Introduction to Acidizing

Section 3

Printed: 9/1/2006

Introduction to Acidizing
Acidizing History
Purposes of Acidizing
Treatment Categories
Acid Reaction Chemistry & Physics

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 Acidizing History
First treatments performed in 1894 using
hydrochloric acid
First acidizing patent
March 17, 1896
Herman Frasch
Chief Chemist at Standard Oil Refinery
Acidizing used for about 2 years, then no
evidence of use for about 30 years

Acidizing History (cont.)

1928: Next evidence of HCl Acidizing
Dr. Blaine Wescott (Mellon Institute) used
HCl with Rodine #2
Mr. John van Dyke used sulfuric acid for
carbonate reservoirs (forms calcium
sulfate)
Mr. A.M. McPherson of Wichita Falls,
Texas approached Halliburton about HF
acid.
The job was done for King Royalty Company,
with disappointing results

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 Acidizing History (cont.)
Jesse Russell Wilson
Standard Oil of Indiana

Patent on hydrofluoric acid treatments on

sandstone formations

Acidizing History (cont.)

1932: Dow Chemical (John Grebbe) was
using HCl in brine wells
Pure Oil Co. (W.A.Thomas) was using HCl
in oil wells
Well was acidized with 500 gallons of HCl in
two stages and flushed with oil.
Results:
from 0 bopd to 16 bopd

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 Acidizing History (cont.)
Business was so good Dow Chemical
formed a well services group in 1932
Others soon followed:
Company State, Year
Oil Makers Co. Michigan, 1932
Chemical Process Co. Texas, 1932
Williams Brothers Oklahoma, 1932
Halliburton Oklahoma, 1932

Acidizing History (cont.)

Carey West formed Chemical Process
Company in 1932
In 1958, Chemical Process merged with
Byron Jackson which became BJ Hughes
and eventually...

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 Purpose of Acidizing
Establish connection to the reservoir
Remove damage
By-pass damage
Increase well productivity
Increase production rate
Decrease injection pressures (injection wells)
Increase recoverable reserves

Treatment Categories
Acid Treatments
Non-Acid Treatments
Water Management

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 Acid Treatments
Pickling Treatment
Soaking Agitation
Acid Breakdown Job
Matrix Acidizing
Sandstone
Carbonate
Acid Fracturing
Other Treatments
Placement & Diversion

Pickling Treatment
Process
Circulate weak acid through tubulars
Old & New Tubulars

Purpose
Prevent potential iron sludging problems by
removing loose iron

Additives
Corrosion inhibitor (always)
Iron control (possibly)

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 Soaking-Agitation
Process
Acid washing
Usually spotted and/or circulated by the formation face
but is not intentionally pumped into the formation.

Purpose
Remove scale
Open perforations
React with the formation face

Additives
Corrosion Inhibitor (always)
Formation compatible additives as necessary

Acid Breakdown Job

Process
Acid pumped through perforations to open
more or increase effective diameter

Purpose
Breakdown and open all perforations

Additives
Corrosion Inhibitor (always)
Formation compatible additives as necessary
Diverting agents (usually ball sealers)

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 Matrix Acidizing
Process
Inject acid into the
formation matrix without
fracturing the rock
(pumped below fracture
pressure)
Often used when
fracturing is undesirable
Normally, matrix acidizing
will not give any
significant stimulation to
an undamaged well in
either a sandstone or
carbonate formation

Matrix Acidizing (cont.)

Purpose
To achieve radial penetration
into the formation porosity
(intergranular, vugular or
fracture porosity), to improve
flow capacity through a
damage region near the
wellbore
Stimulation is achieved by
removing the effect of
reduced permeability
(damage) near the wellbore
by enlarging pore spaces and
dissolving particles which
may be plugging pore spaces

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 Matrix Acidizing (cont.)
Additives
Corrosion Inhibitor (always)
Formation compatible additives as necessary
Diverting agents (usually liquids or small sized
solids)

Matrix Acidizing (cont.)

Wormholes
In carbonate matrix
acidizing, damage is
bypassed by
dissolving carbonate
material in a fashion
described as
wormholing

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 Acid Fracturing
Process
Acid is injected at a pressure high enough to cause the
formation to fracture or to re-open pre-existing fractures

Differential acid etching will provide highly conductive

flow channels to provide stimulation

Acid Fracturing
(cont.)
Purpose
To bypass formation damage or stimulating undamaged
formations
Additives
Corrosion Inhibitor (always)
Formation compatible additives as necessary
Viscosifying agents
Diverting agents (ball sealers, liquids or sized solids)
Acid Penetration is based on:
Velocity of the acid
Reaction rate with the formation
Contact area between fractures and acid
Leakoff rate of the acid

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 Other Treatments
Spearhead for fracturing
Break emulsions
pH sensitive emulsions
Emulsions stabilized by fines
Break fracturing gels
Preflush before squeeze cementing

Non-Acid Treatment
Treatment Choices
Scale removal
Water blocks / wettability changes
Emulsions
Paraffins and asphaltenes
Water or gas shutoff (water management)

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 Water Management
Producing wells
Selective water control treatments
Stimulation & water control (ConformStim)
Aqualift gas well de-watering system
Injection wells
Selective zone stimulation (CT methods)
Single-step sandstone acidizing (BJ
Sandstone Acid)
Profile modification with relative permeability
modifier {RPM} (AquaCon)

BJ Water & Gas Management

Chemical Solutions
BJ RPM Systems BJ Shut-off Systems
AquaCon PA Blocking Gels
Aquatrol II
AquaCon HP
Aquatrol III
Aquatrol IV
ConformFrac Delayed Silicate Gels
ConformAcid SilJel
SilJel V
Cement Systems
AquaCon-enhanced scale
Magne-Block (new)
inhibition (Scaletrol 11)
Fine cement
Liquid Stone
AquaCon-enhanced salt Selective Systems
inhibition (Saltrol 2) SAF Mark II (water and
gas)
SAF Mark III

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 Conformance Problem Categories: Flow
Through Void Space or High Flow Conduit

Near wellbore Deep in reservoir

Channel Fracture or fault Water flow through

behind pipe between Inj & Prod natural factures

Magne Plus SilJel SilJel

Fine Cement Magne Plus Aquatrol V
Poly Fx Poly Fx SAF Mark III
Gel options Poly Fx
SAF Mark III Gel options

RPM-based RPM-based
technology technology
development development

Conformance Problem Categories

Flow Through Permeable Rock
Near wellbore

Watered out layer Coning High perm streak Rising oil Perforation
water contact sealing

SilJel AquaCon AquaCon Technology SilJel

AquaCon HP AquaCon HP AquaCon HP development Cement options
M-AquaCon HP M-Aquatrol
M-Aquatrol M-AquaCon
SAF Mark II Other VES-RPM
SAF Mark III
Magne Plus
Fine Cement

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 Conformance Problem Categories Flow
Through Permeable Rock (cont.)
Deep in reservoir

Water flow through Anisotropy effects Coning

natural factures arial sweep

Gel options Gel options AquaCon

AquaCon HP
RPM-based
M-Aquatrol
technology development
M-AquaCon
Other VES-RPM

Placement & Diversion

Mechanical
Packers, CT straddle options
CT RotoJet & RotoPulse
Concentric Coiled Tubing (CCT)

Chemical
Gels
Conventional diverters (wax, benzoates)
Selective diverters

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 Acid Reaction
Chemistry & Physics
General Chemical Reactions
Acids
Bases
Salts
Specific Acids Detail
HCl, HF, Acetic, Formic
Reaction Physics

Acids
Hydrochloric Acid
HCl + H2O H+ + Cl-
Hydrofluoric Acid
HF + H2O H+ + F-
Acetic Acid
H3C-COOH + H2O H+ + H3C-COO-
Formic Acid
HCOOH + H2O H+ + HCOO-
Water
HOH + H2O H+ + OH-

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 Bases
Sodium Hydroxide
NaOH + H2O OH- + Na+
Potassium Hydroxide
KOH + H2O OH- + K+
Calcium Hydroxide
Ca (OH)2 + H2O 2OH- + Ca2+
Ammonia Gas
NH3 + H2O OH- + NH4+

Salts
Sodium Chloride
HCl + NaOH NaCl + H2O
Calcium Chloride
2HCl + CaCO3 CaCl2 + CO2 + H2O
Silicon Tetrafluoride
4HF + SiO2 SiF4 + 2H2O
Barium Sulfate
H2SO4 + Ba(OH)2 BaSO4 + 2H2O

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 Reactions of
Hydrochloric Acid (HCl)
Hydrochloric Acid + Calcium Carbonate Calcium Chloride +
Carbon Dioxide + Water
2HCl + CaCO3 CaCl2 + CO2 + H2O

Hydrochloric Acid + Dolomite Calcium

Chloride + Magnesium Chloride + Carbon Dioxide + Water
4HCl + CaMg(CO3)2 CaCl2 + MgCl2 + 2CO2 +
2H2O

Hydrochloric Acid + Sand No appreciable reaction.

HCl + SiO2 No appreciable reaction

Reactions of
Hydrofluoric Acid (HF)
Hydrofluoric Acid + Calcium Carbonate Calcium
Bifluoride + Carbon Dioxide + Water
HF + CaCO3 CaF2 + CO2 - + H2O

Hydrofluoric Acid + Sand Fluosilicic Acid + Water

6HF + SiO2 H2SiF6 + 2H2O

Fluosilicic Acid + Sodium Sodium Fluosilicate +

Hydrogen
H2SiF6 + 2Na Na2SiF6 + H2-

Hydrofluoric Acid + Bentonite Clay Fluosilicic Acid +

Fluoaluminic Acid + Water
36HF + Al2(Si4O10)(OH)2 4H2SiF6 + 2H3AlF + 2H2O

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 Reactions of
Acetic Acid
Acetic Acid + Calcium Carbonate Calcium
Acetate + Carbon Dioxide + Water

2HCH3CO2 + CaCO3 Ca(CH3CO2)2 + CO2 +

H2O

Reactions of
Formic Acid
Formic Acid + Calcium Carbonate Calcium
Formate + Carbon Dioxide + Water

2HCCO2H + CaCO3 Ca(HCO2)2 + CO2 + H2O

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 Reaction Physics
Factors affecting reaction rate
Acid Fracturing Physics
Matrix Acid Physics

Factors Affecting
Reaction Rate
Temperature
Acid reaction rate increases with temperature
Pressure
Below 500 psi, increased pressure increases
reaction
Acid type
Acid concentration

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 Factors Affecting
Reaction Rate (cont.)
Acid velocity
In acid fracturing, increased velocity increases
live acid penetration
Reaction products
Area-volume ratio
Spending rate is proportional to the rock
surface area that the acid contacts
Formation composition

Factors Affecting
Reaction Rate (cont.)
Overall dissolution of material is broken down
into two parts
Reaction at the surface
Mass transport of reactants and products through the
solution to and from the surface to the bulk solution

Carbonates
The mass transport is the controlling factor in
penetration of acid either matrix or fracture treatments
Sandstones
Reaction controlled by the reactivity at the surface

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 Mass Transport

BULK SOLUTION

ACID TRANSPORT BY PRODUCT TRANSPORT BY

CONVECTION OR CONVECTION OR
DIFUSION DIFFUSION

HETEROGENEOUS
REACTION AT ACID
SOLID/LIQUID CONCENTRATION
INTERFACE NEAR THE SURFACE

REACTIVE MINERAL

Acid Fracturing Physics

Etched pattern and width affected by:
Mass transport of acid from the body of the
fracture to the walls of the fracture
Reaction of acid on the rock surface
Leak-off of acid from the fracture to the
formation matrix
Heat transfer in the fracture

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 Acid Matrix Physics
Sandstone
Contact with the matrix is the operative
mechanism

Carbonate
Wormholing through the rock is the operative
mechanism

Summary
Reaction Physics
Acid reactions are heterogeneous in our
applications
Acid transfer rate dominated by pump rate
Reaction rate between acid and rock
controlled by:
Rock properties
Acid concentrations
Acid activities
Temperature
Pressure

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 Section Summary
Introduction to Acidizing
Acidizing History
Purposes of Acidizing
Treatment Categories
Acid Reaction Chemistry & Physics

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