blocks
Enhance fluid recovery
Retard acid reactivity
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

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Alcohols Limitations
Effect of Various Concentrations of Methanol
on Acid Strength at Increasing Temperatures

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Organic Dispersants

Use dispersant surfactant with xylene

Penetrate and loosen organic deposits which are then
dissolves by xylene
Concentrations range from 1% to 10% volume/volume
Concentration depends on deposit type, hardness and
adhesion and bottomhole temperature
Soaking time of several hours recommended for matrix
acidizing, wellbore and tubing cleanup treatments

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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

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Summary Additives to be Used

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Effects of Additives on FeS Dissolution

Function

Type

Effect

Corrosion inhibitors

Quaternary amines
Or
Unsat. Oxygen derivatives

Negative

surfactants

Nonionic

mixed

Mutual Solvents

Alcohols
Glycols

Small
none

Anti-sludge Additives

Anionic

Positive

Sulfide scavengers

Aldehyde

Negative

Iron Control Additives

Organic acids

Small

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Conclusions
FeS dissolution is inhabited by additives
that adsorb/interact with scale
Corrosion inhibition is impeded by
additives that dissolve or emulsify the
inhibitor film
The two effects can be opposing, so
careful testing under use conditions of
temperature and additives is mandatory
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