Section 8

Section 8
Chemical Stimulation
Table of Contents
Introduction ............................................................................................................................................... 8-5
Topic Areas............................................................................................................................................ 8-5
Learning Objectives ............................................................................................................................... 8-5
Unit A: Types of Acids.............................................................................................................................. 8-6
Hydrochloric Acid.................................................................................................................................. 8-6
Hydrofluoric-Hydrochloric Acid ........................................................................................................... 8-6
Additional Acids .................................................................................................................................... 8-6
Unit A Quiz............................................................................................................................................ 8-7
Unit B: Safety ............................................................................................................................................ 8-8
Safety Precautions.................................................................................................................................. 8-8
Unit B Quiz ............................................................................................................................................ 8-9
Unit C: Reactions of Hydrochloric Acid ................................................................................................. 8-10
HCL Reactions..................................................................................................................................... 8-10
Unit C Quiz .......................................................................................................................................... 8-12
Unit D: Corrosion Inhibitors.................................................................................................................... 8-13
Corrosion of Metals ............................................................................................................................. 8-13
MSA Inhibitors .................................................................................................................................... 8-14
Unit D Quiz.......................................................................................................................................... 8-15
Unit E: Carbonate Acidizing ................................................................................................................... 8-16
Matrix Acidizing.................................................................................................................................. 8-16
Expected Results .................................................................................................................................. 8-17
Types of Porosity ................................................................................................................................. 8-17
Fracture Acidizing................................................................................................................................ 8-17
Formation Core and Fluid Testing ....................................................................................................... 8-17
Tubing Movement Program ................................................................................................................. 8-19
Fracture Acidizing Plan Calculations .................................................................................................. 8-19
Acid Systems ....................................................................................................................................... 8-19
Additional Reference ........................................................................................................................... 8-21
Preflushes............................................................................................................................................. 8-21
Acid Placement Techniques................................................................................................................. 8-22
Unit E Quiz .......................................................................................................................................... 8-24
Unit F: Sandstone Acidizing.................................................................................................................... 8-25
Hydrochloric Acid................................................................................................................................ 8-25
Hydrofluoric Acid................................................................................................................................ 8-25
Damage Removal................................................................................................................................. 8-25
Reaction Rates ..................................................................................................................................... 8-25
Sandstone-2000 TM ............................................................................................................................... 8-26
© 2005, Halliburton 8•1 Stimulation I

Formation Conditioning....................................................................................................................... 8-26

Clays .................................................................................................................................................... 8-26
Secondary Precipitation ....................................................................................................................... 8-28
Acid Systems ....................................................................................................................................... 8-29
Unit F Quiz .......................................................................................................................................... 8-33
Unit G: Damage Removal – Mud............................................................................................................ 8-34
Mud Removal....................................................................................................................................... 8-34
Limestone Formations.......................................................................................................................... 8-34
Acid–Surfactant Mud Removal Solutions (MCA-III) ........................................................................ 8-34
Non-Acid Mud Removal Solutions (Mud-Flush) ................................................................................ 8-35
Sandstone Formations .......................................................................................................................... 8-35
Hydrofluoric-Hydrochloric Acid Mixtures (HF Acid)......................................................................... 8-35
Oil Base Muds...................................................................................................................................... 8-35
True Oil Base Muds ............................................................................................................................. 8-36
N-VER-Sperse ..................................................................................................................................... 8-36
Additional References.......................................................................................................................... 8-36
Unit G Quiz: Damage Removal-Mud .................................................................................................. 8-37
Unit H: Paraffins and Asphaltenes .......................................................................................................... 8-38
Paraffins ............................................................................................................................................... 8-38
Cloud Point and Pour Point.................................................................................................................. 8-38
Factors Affecting Paraffin Deposition ................................................................................................. 8-39
Loss of Volatile Constituents from the Crude...................................................................................... 8-39
Suspended Particles in the Crude......................................................................................................... 8-39
Conditions Favoring Paraffin Deposition ............................................................................................ 8-39
Paraffin Precipitation during Fracture Stimulation .............................................................................. 8-40
Methods Used to Remove Deposits ..................................................................................................... 8-40
Methods for Decreasing the Severity of Deposition ............................................................................ 8-42
Asphaltenes .......................................................................................................................................... 8-44
Targon® II Solvent ............................................................................................................................... 8-44
Unit H Quiz.......................................................................................................................................... 8-45
Unit I: Scale Removal and Prevention..................................................................................................... 8-46
Scale Effects......................................................................................................................................... 8-46
Types of Scale...................................................................................................................................... 8-46
Scale Formation ................................................................................................................................... 8-47
Scale Form ........................................................................................................................................... 8-47
Acid Soluble Scale Removal................................................................................................................ 8-48
Regular Inhibited Acid......................................................................................................................... 8-48
Penetrating Acid................................................................................................................................... 8-48
Non-Emulsifying Acid (NE) ................................................................................................................ 8-49
Fe Acid................................................................................................................................................. 8-49
Multiple Service Acid (MSA).............................................................................................................. 8-49
Paragon Acid Dispersion (PAD).......................................................................................................... 8-49
Acid Insoluble Scale Removal ............................................................................................................. 8-50
GYPSOL .............................................................................................................................................. 8-50
Liquid Scale Disintegrator ................................................................................................................... 8-50
Equations for Determining Volume of Scale Present .......................................................................... 8-52
gallons 15% HCL
Acid Volume = 180 × 27.5906 ft 3
ft 3 ........................................................................... 8-53
= 4966.308 gallons
Scale Inhibition .................................................................................................................................... 8-53

Scalechek® Scale Prevention Service................................................................................................... 8-53

Scalecheck® HT ................................................................................................................................... 8-53
Calchek Service.................................................................................................................................... 8-54
Protex-All Inhibitor.............................................................................................................................. 8-54
Chemical Placement Technique (CPT)................................................................................................ 8-55
Unit I Quiz ........................................................................................................................................... 8-56
Unit I Quiz ........................................................................................................................................... 8-57
Unit J: Placement Aids ............................................................................................................................ 8-59
Temporary Bridging Agents ................................................................................................................ 8-59
Selection of Bridging Agent ................................................................................................................ 8-59
Well Completion Type......................................................................................................................... 8-60
Placement Techniques.......................................................................................................................... 8-60
Carrier Fluid......................................................................................................................................... 8-60
Concentration of Bridging Agent......................................................................................................... 8-60
Particle Size Distribution ..................................................................................................................... 8-61
MATRISEAL® O ................................................................................................................................. 8-61
Matriseal® OWG Diverter.................................................................................................................... 8-62
Temporary Bridging Agents in Conjunction with Temblok Diverting Materials................................ 8-62
Unit J Quiz ........................................................................................................................................... 8-63
Unit K: Job Calculations.......................................................................................................................... 8-64
Calculations for Spotting Acid to the End of Tubing or Packer .......................................................... 8-64
Calculations for Balanced Acid Spot ................................................................................................... 8-65
Calculations for Flush and OverFlush.................................................................................................. 8-66
Unit Quiz K:......................................................................................................................................... 8-67
Self-Check Test for Section 8: Chemical Stimulation............................................................................. 8-68
Answer Key ............................................................................................................................................. 8-70
Self Check Test .................................................................................................................................... 8-73

Use for Section notes…

Introduction
Chemical stimulation is an important method of • Job Calculations
increasing oil and gas well production which,
even today, is still experiencing rapid technical
growth. Different processes have been used Learning Objectives
extensively since 1935.
Upon completion of this section, you will be
able to:
Topic Areas
• identify the acid types
The section units are: • list critical safety precautions
• Types of Acids • identify the primary corrosion factors and
• Safety list the inhibitors that help decrease
corrosion
• Reactions of Hydrochloric Acids
• identify damage removal methods of mud,
• Corrosion Inhibitors scale and paraffin
• Limestone Acidizing • identify acidizing treatments for limestone
and sandstone
• Sandstone Acidizing
• identify types of acids
• Damage Removal – Mud
• identify inhibitors
• Paraffin and Asphaltene Deposits
• calculate placement of acid
• Scale Removal and Prevention
• Placement Aids

Unit A: Types of Acids

Major acids used in chemical stimulation
include hydrochloric acid, hydrofluoric- Hydrofluoric-Hydrochloric Acid
hydrochloric acid mixtures, and organic acids.
This unit will explain the roles of these acids in
chemical stimulation. A Hydrofluoric-Hydrochloric (HF) acid mixture
is the basic acid for treating sandstone
formations with less than 20% HCL solubility.
Hydrochloric Acid These mixtures are used for removal of damage
caused by drilling mud, filtrate water, water-
swollen clays, migrating clays, and other small
Hydrochloric (HCL) acid containing inhibitors
formation particles. HF acid is typically
is the base solution for most oil field acidizing
prepared in the field by adding ammonium bi-
treatments. Depending on the use and
fluoride (ABF) to HCL. Hydrofluoric acid is
requirements of the treatments, the concentration
discussed further in Unit F, Sandstone
may range from 1% to about 35%. Hydrochloric
Acidizing.
acid reacts rapidly with carbonate formations
and is used in treating sandstone formations.
HCL can serve as the basic acid for damage Additional Acids
removal in addition to matrix and fracture
acidizing.
Two organic acids also used are formic and
Hydrochloric acid is a mixture of hydrogen and acetic. These are weaker than hydrochloric acid
chlorine gases dissolved in water. This gas is and exhibit less corrosion problems than HCL;
called hydrogen chloride and is readily soluble which means their hydrogen ions are released
in water up to 42% by weight at 60°F. more slowly than HCL with most materials
However, a solution of this concentration is found in wells. Ten- percent formic acid will
impractical since hydrogen chloride gas will dissolve as much limestone as eight- percent
come out of hydrochloric acid at temperatures HCL. Six percent HCL will dissolve as much
above 60°F. limestone as ten-percent acetic acid. Due to their
Commercially available hydrochloric acid has low degree of corrosiveness, organic acids can
been standardized at 20° Be (Baume). This is be used at higher temperatures for acidizing
equivalent to 31.45% acid, by weight, with a treatments. Acetic acid is the only acid that
density of 9.67 lb/gal. Higher concentrations of won’t damage chrome plating. It is useful for
acid can be purchased at 22° Be, or 35.2% acid. acidizing wells that contain pumps using chrome
It has a specific gravity of 1.179 and a density of plated parts. Organic acids may be used with
9.82 lb/gallon. HCL to allow deeper penetration and to provide
unique etching properties with some formations.

Unit A Quiz
Fill in the blanks with one or more words to check your progress in Unit A.
1. Two major acids used in chemical stimulation are ____________________ and
____________________.
2. Hydrochloric acid can serve as the basic acid for ____________________ ____________________
in addition to ____________________ and ____________________ acidizing.
3. Commercially available hydrochloric acid is standardized at __________ °Be or __________%.
4. Hydrofluoric – Hydrochloric acid mixture is the basic acid for treating ____________________
formations having 20% or less HCL solubility.
5. Two organic acids commonly used are ____________________ and ____________________.
6. ____________________ acid is the only acid that will not damage chrome plating.
Now, look up the suggested answers in the Answer Key at the end of this section.

Unit B: Safety
Safety is a top priority in all job procedures. • NO SMOKING around an acid tank. Tanks
Before pumping or handling acids or other containing acid or that have had acid in them
stimulation chemicals, you should study the can have an explosive mixtures of gases and
safety precautions given in the Chemical liquids trapped inside. Crude oil vapors
Stimulation Manual excerpts on HalWorld. mixed with air or hydrogen gas present in a
This unit discusses several important tank is also a possibility. Hydrochloric acid
precautions to use when handling chemicals on reacts with steel to produce iron chloride and
the job. hydrogen gas—a potentially explosive
situation.
• Even though an acid tank is coated with a
Safety Precautions sealant, there may be some exposed metal.
Hydrogen gas could be present.
Some critical safety precautions are as follows:
• Always add the water to the tank first and
• Always wear rubber gloves when working then add the concentrated acid. Never add
around acid. water to acid or fill the tank with acid first.
This increases the risk of splashing and can
• Goggles should be worn due to possible leaks
generate a large amount of heat.
in pump lines which may occur when
acidizing a well under pressure. • Hydrogen, mixed with air in the ratio of one
part per 24 parts, is an explosive mixture.
• Safety precautions should be taken when
For this reason, be aware of metal
handling hoses during the loading of trucks
connections when loading hoses. They could
or tanks or when disconnecting lines on a job.
strike the tank and ignite an explosion with
Acid may be left in the hoses.
the smallest of sparks.
• It is always a good practice to notify
• Clothes contaminated with chemicals should
personnel on location when acid is being
be removed and thoroughly washed before
used under pressure. All personnel should be
wearing them again. Wash off any chemical
kept at a safe distance.
spills with water immediately.
• Acid pump trucks or transport trucks should
• Wear a dust mask when handling powders.
be furnished with first aid kits containing
Inhalation of any powdered material can be
soda (sodium bicarbonate) for acid burns.
irritating even if the chemical is not toxic.
Drivers and operators should ensure that it is
always accessible in case of emergency. A The safety rules given here are a few of the rules
solution of one teaspoonful of soda to a pint listed in the Chemical Stimulation excerpts on
of water should be kept for use in the eyes. HalWorld. Be sure to study the remaining rules.
Dry soda can be applied directly to the skin An important section to be read in the safety
and then rinsed with water. DO NOT use dry section of the Chemical Stimulation manual on
soda in the eyes. HalWorld is “Hydrogen Sulfide”.
NOTE: When washing eyes, use a gentle
flow of water when rinsing. You could
damage an eyeball or even wash it out of its
socket with a heavy stream of water.

Unit B Quiz
Fill in the blanks with one or more words to check your progress in Unit B.
1. Because of possible leaks in pump lines, ____________________ should be worn on chemical jobs.
2. First aid kits on acid trucks should contain ____________________ ____________________ that can
be dissolved in water for treating acid burns.
3. Dry soda can be applied directly to the ____________________ but not to ____________________.
4. The possible presence of ____________________ ____________________ is one reason smoking is

not allowed around an acid tank.
5. When working with acid and water, always put the ____________________ in first and then add the
____________________.
6. Wear a ____________________ ____________________ when handling powders.

Unit C: Reactions of Hydrochloric Acid

Reaction rates and products are important Concentrations of HCL acid solutions may range
considerations in acidizing. The various from 1% to approximately 35% depending on
characteristics can have an effect on the choice the use and requirements of the treatment. It
of acid systems. may be your responsibility to mix the various
acid blends required in stimulation treatment
applications. Tables like the following one have
HCL Reactions been developed to assist you in determining the
proper amounts of concentrated acid and water
When 1,000 gallons of 15% hydrochloric acid to use when mixing an acid solution (see Table
solution reacts with calcium carbonate 8.1). These tables are usually posted in acid
(limestone), it will dissolve 10.9 cubic feet terminals.
(1843 lb) of the limestone. The products Information for both 22 °Be and 20 °Be acid is
resulting from “spending” the 15% HCL given in the table. Before using the table, find
solution upon the limestone will be: out which of the two acid concentrations are
• 2050 pounds of calcium chloride (CaC12) being stocked in the service center.
• 40 gallons of water (H2O) To illustrate the use of the table, assume that 20
°Be acid is stocked in the storage tanks and that
• 6620 cubic feet of carbon dioxide gas (CO2) you need to mix 1000 gallons of 15% HCL acid
at standard conditions solution. You need to determine how much
The total volume occupied by 1000 gallons of water to add to the acid transport and how much
15% hydrochloric acid after the reaction is: strong acid to add to the water to make the
solution.
• 912 gallons of water pumped into formation
In Table 8.1, locate the heading “Gals 20 °Be
• 40 gallons water made by chemical reaction Acid & Water To Make 1000 Gals Acid.”
• 68 gallons of volume occupied by 2050 Under this heading observe that acid and water
pounds of calcium chloride amounts are given in separate columns. In the
extreme left-hand column “HCL% Acid” is
• 1020 gallons total, assuming no volume is given. Under this column locate 15 % and move
occupied by the carbon dioxide gas or horizontally across the chart. You will read 442
diluted by formation brine gallons of 20 °Be acid and 558 gallons of water
15% hydrochloric acid spent on limestone required to mix 1000 gallons of 15% HCL acid
becomes a 20.0% solution of calcium chloride solution.
having a specific gravity of 1.175 and weighing
9.79 lb/gal.
© 2005, Halliburton 8 • 10 Stimulation I

Gals 22°Be Acid & Gals 20°Be

Water To Make 1000 Acid & Water To
Gal Acid Make 1000 Gal Acid
Eqiv.
HCL Gal of
Wt. In Hydrostatic
% S. G. Acid Water Acid Water 15% per
lb/gal psi/ft depth
Acid 1000
gals
1 1.005 24 976 28 972 8.83 .435 62
2 1.010 49 951 55 945 8.42 .437 125
3 1.015 73 927 83 917 8.46 .439 189
4 1.020 98 902 112 888 8.50 .442 253
5 1.025 124 876 140 860 8.54 .444 318
6 1.030 149 851 169 831 8.59 .446 383
7 1.035 175 825 199 801 8.63 .448 449
8 1.040 201 799 228 772 8.67 .450 516
9 1.045 227 773 258 742 8.71 .452 583
10 1.050 253 747 288 712 8.75 .454 651
11 1.055 280 720 318 682 8.79 .457 723
12 1.060 307 693 349 651 8.84 .459 788
13 1.065 334 666 379 621 8.88 .461 858
14 1.070 362 638 410 590 8.92 .463 929
15 1.075 389 611 442 558 8.96 .465 1000
16 1.080 417 583 473 527 9.00 .468 1072
17 1.085 445 555 505 495 9.05 .470 1144
18 1.090 473 527 538 462 9.08 .472 1217
19 1.095 502 498 570 430 9.13 .474 1290
20 1.100 531 469 603 397 9.17 .476 1364
21 1.105 560 440 636 364 9.21 .478 1439
22 1.110 589 411 669 331 9.25 .481 1514
23 1.116 619 381 703 297 9.30 .484 1592
24 1.122 650 350 738 262 9.35 .486 1670
25 1.127 680 320 772 228 9.39 .488 1747
26 1.132 710 290 806 194 9.43 .490 1825
27 1.136 740 260 840 160 9.46 .492 1902
28 1.141 771 229 875 125 9.50 .494 1981
29 1.146 802 198 910 90 9.55 .497 2061
30 1.153 835 165 948 52 9.60 .499 2145
31 1.158 866 134 983 17 9.65 .502 2226
31.45 1.160 880 120 1000 0 9.66 .503 2262
32 1.163 898 102 --- --- 9.69 .504 2308
33 1.168 930 70 --- --- 9.74 .506 2398
34 1.173 962 38 --- --- 9.78 .508 2481
35 1.178 990 10 --- --- 9.82 .510 2558
35.2 1.179 1000 -- --- --- 9.83 .510 2573
Table 8.1

Unit C Quiz
Fill in the blanks with one or more words to check your progress in Unit C.
1. 1000 gallons of 15% hydrochloric acid will dissolve __________ pounds of limestone.
2. The products resulting from the “spending” of 15% HCL on limestone are __________ pounds of
calcium chloride, 40 ____________________ of ____________________, and __________ cubic
feet of ____________________ ____________________ gas at standard conditions.
3. The total volume of 1000 gals of 15% HCL after spending is ____________ gallons.
4. If you have 20 °Be acid, how much acid and water are required for 1000 gallons of 10% HCL?
__________ acid
__________ water

Unit D: Corrosion Inhibitors

Corrosion is defined as “the deterioration of a and 85M, as well as the newer inhibitors HAI-
substance (usually a metal) because of a reaction GE and OS. These inhibitors will not protect
with its environment.” In well stimulation, the such metals as aluminum and magnesium from
primary concern is the reaction of acids on the attack by hydrochloric acid. In addition,
well equipment, including tubular goods, during galvanized coatings and chromium plating will
acidizing treatments. This reaction can be be attacked by inhibited hydrochloric acid. This
minimized by the use of corrosion inhibitors. is true with these inhibitors and with all other
inhibitors, including competitive materials.
There is a dual purpose for adding inhibitors to Some types of chrome and steel alloys can be
acid: the first is to protect our equipment and protected. Contact Duncan Research for further
the second is to protect the customer’s well information about these alloys.
equipment. Several types of inhibitors are
available for use in the oilfield. Acid corrosion inhibitors can be used up to
about 500°F. At temperatures above 275°F a
secondary component may need to be added.
Corrosion of Metals Two such components are Halliburton Inhibitor
Intensifiers 124 and 500 (HII 124 and HII 500).
Several factors govern the degree of attack acid NOTE: When hydrochloric acid is mixed with
has on steel. The primary factors are: acetic or formic acid, the inhibitors used for
• temperature HCL are the inhibitors used in these mixtures.
In general, the mixing procedures to follow
• time of contact
when mixing hydrochloric acid and organic
• type of acid corrosion inhibitors together are:
• pressure • The required volume of water is first added
to the tank
• type of steel
• The proper, measured volume of inhibitor is
• ratio of volume of acid to exposed steel
added to the water and agitated
surface area
• The concentrated acid from storage is
The longer acid is in contact with steel, the
thoroughly mixed until uniformity is
greater the amount of steel dissolved. The
obtained.
corrosion rate increases with increasing
temperatures. You must remember that If the acid mixture requires additional additives,
inhibitors do not stop corrosion; they only they may be added to the water prior to final
decrease the rate of corrosion. This rate of agitation.
corrosion can be decrease to an acceptable level
It is very important that the steps of addition of
if the proper inhibitor type and concentration are
material, agitation and blending be followed.
used. Figure 8.1 shows the corrosion rate of
Even if each chemical has been dumped into the
15% HCL with different concentrations of HAI-
tank, do not assume that uniform mixing will
85 on N-80 steel at 200 °F. Notice that the
occur while being moved to the location.
Halliburton standard is a “Maximum Total
Corrosion Loss” of 0.05 lb/ft2 total steel For more complete and detailed mixing
dissolved over the life of the test. procedures, refer to the confidential field
bulletins for inhibitors found on HalWorld
Inhibitors being used presently in hydrochloric
acid are Halliburton Acid Inhibitors HAI-81M

MSA Inhibitors procedures for MSA-II inhibitor are the same as

for other acid inhibitors. The Chemical
Stimulation Manual on HalWorld should be
Organic acids such as formic and acetic require
used when determining amounts of MSA
an inhibitor other than HA1-81, 85M, or 72 E+.
inhibitor to use.
MSA-II and the newer MSA-III inhibitors are
designed for use in these acids. MSA-II and Other inhibitors are designed for many purposes.
MSA-III inhibitors are not recommended for use You should become familiar with these
in hydrochloric acid solutions. Mixing inhibitors and their functions.
Figure 8.1

Unit D Quiz
Fill in the blanks with one or more words or check the correct answer to check your progress in
Unit D.
1. The primary factors governing the degree of attack acid has on steel are:
________________________________________________
________________________________________________
________________________________________________
________________________________________________
________________________________________________
________________________________________________
2. ______ True ______ False Inhibitors will stop corrosion.
3. Above 275° F, secondary components such as ____________________ and ____________________

may be needed for better corrosion protection.
4. ______ True ______False Adequate mixing will occur if inhibitor is dumped into a transport and
the transport is driven over rough roads to the location.
5. The Halliburton standard limit for corrosion, over which more inhibitor should be added is
__________ lb/ft2
6. MSA Inhibitor is required when you use ____________________ acids.
Now, look up the suggested answers in the Answer Key.

Unit E: Carbonate Acidizing

Successful acidizing in limestone and dolomite maximum production is the result of minimum
formations depends on a productive drainage damage.
pattern formed by the action of the acid. One or
a combination of the following ways that acid
invades a formation accomplishes this:
(1) entering natural existing fractures
(2) entering cracks caused by hydraulic
fracturing
(3) entering the permeability of the formation
The extension of an effective drainage pattern
into a productive zone requires deep penetration
into some formations regardless of whether the
crevices exist naturally or are artificially made.
WELLBORE SKIN OR ZONE
Penetration is dependent upon the permeability, OF DAMAGE
porosity, oil saturation, the amount of productive
interval, the formation pressure and the depth of
the zone.
PRESSURE IN
Unplugged flow paths should exist from the FORMATION
wellbore face to the outer limit of the formation.
Therefore, it is important that reaction products
and acid insoluble fines, which have been
PRESSURE DROP
dislodged by the chemical action on the ACROSS SKIN
formation, be removed after acidizing.
Matrix Acidizing WELLBORE

PRESSURE
Matrix acidizing consists of treating at a rate and Figure 8.2 - Schematic of a damaged well.
pressure low enough to avoid fracturing the Top view with oil or gas flow. Side view with
formation. This allows treatment of the natural pressure drop.
permeability, whether it is between the grains of
rock, in the vugular spaces of limestone or in
natural fractures. The skin factor can be reduced if near-wellbore
Matrix acidizing enhances well productivity by damage is removed or if a highly conductive
reducing the skin factor. Skin is the term used to structure is placed in the formation. In either
quantify damage that occurred to the formation case, the result is an increase in the production
during drilling and completion. Damage occurs in rate of a well and/or the reduction of the
all stages of the life of a well, and it is drawdown pressure differential. Decreased
impossible to completely eliminate this drawdown can help prevent formation collapse in
phenomenon. But, to produce hydrocarbons at weak formations, reduce water or gas coning,
an economical and profitable rate, maximum minimize both organic and mineral scaling, and
productivity is usually desired. In radial flow,

help ensure that a greater percentage of the Fracture Acidizing

completed interval contributes to production.
Matrix acidizing should be considered when Most limestone and dolomite formations have
damage is present or when a water zone or gas low permeability. Acid injected into these low
cap is close and fracturing could result in high permeability formations, even at moderate rates,
water production or excessive gas/oil ratio. usually result in a fracture type acid treatment.
Fracture Acidizing is the most widely used
treatment for limestone and dolomite
Expected Results formations. The success of a fracture acidizing
treatment depends upon the ability to create a
Results from matrix acidizing depend upon the conductive fracture with enough length and
type of permeability and porosity present and the height. Most fractures are vertical, and the
presence and extent of any formation damage. productivity should increase as the vertical
For example, assume that flow from a producing fracture height approaches the formation height.
limestone or dolomite is radial and the The productivity should also increase as the
permeability near the wellbore is the same as it fracture length approaches the drainage radius of
is deep in the formation (no damage). In this the well. Of course, the fracture must have
case, an increase in the permeability due to adequate flow capacity so that produced fluids
acidizing in the immediate vicinity of the well will have a passageway from the formation into
will give a relatively small increase in the the well bore.
production capacity of the well. In fact, if the To achieve good fracture extension and adequate
acid completely dissolves the limestone or flow capacity, an acid that has low fluid loss and
dolomite up to a radius of five feet, the
produces good flow capacity should be used.
production capacity of the well can be increased
by only 65% maximum. However, if the well is
partially plugged, and the damage can be Formation Core and Fluid
removed to a radius of five feet around the well
bore, the production capacity can increase by as Testing
much as 350%.
The following tests performed on formation core
samples are useful in planning acid treatments.
Types of Porosity In the fluid loss test, fluid is forced through a
core plug cut from a submitted core sample. A
When the porosity is intergranular (between differential pressure of 1,000 psi is used, and the
grains) and the formation is the same all over test temperature duplicates the bottom hole
(homogeneous), then matrix acidizing of this temperature of the well. Various types and
type of formation might produce approximately quantities of fluid loss additives are tried in
a 60% increase in production if no damage order to establish the most effective additive to
exists. Should damage exist, much larger use in the preflush and the acid. The fluid
production increases could be expected. efficiency of the acid and water preflush can be
If the porosity is vugular (large holes), the determined from these tests. These fluid
formation is homogeneous, and no damage efficiencies are used in calculating the created
exists, then production increases in the 100- fracture area.
150% range are possible. If damage exists, then A rotating disc reaction rate apparatus is used to
greater production increases can be expected. determine the true surface reaction rate and
If there are naturally occurring fractures in either order of reaction of the formation to be acidized.
a vugular or intergranular type formation, then Another test involves determining fracture flow
production increases of several hundred percent capacity from acid etched cores. On of the
might be possible. differences between fracture acidizing and

conventional water frac or oil fracs is that are placed together, and pressure is applied. The
usually no propping agent is used. The acid resulting fracture flow capacity can then be
produces flow capacity by removing limestone measured.
or dolomite from the fracture faces. However,
There are some formations in which fracture
laboratory tests indicate that certain types and
flow capacity cannot be created with acid, either
concentrations of acid can create more fracture
because the formation etches smoothly or
flow capacity.
because large quantities of insoluble fines plug
The etching time is also important. Laboratory the channels. In these formations, a SUPRA
etching tests determine the etching time and type technique or a conventional fracturing solution
acid which produce the maximum flow capacity. carrying a propping agent should be considered.
These tests are conducted by placing two core The acid etching tests can be used to determine
faces in a chamber approximately 0.1 inch apart. the feasibility of fracture acid stimulation and
Acid flows radially across this simulated the best type acid to use. Figure 8.3 shows a
fracture at 1,000 psi pressure and at simulated decision tree to help determine what type of
bottom hole temperature. After a certain etching treatment to perform.
time, the cores are removed, the etched surfaces
Figure 8.3 - Acid Treatment Decision Flowchart

For a successful acid treatment, the acid solution Fracture Acidizing Plan
must be compatible with the produced fluids. Calculations
Emulsion tests should always be run with the
produced fluids and the treating solution. These
The information obtained in the tests described,
tests are run by mixing equal volumes of the
along with certain well and formation data are
treating solution and the produced oil with high
used in computerized design programs. The
shear. The time and amount of separation are
calculations in Halliburton’s Acid Design
noted. Complete separation of the mixture
Program have been incorporated into FracPro
within ten to fifteen minutes is desirable. The
PT, a 3-dimensional fracture simulator which
tests are run with both live and spent acid
can determine the conductive fracture length and
because the fines released from some formations
the productivity increases that are possible. If
tend to stabilize emulsions. The acid used in the
cores are not available, a treatment design can be
emulsion tests should contain all of the additives
run using information determined previously on
that are going to be used in the job since many
cores from the same formation and same area.
of these additives affect the emulsion tests.
Acid can cause some of the asphaltene
components of the crude to fall out of solution. Acid Systems
These solids are commonly called “acid sludge.”
A sludge test should be run to see if anti-sludge In recent years, Halliburton has made an effort
agents are needed in the acid. to simplify it’s terminology in describing the
wide variety of acid systems and additives. The
Carbonate 20/20 program helps fill a void in the
Tubing Movement Program oil industry created by the lack of personnel that
can effectively design acid treatments. Several
The Tubing Movement Program (TMP) helps standard acid blends resulted from the Carbonate
predict the amount of tubing movement that can 20/20 initiative.
occur because of the high pump rates and fluid
volumes. This tubing movement is primarily Carbonate Completion Acid
caused by changes in the tubing through the
cooling effects from the pumped fluids, from the
Carbonate Completion Acid (CCA) minimizes
pressures exerted by fluids in the tubing and
compatibility problems, especially for reservoirs
annulus, and from the friction effect of these
containing asphaltene crudes. CCA uses HAI-
pumped fluids. One of the main advantages of
GE corrosion inhibitor which is compatible with
the program is that it uses bottom hole treating
non-ionic and anionic surfactants.
pressure as a starting value along with a specific
pump rate. A computer print-out includes: Although the CCA system is primarily used for
acidizing carbonate reservoirs that contain
• surface injection pressure asphaltene crude, it can also be used on “sour”
• total tubing movement, which includes wells (wells containing hydrogen sulfide) if
sulfide scavenger is added and on sweet wells if
• piston effect ferric iron control is used. Because the inhibitor
• ballooning effect and antisludging agent are compatible, they can
prevent sludging without compromising
• frictional effect corrosion protection. For effective corrosion
• buckling effect inhibition, the upper temperature limit of the
CCA system is approximately 200°F in 15%
• thermal effect HCL. Depending on acid concentration, contact
• the amount of force required to be exerted in time, and metal type, this temperature limit can
order to overcome these five effects be higher or lower.

Carbonate Stimulation Acid Zonal Coverage Acid
The Carbonate Stimulation Acid (CSA) system The Zonal Coverage Acid (ZCA) System is a
is used in carbonate formations for stimulating crosslinked acidizing fluid system that can be
production. Operators can use CSA to stimulate used in carbonates for fracture acidizing and for
carbonate formations by fracture acidizing or diversion during matrix acidizing. The use of
matrix acidizing. Regardless of the approach, the crosslinked acidizing fluids in the past was
acid should be viscous to promote effective limited. The high fluid viscosity required during
stimulation. pumping increased frictional pressures, which
required greater pumping horsepower. In
Gelling agents made from synthetic polymers
addition, obtaining a live-acid crosslinked fluid
are the most useful viscosifiers for acidizing
was an expensive process. In many cases, fully
carbonate formations. These materials resist acid
crosslinked acids were not necessary to retard
hydrolysis (breaking) over a wide range of
the reaction of HCL on carbonates; viscosifying
temperatures. Currently, Halliburton offers four
the acid provided ample retardation. In such
gelling agents made from synthetic polymers:
treatments, however, much of the acid was lost
SGA-HT, SGA-II, SGA-III and SGA-IV.
as a result of leakoff through wormholes (Figure
The most effective gelling agent for acidizing 8.4).
carbonate formations depends on the agent's
working temperature range, ease of mixing,
compatibility with other additives, and control
of reactivity. Based on these characteristics,
SGA-HT is usually the best gelling agent to use
for acidizing carbonate formations. However,
this viscosifier is also significantly more
expensive than SGA-II, III and IV. SGA-II and
SGA-III can be used at lower temperatures and
SGA-IV is the only gelling agent compatible
with sulfide scavengers. Table 8.2 presents
various properties of these three gelling agents.
Viscosity Ability
170 S-1 Temp Limit to
Figure 8.4 – Leakoff due to wormhole
Product Charge growth during acid fracturing
150°F (°F) cross-
2% Conc. link
SGA-HT 27 cp 400-425 + No
SGA-II 19 cp 200-225 - Yes
Zonal Coverage Acid (ZCA) system is an in-
situ crosslinked gelled acid system. When this
SGA-III 39 cp 300-325 + Yes* system is used, fluid loss can be controlled as
SGA-IV 33 cp 200-225 + Yes** the acid leaks off through wormholes and
Table 8.2 – Acid Gelling Agents spends. Once the acid is nearly spent, the system
crosslinks, blocking wormholes and preventing
*SGA-III must be premixed in HCL for 2 to 4 further loss of acid from the fracture face. The
hours to develop adequate crosslink sites. system will not break until the acid is
**SGA IV is the only acid gelling agent completely spent.
compatible with SCA-130 sulfide scavenger. SGA-II, III or IV can be used as a gelling agent
in the ZCA system. SGA-III must be premixed
in acid for 2 to 4 hours to develop adequate
crosslink sites for use in the ZCA system.

Therefore, if planning to run ZCA system fluids Handbook can be used when you design an
on-the-fly, use SGA-II or IV gelling agents. FRA treatment.
Carbonate Emulsion Acid Hot Rock Acid
Carbonate Emulsion Acid (CEA) is an The Hot Rock Acid (HRA) system is a totally
emulsified acid system used in carbonate organic acid system with a dissolving power
reservoir stimulation jobs that require retarded equal to 15% HCL. HRA is an acid system
acid reaction rates. The upper temperature limit specifically for high temperature wells. It
of the system is approximately 400°F. In consists of both acetic and formic acids set at
fracture acidizing applications, formations that different ratios to eliminate secondary
produce heavy crude oils with high quantities of precipitation problems and maintain maximum
asphaltenes tend to respond best to CEA. dissolving power. The Hot Rock Acid system
Because of its excellent acid retardation increases stimulation effectiveness and reduces
properties, the system has also been successfully corrosion rates. Specifically, it allows extended
used in higher-temperature matrix acidizing reaction times, provides built-in iron control,
applications. Under high-temperature conditions, and enhances the performance of acid gelling
the CEA system allows live acid to penetrate agents. Because of the reduced interfacial
deeper into the formation matrix than other acid tension the service provides, emulsion and
formulations. As a result, wormholing is sludging problems are less likely.
improved. Although the base acid cost for the Hot Rock
By volume, 70% of the CEA system consists of Acid system is about twice that of HCL, the
22% hydrochloric acid as the internal phase and reduction in corrosion inhibitor loading and the
30% of No. 2 diesel as the external phase of the reduced gelling agent requirement generally
emulsion. The CEA system is formed through result in lower overall treatment costs. In
the use of AF-61 emulsifier along with a addition to the two acids, the system includes
corrosion inhibitor. MSA-II inhibitor, SGA-HT gelling agent and an
appropriate surfactant. Iron-control additives can
be used but are not necessarily required.
Fines Recovery Acid
Fines Recovery Acid (FRA) is an energized acid Additional Reference

system for stimulating carbonate formations
with bottomhole static temperatures (BHST) up For more detailed information and mixing
to 150°F. The energized phase of FRA is procedures, consult the Carbonate 20/20
70% nitrogen. The acid is usually 20% technical bulletins on HalWorld.
HCL with a gelling agent and inhibitor. In
addition to demonstrating low liquid
concentrations and good fluid loss, the FRA Preflushes
system can also be used in low-pressure,
liquid-sensitive wells that normally produce In fracture acidizing, good productivity can be
fines during acidizing, or wells that have obtained if adequate fracture geometry can be
fluid and fines recovery problems. created that has enough conductivity. The
fracture geometry is determined by the fluid
Under matrix acidizing conditions, the FRA properties such as fluid loss, fluid viscosity and
system can be used to divert in long the injection rate. However, the conductivity of
horizontal open hole sections. the fracture is a function of the amount and
pattern of rock removed from the fracture faces,
STIMWIN, STIM2001, FOAMUP, not from acid leaking off into the formation.
FracproPT and the Halliburton Nitrogen

The distance that a conductive fracture can be natural fractures, and fluid-loss control is
created is dependent upon the reaction rate of reestablished.
the acid as well as the fluid properties. One
method of obtaining slower reaction rates is to SUPRA CE (Conductivity
use water preflushes to cool the fracture faces. Enhancement)
Preflushes also produce wider fractures for the
acid, which improves the rock surface area to
When using the SUPRA CE technique, service
acid volume ratio. This gives better penetration
operators pump a viscous pad fluid ahead of the
distance of live acid. Acid fluid loss is also
acid and behind an optional nonviscous, cool
decreased by the use of water preflushes.
down prepad. As the viscous pad is pumped, it
A viscous preflush can be used like a non- generates fracture geometry. Because the acid
viscous preflush. The increased viscosity has that follows it is less viscous, it “fingers”
the added advantage of creating a wider and through the viscous pad. This fingering process
possibly higher fracture. limits the acid contact to the formation face,
which creates etched and nonetched areas. This
process results in longer acid penetration
Acid Placement Techniques distance and possibly more effective
conductivity at a greater distance along the
The SUPRA (sustained-production acidizing) induced fracture.
techniques are another result of the Carbonate
20/20 initiative. They detail the different
methods that can be used under various well
conditions to generate the optimum conductive
geometry in the reservoir being treated.
SUPRA FLC (Fluid-Loss Control)
SUPRA FLC controls acid fluid-loss in induced

and natural fractures. In rock matrix or natural
fracture systems, acid leakoff must be controlled
so that live acid will remain within the fracture
and generate effective etched fracture length.
Under some conditions, Carbonate 20/20
treating fluids provide fluid-loss control. Under
Figure 8.5 - SUPRA CE Technique
excessive fluid-loss conditions, some additional
fluid-loss material may be required in addition
to alternating phases of acid and nonacid fluids.
The acid provides conductivity, and the nonacid SUPRA EHC (Etched Height Control)
fluid (containing fluid-loss additive) establishes
or re-establishes fluid-loss control.
The SUPRA EHC technique uses fluid density
The nonacid phase also acts as an acid extender, differences to control fluid placement in certain
allowing a sufficient volume of acid to penetrate sections of an induced vertical fracture. This
the required distance while reducing the volume technique can place acid in areas of a fracture
of acid necessary for that distance. Phases can be that do not contain water or possibly a gas cap.
alternated at any time, depending on the treating Figure 8.6 shows the fracture-acidizing process
conditions. The acid leaks off and forms including SUPRA EHC. Advantages of the
wormholes or goes into natural fracture systems. SUPRA EHC system are that it prevents the acid
The nonacid phase (containing fluid-loss treatment from entering unwanted zones such as
additives) sands off and seals up wormholes or

water-producing intervals and gas caps, and that Closed-Fracture Acidizing (CFA)
it uses less acid.
With the aid of nitrogen, many heavier fluids The closed-fracture acidizing (CFA) technique
can be lightened by foaming (gas content greater reopens previously created fracture systems with
than 55%) or commingling (gas content less a prepad fluid pumped at high rates. The
than 55%) gas in the fluid. Even with the best fractures are then allowed to close naturally, or
engineering and design, this treatment may not part of the prepad is flowed back to force the
always work. fractures to close. Next, acid and any necessary
additives and diverters are pumped below
fracturing pressure. This technique can also be
used immediately after a fracture acidizing
treatment performed for enhanced etched
conductivity.
For more information on these acid placement
techniques, consult the Carbonate 20/20 best
practices page on HalWorld.
Figure 8.6 - Fracture-Acidizing Process

Including SUPRA EHC

Unit E Quiz
Fill in the blanks with one or more words to check your progress in Unit E.
1. Matrix acidizing enhances well productivity by reducing the ____________________ factor.
2. Matrix acidizing requires that rates and pressures be controlled so that ____________________ does
not occur.
3. Decreased well pressure drawdown can help prevent formation ____________________ in weak
formations, reduce water or gas ____________________, minimize both organic and mineral
____________________.
4. The most widely used treatment for limestone and dolomite is _____________________
____________________.
5. One method of obtaining slower reaction rates is to use water _____________________ to

____________________ the fracture faces.
6. _____ True ______ False Fracture conductivity is generated by acid leaking off into the
formation.
7. Which Carbonate 20/20 acid system is used when asphaltenes are a problem?
_____ a) Carbonate Stimulation Acid
_____ b) Carbonate Completion Acid
_____c) Zonal Coverage Acid
_____d) Carbonate Emulsion Acid
8. Which acid system uses a crosslinked gel to control leakoff?
_____a) Carbonate Stimulation Acid
_____b) Carbonate Completion Acid
_____c) Zonal Coverage Acid
_____d) Carbonate Emulsion Acid
9. What does SUPRA stand for?
____________________-____________________ ____________________

Unit F: Sandstone Acidizing

Basically, two types of acids are used in reaction products and also has a significant
sandstone acidizing: hydrochloric acid alone and effect upon the reaction rate.
hydrofluoric-hydrochloric acid mixtures.
Normally, these treatments are used to stimulate
near the wellbore (maximum 5-6 feet out). Damage Removal
These treatments are done at rates that will not The hydrochloric-hydrofluoric acid mixture (HF
fracture the formation. They can be very Acid) has application in mud-or clay-damaged
effective in removing damage near the wellbore. sandstone formations. There are two
fundamental types of clay damage in sandstone.
One type is mud damage where bentonite
Hydrochloric Acid drilling mud particles have coated the formation
face or have invaded the formation. This type of
Even though hydrochloric acid will not dissolve damage is considered to be very shallow,
sand or clays, it is still useful in acidizing possibly only an inch or so deep.
sandstone formations. It will dissolve any
carbonates that might be present in the formation The second type results from naturally occurring
and will also partially dehydrate water-swollen clays that have either migrated toward the
clays. wellbore and are plugging flow channels or have
become hydrated and swollen due to contact by
In sandstone stimulation, hydrochloric acid is fresh water. This type of damage is deeper into
usually combined with Morflo III to produce the formation than mud damage.
MCA (Mud Cleanout Acid). The hydrochloric
acid in MCA shrinks swollen clay particles.
Morflo III disperses clays and acts as a Reaction Rates
surfactant to aid in emulsion prevention and
faster cleanup. The Speed with which hydrofluoric acid reacts
upon sandstone is affected by
Hydrofluoric Acid • physical and chemical composition of the
formation
In contrast to hydrochloric acid, hydrofluoric • temperature
acid does have the ability to dissolve silica
(sand) or silicates such as clays, silt, shale and • surface area of rock exposed to a particular
feldspars. Since bentonite is a silicate, it can volume of acid
also be dissolved by hydrofluoric acid.
• concentration of excess hydrochloric acid
Sandstone formations having permeability
damage due to clay migration or benetonite Sandstone formations are basically composed of
drilling mud can usually be helped by a quartz, with some limestone, dolomite,
hydrofluoric acid treatment. feldspars, and several clay minerals.
Hydrofluoric-hydrochloric acid mixtures react
Hydrofluoric acid is usually pumped as a
with these materials at varying rates. Therefore,
hydrochloric-hydrofluoric acid mixture (HF
the reaction rates of the HF Acid mixtures will
Acid) with the hydrofluoric acid being obtained
vary considerably with the composition of the
from the reaction of hydrochloric acid on
formation. The physical distribution of the acid
ammonium bifluoride. Hydrochloric acid
increases the solubility of some of the secondary

soluble material throughout the formation also Sandstone-2000 TM

influences reaction rate.
Another factor greatly influencing the rate of Sandstone acidizing technology has improved
reaction is bottom-hole temperature. The higher significantly in recent years as a result of field
the temperature, the more rapid is the reaction. analysis, fundamental research and applied
For example, laboratory data taken from tests research. Traditional sandstone acidizing
reacting 25 ml of acid on 4.0 gm of sand reveal treatments were performed by pumping a
that 33.6 lb of 20-40 mesh Ottawa sand would standard blend of 3% HF and 12% HCL acids.
be dissolved by 1,000 gallons of a 3% HF-12% These treatments often had minimal success and
HCL acid mixture in eight hours at 75°F. sometimes actually damaged the well further.
However, at 200°F, 1,000 gallons of the same Older theories regarding reactions occurring
acid mixture would dissolve 43.1 lb of the same between the acid and the formation proved to be
sand in only one hour. inaccurate in 1984 when samples from a Gulf
Coast well were obtained after sandstone
The surface area of material exposed to the acid
acidization. Based on this research, the
also influences the rate of the reaction. This is
Sandstone 2000TM acidizing processes were
probably the primary reason that hydrofluoric
developed. Like the Carbonate 20/20 initiative,
acid dissolves clay minerals more rapidly than it
Sandstone 2000TM created a set of “best
does quartz. As shown above, 1,000 gallons of
practices” to help improve Halliburton’s
3% HCL will dissolve 33.6 lb of 20-40 mesh
sandstone acidizing success rate.
sand in eight hours at 75°F. However, under the
same test conditions, 1,000 gallons of the same
acid will dissolve 50.7 lb of silica flour in only
30 minutes. Formation Conditioning
Further data show that 72.6 lb of silica flour Treatment of a well before sandstone acidizing
containing 5% bentonite will be dissolved by can greatly increase the success rate of this type
1,000 gallons of 3% HF-12% HCL in 30 of treatment. Formation conditioning design
minutes at 75°F. These examples illustrate the depends on the presence of key minerals. Proper
influence of the exposed surface area on the rate use of a formation conditioner or a combination
of the reaction. Under reservoir conditions the of conditioners before treatment with HF acids is
surface area-to-volume ratio will be much critical to the success of the treatment.
greater than that of any of these examples. As a
result, the reaction in the formation will be more
rapid. Clays
Therefore, the influence of exposed surface area
of rock on the reaction rate cannot be over- Clays were previously thought to be of minor
emphasized. consequence. However, recent work has shown
that the impact of clays can be dramatic for
The importance of the concentration of excess
hydrochloric acid can be illustrated with the brines undergoing deep matrix invasion in
following examples. Using calculations from sandstones. Table 8.3 shows some mineralogies
that could cause problems.
laboratory tests conducted by reacting 25 ml of
acid on 4.0 gm of sand for 30 minutes at 75°F,
1,000 gallons of 3% HF-0% HCL will dissolve
27.1 lb of silica flour containing 5% clay. The
same volume of 3% HF-12% HCL and 3% HF-
20% HCL will dissolve 72.6 lb and 90.8 lb
respectively.

Mineral Problem The CLA-STA additives described in Section 6

Contains sodium and can also be used to enhance clay stabilization.
Feldspars
potassium. Fluosilicate
precipitation and K-Spars can
create major problems.
HCL Sensitivity
Carbonate Consumes HCL and can cause
precipitation of fluosilicates and Many formations are “HCL-sensitive;”
aluminum from spent HF. formation minerals decompose when contacted
Illite Can cause fines migration
problems, is ion exchanging,
by HCL. During this process, metal ions such as
and contains potassium which iron, aluminum, calcium, and magnesium are
can cause fluosilicate dissolved from the mineral, leaving an insoluble
precipitation from spent HF. silica gel mass that can be extremely damaging.
Kaolinite Can cause fines migration HCL-sensitive minerals include zeolites and
problems and disperses in fresh
water and causes plugging.
chlorite. However, research has shown than all
Is ion exchanging and swells in clays have a temperature above which they are
Smectite
fresh water. unstable. When conditions make formation
Mixed-Layer Clay Is ion exchanging, swells in minerals highly unstable, only organic acid-
fresh water, and frequently based systems should be used.
contains potassium which can
cause fluosilicate precipitation
from spent HF. CLAY-SAFE
Chlorite Is ion exchanging and is
unstable in HCL.
Is ion exchanging, is unstable in Despite the sensitivity of clays to HCL, they are
Mica
HCL, and contains potassium stable in acetic acid and fairly stable in formic
which can cause fluosilicate acid. Unfortunately, both of these acids are
precipitation from spent HF. similar to fresh water in the presence of water-
Zeolite Is ion exchanging, is unstable in
HCL, and occasionally contains
sensitive clays. Substituting acetic acid (MSA)
sodium which can cause for CLAYFIX is not a good alternative, since
fluosilicate precipitation from MSA does not exchange ions with the clays or
spent HF prevent clay swelling. MSA is not an equivalent
Table 8.3 – Problem Formation Mineralogy substitute for HCL because it does not dissolve
iron scales and is slow to dissolve carbonates.
However, use of CLAY-SAFE conditioners
should provide sufficient ion ex-change to help:
CLAYFIX
• prevent precipitates in the HF/HCL process,
When ion exchange occurs, the cations naturally • control clay swelling, and
present on the surfaces of the clays are replaced
or exchanged with ions from the invading brine. • stabilize the clay to sandstone acidization.
For example, 7% potassium chloride brine Their recommended uses are given in Table 8.4,
(KCl), after exchanging ions with the formation, but the Sandstone Stimulation Process section
becomes approximately 5% sodium chloride on HalWorld should be consulted for proper use
(salt). Because of this exchange it is important of these fluids.
that the transformed brine should also be
compatible with the formation.
The most effective brine for sandstone acidizing
is ammonium chloride (NH4CL), also called
CLAYFIX. CLAYFIX 5 (5% NH4CL) provides
sufficient ion exchange and maintains enough
salt concentration to prevent clay swelling
before and after ion exchange.

Fluid System When to Use For example, 50 gal/ft (gallons per foot of
Mud Cleanout formation height) of 15% HCL preflush in a
Whole water-based mud sandstone containing only 5% calcite will
Mud-Flush
losses remove the calcite in a radius of about 2 ft from
N-Ver-Sperse Whole oil-based mud losses the wellbore. If spent HF follows, aluminum
Wellbore Conditioning fluoride precipitation will begin 2 ft from the
Paragon or other organic Asphaltene/paraffin problems, wellbore.
solvents heavy oils, pipe dope
Removing iron scales and
HCL for pickling preventing them from entering Gidley’s CO2 Conditioner
the formation
Oil Well Conditioning Carbon dioxide preflushes have successfully
Emulsion problems, terminal prevented fluid compatibility and emulsion
Gidley's CO2 Conditioner upsets, improves acid problems after sandstone acidizing treatments
penetration into oil zone
Matrix Conditioning
and have improved the HF treatment response.
One operating company’s study revealed that
CLAYFIX 5 High ion-exchanging clays
oil-wet particulates (silica and fines) stabilized
Carbonate removal, ion emulsions. These particles were precipitated
5-15% HCL exchange, removal of polymer
damage from HF acid reacting with the formation in the
presence of hydrocarbons, such as crude oil and
Carbonate removal, ion
CLAY-SAFE 5
exchange for HCL-sensitive xylene. The solution is in Gidley’s CO2
*See note below. Conditioner, a Halliburton-exclusive process
mineralogy
that removes the hydrocarbons from the near-
HCL-sensitive mineralogy, but
it requires removal of polymer wellbore area. The carbon dioxide treatment
CLAY-SAFE H uses 100 to 200 gal/ft of CO2 under miscible
damage (K-Max, HEC, etc.) or
high carbonate levels. (easily mixed) conditions to displace the oil
HCL-sensitive mineralogy, but
away from the matrix in the near-wellbore area.
it requires increased Displacing the hydrocarbons allows better HF
CLAY-SAFE F
*See note below.
carbonate dissolving power invasion of the matrix and prevents emulsions
without increased volume. from forming.
See note below.
*Note: MSA II Inhibitor and 5% NH4Cl are not compatible when The CO2 can also be used throughout the acid
the MSA II Inhibitor concentration is above 1%. Below 1% MSA II stages to provide enhanced energy for cleanup.
Inhibitor, dispersing agents may be required.
Some oils form asphaltene precipitation easily
Table 8.4 – Formation Conditioning System and other oils have minimal miscibility with
CO2 under reservoir conditions. Both of these
conditions can be at least partially eliminated
with a xylene preflush ahead of the Gidley’s
Carbonates CO2 Conditioner.
Sandstone formations containing greater than

5% carbonates are prone to matrix precipitation Secondary Precipitation
of complex aluminum fluorides as spent HF
flows across the carbonates. The solution to this When hydrofluoric acid reacts with either
problem requires silicates (clay minerals) or silica (quartz), one of
the reaction products is fluosilicic acid. This
• deep removal of the carbonate with large
acid will react with sodium or potassium to form
preflushes of HCL or
sodium fluosilicate or potassium fluosilicate.
• the use of an additive that prevents
The sodium and potassium fluosilicates have
precipitation. very low solubility, and precipitation can occur.
This can happen if the hydrofluoric acid contains

sodium or potassium, or if the spent or partially • Contains ALCHEK to prevent secondary

spent acid becomes mixed with solutions precipitation of aluminum. This is
containing these chemicals. This means that salt particularly important when the mineralogy
water should not be used as mixing water for the is unknown or the formation contains high
acid or for displacing the acid. The acid should carbonate streaks or more than 5%
not be weighted with sodium chloride or carbonates.
calcium chloride. When calcium chloride is
added to hydrofluoric acid, calcium fluoride will • Aids in iron control, in most cases
precipitate immediately. Diverting aids such as eliminating the need for other iron control
rock salt should not be used because of additives such as Fe-2 (citric acid) and Fe-
secondary precipitates. If additional weight is 1A (acetic acid).
necessary, it is possible to use ammonium • Contains a penetrating agent to help acid
chloride as the weighting agent. contact damage.
The overall advantage of Sandstone Completion
Acid is that it provides the customer with
Acid Systems maximum dissolving power while maintaining
compatibility which is particularly important
when the mineralogy is unknown. The 1.5% HF
Silica Scale Acid is the maximum HF concentration recommended
in most sandstone matrix acidizing treatments.
Silica Scale Acid is the old regular HF or mud
acid (12% HCL-3% HF). It is effective at
removing damage, but its high HF
Fines Control Acid
concentrations almost invariably result in
secondary precipitation very near the wellbore RHF (Retarded HF Acid) is an acid system that
resulting in failures or limited, short-term has proven successful. The patented system has
successes. Therefore, this system is been modified slightly and renamed Fines
recommended for use only when the mineralogy Control Acid.
shows there are essentially no clays and 100% Conventional matrix acidizing with hydrofluoric
quartz, or in geothermal wells. acid is only effective for removing shallow clay
damage 1 or 2 in. from the wellbore. Fines
Sandstone Completion Acid Control Acid is a retarded hydrofluoric acid
system designed for treating sandstone
Sandstone Completion Acid consists of 13.5% formations that have been damaged from the
HCL-1.5% HF, Pen-88 as penetrating agent, and migration and/or swelling of silica, feldspars,
5% ALCHEK to prevent precipitation of and clays up to 2 to 6 in. from the wellbore.
aluminum in the formation and in the wellbore Formations with significant Kaolinite and /or
(alumino-silicate scaling). This fluid is illite are particularly sensitive to this type of
compatible with a majority of formations and damage. The fluoride content of Fines Control
was particularly designed for the cases where the Acid is equivalent to the fluoride content of
formation mineralogy is unknown or uncertain. 1.5% HF, but its effective dissolving power is
The primary advantages of sandstone equivalent to 1.1% HF. However, because of its
completion acid are: retarded nature in its reactions with sand, it is as
effective in removing clay damage as 1.5% HF.
• Contains high HCL-HF ratio to provide
compatibility with most formation Fines Control Acid can also be effective in
mineralogies. Exceptions include formations formations that appear to be HCL-sensitive. In
high in feldspars, particularly at these cases CLAY-SAFE 5 Conditioner can be
temperatures below 200°F and formations used followed by Fines Control Acid. Formation
containing "HCL-sensitive" minerals. minerals do not show acid sensitivity when

treated in this manner, as discussed in an earlier overall content is greater then 10%. Since the
section on HCL-sensitivity. fluosilicates are less soluble at lower
temperatures, K-spar Acid should also be used
The primary advantages of fines control acid
in most formations containing any significant
are:
sodium feldspars below 175°F. In formations
• Deeper penetration of live HF into the containing high concentrations of potassium
formation. feldspars below 200°F, lower HF concentrations
are suggested. If fluosilicate precipitation cannot
• Retarded reaction with sand and silica to
be avoided, an HCL overflush should be used to
promote deep damage removal and improve
help re-dissolve the precipitate.
compatibility with feldspar-containing
formations. Cla-Sta FS is included to control fines migration
associated with illite or mixed-layer clays. These
• Minimized damage to formation clays are almost always present when potassium
consolidation - it reacts less with the sand feldspar is a dominant mineral and are very
that holds the formation together. susceptible to fines migration during a
• Fe-1A for iron control and preventing stimulation treatment. K-Spar Acid will prevent
aluminum scaling. this migration. If fines migration is the source of
damage, Fine Control Acid is recommended.
• Penetrating agent to help acid contact The HF fluid treatment design could consist of
damage. 50 gal/ft of K-spar Acid followed by 200 gal/ft
• Clay stabilizer to control fines migration of Fines Control Acid.
during and following the treatment. The primary advantages of K-Spar acid are:
• Temperature limitation only because of • Is compatible with formations containing
corrosion inhibitor and formation mineral significant feldspar and/or illite minerals
stability, as in non-retarded HF systems.
• Contains Fe-1A for iron control and
Higher volumes of Fines Control Acid should be
preventing aluminum scaling.
used where deep, severe damage has occurred. A
lower volume of overflush can be used when the • Contains penetrating agent to help acid
well is predicted to clean up rapidly. When contact damage.
difficulty in cleaning up the well is anticipated,
the large volume of overflush should be used to • Contains clay stabilizer to control fines
push the HF-containing fluids far from the migration during and following the
wellbore. Since Fines Control Acid does not treatment.
require a shut-in time to function, the well
should be returned to production as soon as Volcanic Acid
possible.
Volcanic Acid is a new organic-HF acidizing
K-Spar Acid blend developed to replace acetic-HF and
formic-HF fluids. This system is unique to
K-Spar Acid is a 9% HCL-1% HF blend which Halliburton. Recent research (including
was designed for treating formations containing laboratory reactions, core flow tests, and
significant sodium or potassium feldspar or flowback sample analyses from organic-HF
illite. As the sodium and potassium are treatments) has shown that the acetic-HF and
dissolved from these minerals, the potential for formic-HF systems have severe secondary
fluosilicate precipitation increases. Potassium precipitation of HF reaction products. The
fluosilicate is less soluble and presents a bigger systems are effective in removing skin damage
problem. K-spar Acid should be used in almost and increasing production in wells in which
all cases where the formation contains K-spar HCL-based fluids could not be used. However,
and/or illite as the dominant mineral, or the secondary reactions further from the wellbore

precipitate the HF reaction products giving a less and asphaltenes or scale removal treatments
than optimum overall treatment. Volcanic Acid may also be required.
solves these problems while maintaining all the
3. Pump 100 to 200 gal/ft of Gidley's CO2
advantages of organic-HF fluids.
Conditioner (optional). Applicable for oil
The primary advantages of Volcanic Acid are: wells with emulsion problems, terminal
upset problems, or to enhance contact of
• Is compatible with HCL-sensitive minerals
acid into the oil zones.
• Can be used at higher temperatures than 4. Pump 50 to 150 gal/ft of non-acid CLAYFIX
HCL-based fluids, without decomposing 5 Conditioner (optional). CLAYFIX 5
clays or zeolites or having high corrosion Conditioner is recommended in formations
rates. with a high ion-exchange capacity. It also
• Typically will not cause sludging with should be used when completion brines or
formation crude oils, even with those prone kill fluids have not been recovered from the
to acid sludging. well and need to be displaced from the near-
wellbore area to avoid contact with acid
• Avoids secondary precipitation observed fluids. If the crude oil or formation brine
with formic-HF and acetic-HF. shows incompatibility with the acid fluids,
• Contains NH4Cl to prevent swelling of the non-acid preflush may also be necessary.
water-sensitive clays. 5. Pump 50 to 150 gal/ft of appropriate acid
• Contains a penetrating agent to help acid conditioner. Acid fluids are required prior to
contact damage. the HF-containing damage removal fluid
systems in order to ion exchange and
• Can be used anywhere formic-HF or acetic- remove carbonates. HCL, CLAY-SAFE 5,
HF fluids were previously used. or CLAY-SAFE H should be used. The
The name Volcanic Acid came from the fact that choice of these fluids depends upon damage
formations with high zeolite content and high mechanism, mineralogy, and temperature.
clay content are often associated with areas of 6. Pump 75 to 200 gal/ft of appropriate
volcanic activity. The name also has the damage removal fluid system. When using
connotation of high temperature. The Volcanic Fines Control Acid, pumping a small
Acid fluid systems are specifically suited for nonretarded HF stage is often beneficial in
these types of formations. removing very near-wellbore damage.
7. Overflush with 25 to 200 gal/ft of 5-15%
General Treatment Guidelines HCL or CLAYFIX 5. Overflush is required
to push the treatment fluids deeper into the
Designing sandstone acidizing treatment may formation. The larger volumes are required
seem very complicated due to the numerous with brines incompatible with spent acid or
considerations that must be dealt with, but for disposal wells where the fluids are not
following the 8 general steps listed below and recovered.
the decision tree in Figure 8.7, the goal of
improving well performance can keep things in 8. Displace with clean fluid such as nitrogen
perspective. or CLAYFIX 5. Volumes should be
sufficient to fully displace any acid fluid
1. Perform mud cleanout treatment if whole away from the wellbore and the gravel pack.
drilling mud was lost. Additional fluid Never use KCL, or formation brine to
should be circulated until returned fluid is displace since these fluids will be
clean. incompatible with spent acid.
2. Perform wellbore cleanout treatment. This
should include pickling the tubing with HCL
at the least. Solvent treatments for paraffins

HF Acid Flow Diagram
W ellbore A rea D amaged?
Don’t use HF
Yes No
Is dama ge H F a cid soluble?

Don’t use HF
No Yes
Damag e remov ed, will production be e conomica l?

D on’t use H F
Yes No
Pump at re asonable ma trix inje ction rate?
Don’t use HF
Yes No
Carbo nate Conce ntra tion > 20%?

Don’t use HF
Yes No
C an treatment be control le d to tre at all in terval of Interes t?

U se HF
Yes No
Nec ess ary to tre at t he whole i nt erval t o ma ke well ec onomical?

D on’ t use H F U se HF
Yes No
Figure 8.7 – HF acidizing decision tree

Unit F Quiz
Fill in the blanks or mark the correct answer to check your progress in Unit F.
1. Hydrochloric acid used in sandstone acidizing is basically used to (check all that apply):
_____ a) partially dehydrate water-swollen clay
_____ b) dissolve clays
_____ c) dissolve carbonates that are present
_____d) create a fracture
2. Hydrofluoric acid will dissolve
_____a) silica
_____b) clays
_____c) silt
_____d) shales
_____e) all of the above
3. The speed of hydrofluoric acid’s reaction on sandstone is affected by:
_______________________________________________________
_______________________________________________________
_______________________________________________________
_______________________________________________________
4. Halliburton’s name for ammonium chloride is ____________________.
5. Gidley’s CO2 process displaces ____________________ away from the wellbore to allow better HF
____________________ of the matrix and prevent ____________________ from forming.
6. Which Sandstone acid system would you choose for removal of deep damage (up to 2 to 6 in. from
the wellbore) caused by clay migration or swelling?
_____a) Sandstone Completion Acid
_____b) Fines Removal Acid
_____c) Silica Scale Acid
_____d) Volcanic Acid


Unit G: Damage Removal – Mud

Since many mud systems are used for well considered before a mud removal operation is
completion, it is almost impossible to describe started.
all of them, their properties, and how they might
affect production. Therefore, this unit is limited
to: Limestone Formations
(1.) water base muds which contain clay If damage from mud or mud filtrates exists in a
minerals limestone formation, the exact nature of the
(2.) oil base muds. Oil muds are either straight damage should be determined. If the producing
oils or oil external emulsions. formation has not experienced excessive lost
circulation problems during the drilling
It is desirable to remove muds from wells for a
operation, then the problem is probably one of
number of reasons.
the following:
• very shallow clay particle invasion
Mud Removal
• possible filtrate invasion resulting in water
blocks
Water base mud, if properly combined, will
build a filtercake on the wall of the wellbore as • possible changes in the formation
the well is drilled. The consistency of this (particularly if naturally occurring water
filtercake will vary from a tight, dense material sensitive clays are present)
to a soft, mushy cake that allows excessive fluid
to penetrate into the formation. The mud’s fluid
loss properties must be constantly monitored to Acid–Surfactant Mud Removal
do its job. Solutions (MCA-III)
As the well is drilled, the wiping action of the
bit, pipe, and tool joints on the on the sides of If the formation is limestone, any acid solution
the wellbore can remove the filtercake. This that penetrates the mud or filtercake should
allows more filtrate and even clay particles to result in increased production. To penetrate a
invade the formation. Also, excessive speed in mud filtercake, a surfactant is often added to
running the pipe can cause fracturing and loss of hydrochloric acid. The surfactant Morflo III
whole mud to the formation. Many factors can also acts to cure other problems associated with
contribute to lost circulation problems, including mud damage. In addition to aiding penetration
natural fractures and the vugular porosity of of the filtercake, Morflo III can
some formations. • aid in thinning whole mud
Damage results when filtrate, clay, and whole
• lower surface and interfacial tension to
mud invade a formation. This damage can
prevent or remove water blocks
seriously restrict the well’s production capacity
or injectivity if it is an injection or disposal well. • aid emulsion breaking or prevention of
The degree of damage can be determined emulsions
through pressure buildup tests. If damage does
exist, steps can be taken to remove the damaged • assists in dispersing the clay minerals and
condition. Potential damage and the other insoluble fines after acid has done the
composition of the formation should be job of shrinking the clay

One potential problem with whole mud removal Sandstone Formations

is that even when acid is used to shrink clay
particles in the mud system, it does not
Removal of water base muds from a sandstone
necessarily mean the mud will be thinned. In
reservoir should follow much the same pattern
fact, the opposite can occur because the acid
as that of a limestone formation with some slight
may flocculate or cause the clay particles in the
changes. Where the calcium carbonate content
mud to clump together.
of the formation is low, hydrofluoric acid can be
To minimize this flocculation and mud used.
thickening, Morflo III is added to the acid, and
the acid strength is maintained at the lowest
possible level. Usually 5 to 10% acid is used for Hydrofluoric-Hydrochloric Acid
this work. Less than ½ % of the acid in the Mixtures (HF Acid)
solution is required for dehydrating the clay.
The rest can be used for dissolving lime in the One precaution that should be pointed out is that
mud and limestone from the formation. If the the fluoride ion (F-) will react with calcium ions
acid concentration used is 15% or higher, even (Ca++) to form a damaging precipitate. Serious
the special surfactant may not be capable of damage could result if it forms in excessive
thinning the mud effectively. Therefore, low amounts in the intergranular porosity of a
concentrations of acid solutions are sandstone formation. Limestone content of
recommended. sandstone formation is generally low enough so
that this problem will not occur. If limestone
content is too high where you can’t put enough
Non-Acid Mud Removal HCL ahead to get rid of it, then HF should not
Solutions (Mud-Flush) be used. If the well has had a weighted clear
completion fluid (such as 40% calcium chloride)
Mud-Flush lowers the viscosity of water-based used in it, damage could result. A spearhead of
mud systems and helps keep the solids in a dilute hydrochloric acid is almost always
dispersed state. Mud-Flush has several recommended ahead of HF.
applications comparable to MCA-III, but it
If whole mud or a mud filtercake is present on
cannot remove hard, dehydrated, filtercake from
the formation face or in perforation, it can be
a formation. Although Mud-Flush is not
removed by MCA-III. An appropriate surfactant
considered a replacement for MCA-III, it is a
can also be added to HF-HCL mixtures for the
more economical alternative for use in lost-
mud removal. The comments on concentrated
circulation situations. For example, if 100 bbl of
acid are still true. Even with HF solutions,
water-based mud was lost to a producing
flocculation can result, and whole mud
formation, the volume of MCA-III required to
thickening may be observed. Filtercake and
contact and chemically react with the mud
mud invasion, as well as clay within the
would be expensively large.
formation, may be removed by HF Acid.
Mud-Flush is a mixture of a mud thinner (MF-1)
The Mud-Flush solution previously mentioned
and MORFLO® III. The action of these two
can be used for whole mud removal in sandstone
chemicals dissolved in water is sufficient to
formations in the same manner as discussed for
perform the following functions:
limestone formations.
• Aid removal of water-based drilling muds
from all types of formations
Oil Base Muds
• Help prevent and break emulsions and water
blocks
Two basic oil mud systems require attention: the
Mud-Flush should not be used for removing oil- Oil External Emulsion Muds and the True Oil
based mud. Base Muds.

Oil External Emulsions (Invert N-Ver-Sperse O consists of

Emulsions) • hydrocarbon solvents, such as diesel oil,
kerosene, or xylene
Emulsions used for drilling are usually fairly
low solid, oil external, oil wet clay stabilized • 5% MUSOL® or MUSOL A solvent
emulsions. They can be broken, with • and HYFLO® IVM surfactant
undesirable results, if too much of a high surface
area solid such as clay is added to the system. If the muds contain asphaltic materials, use
They can also be broken with appropriate xylene for the hydrocarbon solvent.
emulsion breakers in some instances. Use N-Ver-Sperse A fluid, containing wetting
agents and dispersants, when hydrocarbon-based
fluids must be avoided because of economics,
True Oil Base Muds environmental concerns or lower hydrostatic
pressures. The aqueous system also can be used
True oil base muds are usually prepared by as either a mud cleanout fluid or a formation
gelling a viscous, high asphaltene oil and adding breakdown fluid. When used as a mud cleanout
to it blown asphalt, fine calcium carbonate, and fluid, gelling agents can be added to give the
other materials which can have fluid loss fluid sufficient viscosity to carry the mud solids
properties. One of the most effective thinning from the wellbore. It can also be weighted to 11
and removal solutions consists of glacial acetic lb/gal using zinc chloride. Materials, such as
acid or acetic anhydride mixed with an aromatic calcium chloride and sodium bromide, are not
solvent containing Hyflo IV. These will also satisfactory weighting salts. Sodium bromide
water wet the pipe and formation. can be used for weighting, however, if methanol
Some oil base type muds tend to spontaneously is included in the formulation. Test weighted
form a very viscous emulsion with certain solutions at specific well conditions before use.
cements. This emphasizes the need for a wash N-Ver-Sperse A consists of
ahead of the cement.
• water containing 2% KCl by weight
• 10% MUSOL
N-VER-Sperse
(NOTE: MUSOL A is not recommended
N-Ver-Sperse A and N-Ver-Sperse O have been because of separation problems noted at
developed to help clean up a well where oil higher temperatures)
based muds have been used. • 1% MORFLO III by volume
Use N-Ver-Sperse O fluid when the presence of • 50 lb SPACER SPERSE per 1,000 gal of
a hydrocarbon fluid would be advantageous. Use fluid.
it either as a cleanout fluid to remove mud from
the wellbore and formation or as a formation
breakdown fluid. When used as a mud cleanout Additional References
fluid, circulate N-Ver-Sperse O at a fairly high
rate to prevent the solids in the mud from
Acidizing Methods and Materials (Mud
settling out.
Removal) - HalWorld

Unit G Quiz: Damage Removal-Mud
Fill in the blanks or mark the correct answer to check your progress in Unit G.
1. Damage can result when ____________________, ____________________ and
____________________ ____________________ invade a formation.
2. Two solutions that can be used to remove mud damage in a limestone formation are
____________________ and _____________________ ____________________.
3. ______ True ______ False Mud damage in a sandstone formation can be removed with HF Acid
if the limestone content is high.
4. The two types of oil base muds are ________________ ____________________ ________________
and ________________ ________________ ________________ muds.
5. ____________________ and ____________________ are two solutions for removing oil base muds.

Unit H: Paraffins and Asphaltenes

Other than the physical properties and condition the deposition problem varies between reservoirs
of the producing formations, one of the most in the same area and between wells in the same
aggravating problems for the petroleum reservoir. The severity is difficult to estimate
producer is the build-up of organic deposits in until it cannot be controlled by normal
areas like the well bore and feed lines. These production techniques. Many operators have
deposits act as chokes during build-up in the learned to live with their situation and have
well bore. They gradually decrease production “grown-up” with their removal techniques.
and, in time, could completely stop the flow of Therefore, they tend to treat the problem as an
oil. This may cause rod failure, split tubing, and unavoidable part of life.
worn pump parts unless some remedial action is
taken. Two common actions are
Cloud Point and Pour Point
• an orderly program for the removal of the
deposits Cloud point and pour point tests are used to get
• the use of some type of inhibitor. general measurements of the ability of the crude
oil to hold paraffin in solution. These are
The petroleum industry spends millions of experimental measurements that give us some
dollars annually correcting these deposition idea where or when paraffin might cause
problems. problems.
Organic deposits are formed when the chemical The cloud point is defined as the temperature
equilibrium of the oil is upset. This causes where paraffin begins to come out of solution.
certain chemicals normally in solution to This point is visible in clear crude oils as a slight
precipitate. The physical and chemical cloudiness. Obviously the cloud point of a dark
characteristics of many crude oils are such that crude oil has no meaning since the cloudiness is
the oils can deposit waxy material called not visible. Other instrumental methods are
paraffins or, in some instances, asphaltenes. sometimes used to obtain the cloud point of
crude oils.
Paraffins If the liquid or crude oil is slowly cooled below
the cloud point without agitation, small wax
The family of hydrocarbons classified as crystals gradually form an interlocking network
paraffins is generally inert. They are resistant to that will support the liquid. A temperature is
dissolving in acids, bases, and oxidizing agents. finally reached where the oil will not flow when
This makes it difficult to remove these deposits tilted to a horizontal position in a bottle. This is
chemically. referred to as the pour point. This point has
more meaning when dealing with crude oils.
Depending on the conditions where paraffin Generally, the higher the cloud point or pour
deposits were formed, they have different point of an oil, the less stable the paraffin is in
physical forms. These forms include soft mush the oil.
to hard, brittle deposits. Also, paraffin deposits
will often include other materials such as scale,
sand particles, or asphaltenes.
Paraffin problems are encountered in almost
every oil producing area. Some areas are more
severely affected than others. The severity of

Factors Affecting Paraffin expand and cool. The largest amount of cooling
is usually at the formation face.
Deposition
Paraffin deposition is primarily due to a Loss of Volatile Constituents
reduction in the amount of paraffin that can be from the Crude
dissolved in a crude oil. This loss of solubility
can be caused by many different factors. Some
of the more important factors are discussed Generally, the light parts of a crude oil are the
below. ones that dissolve the most paraffin. Loss of
these lighter constituents reduces the quantity of
paraffin that the oil can hold in solution at a
Temperature specific temperature.
In most solutions, as you lower the temperature Evaporation of the volatile constituents in crude
the material dissolved in the fluid begins to drop oil also tends to reduce the temperature of the
out of solution. This is also true of paraffins. oil. This is due to the heat required to change
As oil is produced, its temperature can drop for a the liquid to a vapor. This effect is not as
variety of reasons. Cooling can be produced: important as the loss in solubility mentioned
above.
• by gas expanding through an orifice or
restriction (choke) As a producing field becomes older, the lighter
constituents are constantly being removed from
• as a result of the gas expanding, forcing the the oil, even within the formation. Therefore,
oil through the formation to the well and the oil becomes more saturated with paraffin
lifting it to the surface before it ever leaves the formation. For this
reason, many paraffin deposition problems
• by loss of heat from the oil and gas to the
become more severe as the well becomes older.
surrounding formations as it flows from the
bottom of the well to the surface
• by dissolved gas being liberated from Suspended Particles in the
solution Crude
• by water production
As was stated previously, paraffin begins to
• by the evaporation or vaporization of the separate from crude oil when the temperature of
lighter constituents the oil cools and the paraffin is no longer stable
• in oil flow lines due to loss of heat to air in solution. There is some evidence that
(especially in winter) formation fines such as sand and silt often speed
this separation process. These small particles
suspended in the crude act as a nucleus for the
Pressure
small wax particles to form into larger particles.
These separate more readily from the oil.
Pressure helps keep gas and lighter constituents Paraffin problems are greatly increased when
dissolved in the crude oil. If the wellhead these fines are present, especially since fines
pressure were the same as formation pressure, tend to increase the bulk of the deposit.
paraffin would probably not cause many
problems.
However, oil will not flow unless there is some Conditions Favoring Paraffin
type of pressure drop. The largest percentage of Deposition
this pressure drop occurs near the bottom of the
well. As the pressure decreases, oil and gas Even though wax may separate from the crude
oil, the paraffin will not necessarily deposit on

the tubular goods and other objects. The wax flow channels become partially blocked or
will probably remain suspended in the crude oil plugged, and the flow of oil is restricted. Even
itself. This ideal situation often exists. In some after the original formation temperature is
wells producing very waxy crude, little or no restored, it may be difficult to redissolve the
paraffin problems are experienced. precipitated paraffin in the same fluid. This is
because the melting point of solid paraffins is
On the other hand, some crude oil areas with
much higher than the cloud point. However,
“low” paraffin content have some severe
formations having temperatures higher than the
problems. Listed below are some conditions
melting point of the precipitated paraffin would
that are favorable for paraffin deposition:
not be affected.
• The alternate coating of the pipe and
One obvious method of minimizing this problem
draining of the oil. As the pipe fills, then
would be to heat the stimulation fluids on the
drains, the film left on the pipe surface is too
surface. Another method might be to run a
thin and its movement too slow to carry the
paraffin solvent ahead of the job.
wax particles away.
• The presence of only a film of oil in contact
with the pipe while the well is flowing. Methods Used to Remove
• When the oil contacts with an unusually Deposits
cold surface such as the production of oil
through water zones. This will cause Methods generally used to remove
paraffin crystals to grow directly on the pipe accumulations of paraffin can be classified as
wall. It is estimated that the heat loss from a follows:
pipe in contact with water is approximately • Those that remove the paraffin by use of
eight times greater than when in contact mechanical equipment.
with air or dry earth.
• Those that remove the paraffin by use of
• Rough pipe surfaces. solvents which dissolve the deposits.
• Electrical charges on various materials in the • Those that use heat, which melts the wax and
crude oil. reduces it to a liquid so that it can easily be
These conditions favoring paraffin deposition removed with produced oil.
combined with a sufficient cooling of crude oil Mechanical methods such as scrapers, knives,
can cause serious problems. hooks, and other tools for the removal of
paraffin deposits offer fairly satisfactory results
when the wax accumulation is in the well bore.
Paraffin Precipitation during Tools such as these are common in the oil field
Fracture Stimulation and will not be discussed here.
Studies have been conducted on the effect of Hot Oil

injecting cold fluids into a warm, producing
reservoir. It was found that the crude oil can One of the most common techniques of
deposit paraffin in the formation when the removing paraffin deposits is to dissolve or melt
reservoir is cooled by large volumes of cold waxy accumulation with hot oil. This removal
fluids such as those used in fracturing method is very simple. Lease crude is run
treatments. This is particularly true when the through heat exchangers and pumped into the
surface fluid temperature is cooler than the well at temperatures in excess of 300°F. This
formation temperature. If the fluid in the will usually melt the accumulated paraffin in the
formation is cooled to a temperature below the oil string. The paraffin is then produced back
cloud point, paraffin precipitates may deposit in with the oil. Many small businesses own and
the formation pores. Once this occurs, the fluid

operate specially designed hot-oil trucks. Many Parasperse Additives

wells are hot oiled at regular intervals ranging
from every two to four weeks or more. Parasperse has proven very successful in both
There is some evidence that hot oiling may be laboratory and field tests as a water-dispersible
detrimental to crude oil production. Paraffin paraffin removal agent.
damage is caused when temperatures higher than One of the most successful applications of
the formation temperature is used to melt the Parasperse® cleaner is periodic cleaning of the
paraffin wax. As the hot oil is circulated, some formation face. Other applications include
of the liquid containing a high concentration of wellbore cleanout, flowline cleaning, paraffin
paraffin may leak off into the producing zone inhibitor placement, and as a preflush in
where it cools to the formation temperature. fracturing. This material can be used as an
This allows paraffin to reprecipitate within the alternative to hot-oiling downhole. Parasperse®
formation. When this type of damage is is ordinarily used at a concentration of 2-10% in
suspected, it often requires several soakings with a water carrier. This water may be produced
a good paraffin solvent to clean the wax out of formation brine or clean surface water.
the formation matrix.
Successful treatments have been noted when
Many crude paraffin deposits contain inorganic cold water was used. Preferably, the system
solids such as corrosion products, scale, and should be warmed to about 100-120°F to aid the
formation fines. These solids can comprise as cleaning action of the Parasperse® solution. In
much as 60% of the paraffin deposit. If the laboratory tests, the Parasperse® solution
paraffin is melted by the hot oil, the solids could removed more crude paraffin than is dissolved in
be forced into the formation matrix and create conventional paraffin solvents.
another source of damage.
Parasperse® treatments are also less expensive
than conventional paraffin solvents. Since water
Steam
comprises 90-98% of the removal system, the
chemical expense is very reasonable. In many
Steam has been used successfully in a number of instances, Parasperse® treatments have
fields having severe paraffin problems. The significantly increased the production of a well.
application of steam heat to the formation is a
practical method of heating the sand and Paraspserse T was designed for the removal of
removing paraffin from the formation face. One both paraffins and asphaltenes. It has the same
disadvantage of this method could be the applications as Parasperse.
possibility of plugging the producing zone with Parasperse LR was primarily designed for use in
paraffin in much the same manner as with hot oil hydrocarbon-based fluids. However, it can also
jobs. be added to aqueous fluids and has the same
general applications as the other Parasperse
Aqueous Paraffin Removal Systems additives.
Certain water-based chemicals have been Solvents

successfully used to remove downhole paraffin
deposits. These chemicals, when added to The use of solvents to remove paraffin deposits
water, have the ability to remove accumulated is becoming more common in the oil field.
organic deposits and disperse them for easy Many laboratory studies have been conducted on
removal. a variety of solvents in an attempt to determine
the best solvents for paraffin and how the
solubility varies with different waxes.
In general, the solubility of different waxes in a
given solvent at a definite temperature decreases

as the molecular weight and melting point loss, produce the oil out of the well bore rapidly,
increase. and minimize agitation of oil in the wellbore.
The usual practice has been to dissolve paraffin
accumulations using light, hydrocarbon solvents Electrical Heaters
such as kerosene, naphtha, gasoline, diesel fuel,
etc. These solvents are very effective for The use of bottom hole heaters is a less
dissolving purified paraffins such as canning satisfactory means of controlling paraffin
waxes. However, crude waxes are usually deposition. Heaters are designed to heat the oil
deposited with a considerable quantity of as it comes out of the formation in order to keep
asphaltenes present. Because asphaltenes are the paraffin “in solution.” The use of this
insoluble in most solvents, they tend to hinder technique is severely limited by economics, high
the dissolving of the waxes present in the maintenance costs, and the absence of electricity
deposit. This makes the solvent less effective in in isolated fields.
dissolving the total deposit.
Plastic Coatings
PARAGON Solvents
Plastic pipe used as feedlines and plastic coated
Tests show that aromatic solvents such as xylene pipe used in the well has received much
and toluene dissolve both the wax and the attention in the last few years as a means of
asphaltenes. These two solvents are excellent combating paraffin deposition. Extruded plastic
for treating crude paraffin deposits. pipes and plastic coatings have proven effective
Halliburton’s Paragon is an effective blend of in some areas.
aromatic solvents.
The idea behind the use of plastic coatings on
Paragon 1 and Paragon 100E+ effectively downhole equipment is that paraffin will not
dissolve paraffin without using benzene, ethyl adhere to the smooth surface provided by the
benzene, toluene, or xylene (BETX). The use of plastic. In some cases this is true; however,
one or more of these four materials may be most plastic coatings will not withstand the
restricted in certain areas due to government rough treatment given to downhole equipment.
regulation. Therefore, the coating becomes scratched and
worn and provides an excellent base for paraffin
Paragon EA™ is a cost-effective solvent for the
deposition. In some instances, certain types of
removal of excess pipe dope, paraffin deposits,
plastic coatings actually promote the deposition
and crude oil residues. In most cases, Paragon
of paraffin. This method of combating paraffin
EA will be applied as a neat solvent. Unlike
deposition is also very expensive, especially if
Xylene and Paragon 100E+, Paragon EA does
the existing iron has to be junked and new
not contain any aromatic components and is
plastic coated equipment placed in the well.
environmentally acceptable.
Surfactants
Methods for Decreasing the
Severity of Deposition Many of the chemicals used to combat paraffin
problems are just ordinary surfactants or
dispersants. The surfactants work by water-
Altering Production Techniques wetting the tubular goods. This water film helps
keep paraffin from sticking to the pipe wall.
Altering production techniques is one way to Dispersants work by reacting with paraffin and
avoid paraffin problems. There are many causing the particles to repel each other.
methods that can be used to cut down on heat

These approaches have been partially successful. In all applications a concentration of 0.5 to 0.75
However, there is no information on when they gallons of inhibitor per 100 bbl. of produced
will work. It is mostly a trial-and-error method. crude oil should be maintained.
The squeeze treatment is done by diluting 1
Crystal Modifiers drum of paraffin inhibitor per each 50 bbl. of
produced crude per day in 500 gallons of
Generally, crystal modifiers have many of the diesel, kerosene, xylene, Paragon, or lease
same drawbacks of surfactants. They appear to crude. Thus, for a 50 BOPD (barrels of oil per
be somewhat unpredictable in their day) well 1 drum of inhibitor diluted to 500
effectiveness. However, with the proper gallons would be required; for a 100 BOPD
placement technique, they seem to work fairly well 2 drums of inhibitor diluted to 1000
well and offer the most hope for the chemical gallons would be required, etc. Once the
inhibition of paraffin deposition. When viewed inhibitor is spotted downhole, it is then over-
under a microscope, they appear to modify the displaced with 5-10 bbl. of lease crude per foot
wax crystals precipitating from a solution. The of formation. Inhibitor treatments as outlined
normal crystal growth of paraffin is deformed above should theoretically give about 200 days
sufficiently to inhibit further growth. The crude protection against paraffin deposition.
oil becomes filled with paraffin crystals that are
Parachek® 160 paraffin inhibitor continuous
much smaller than normal and have fewer
injection into the crude stream may be
tendencies to adhere to pipe surfaces. While not
accomplished by metering the inhibitor
completely curing the paraffin problem, crystal
downhole with a small surface chemical pump,
modifiers help reduce the severity of the
by injection into the power oil on wells
problem.
equipped with a subsurface hydraulic system,
or by using a bypass feeder arrangement. One
Parachek® 160 Inhibitor advantage to the continuous injection of the
paraffin inhibitor is that conscientious
Parachek® 160 inhibitor is an effective blend of operating personnel can carefully control the
chemicals that may be classed as crystal concentration of the chemical. In all continuous
modifiers. Parachek® 160 has been found to be injection applications, the inhibitor must enter
effective in relieving paraffin problems the crude stream well ahead of the point of
encountered in most crude oil producing areas. paraffin deposition. This is imperative for a
However, it should be noted that Parachek® 160 successful treatment.
does not prevent the paraffin crystals from
It is possible that Parachek® 160 could be
coming out of solution in the crude oil. Once the
placed during other remedial treatments on a
crude oil becomes saturated with dissolved
well, such as a propped fracturing treatment.
paraffin, paraffin crystals begin to form in
Paracheck® 160 is not ordinarily dispersible in
solution. Parachek® 160 is not a paraffin solvent
aqueous solutions; however, it could be
and should not be used in place of Paragon or
injected into an aqueous fracturing fluid
Parasperse. That is, it is not to be used as a
providing the pump rate is sufficient to keep it
paraffin removal solution, but rather as
dispersed. Parachek® 160 can also be added by
prevention against paraffin deposition.
mixing with Parasperse. Parachek 160 has not
There are three different applications that may been tested to determine if it has a detrimental
be used to introduce Parachek® 160 into the effect on the gel properties of My-T-Oil IV and
crude oil stream. These are: My-T-Oil V, so compatibility testing would
need to be conducted before attempting to use it
• squeezing into the formation with these fracturing fluids.
• continuous application
• introduction into other stimulation
fluids.

Asphaltenes tends to aggregate (form) the asphaltene

particles. The breaking of this bonding allows
better solvent penetration and increases the
Asphaltenes are generally considered to be
dissolution rate of the asphaltenes.
suspended particles in the oil. Unlike paraffins,
they are not soluble in the light constituents of Targon® II is used from 1 - 10% by volume of
oil. Asphaltene deposition can be caused by the carrier. It will not work in solvents such as
some of the same conditions as paraffin. kerosene, diesel, gasoline, condensate, etc.
However, it is believed that asphaltene deposits
are caused by the inability of a crude oil to keep Tarchek
the particles dispersed.
Asphaltene precipitation is less widespread in Tarchek is an asphaltene inhibitor for use in
the United States than is paraffin precipitation. wells with asphaltene precipitation problems. It
It appears that certain fields in Mississippi and can be run in combination with such paraffin
California are the most susceptible to this type inhibitors as Parachek®160 to treat crude oils
of deposition. However, any well producing that have both paraffin and asphaltene problems.
asphaltic base crude may experience this Laboratory testing has shown that Tarchek does
problem. Asphaltene deposition is also a not affect paraffin inhibition. Remember that,
problem in many areas outside the United States. like Parachek®160, Tarchek inhibitor is not a
Where asphaltene precipitation is a problem, the solvent and should not be used in place of
deposition usually occurs at the bottom of the Paragon solvent. The primary function of
well bore and adjacent to the producing Tarchek inhibitor is not to remove asphaltene
formation. In some instances the asphaltenes deposits, but to prevent asphaltene from
may precipitate within the formation itself and depositing. Before applying Tarchek, clean out
cause damage. any existing asphaltene deposit either
mechanically or by using a solvent soak
consisting of Paragon and the appropriate
Targon® II Solvent amounts of Hyflo®IV M surfactant and
Targon®II solvent.
Targon® II is an organic solvent used to remove Tarchek asphaltene inhibitor stabilizes the
asphaltene deposits. This solvent was designed asphaltenes by preventing their flocculation
for use with an aromatic solvent carrier (clumping) and/or deposition; thereby,
(Paragon). Targon® II was designed to use as an protecting the entire production system from
additive in aromatic solvents to enhance their asphaltene plugging.
asphaltene dissolution properties by breaking
down the strong intermolecular bonding that

Unit H Quiz
Fill in the blanks with one or more words or circle the correct answer to check your progress in
Unit H.
1. ______ True ______ False Most organic deposits in a well contain both paraffin and asphaltene.
2. ______ True ______ False Paraffin problems are rare in the oilfield.
3. The cloud point is the ____________________ when paraffins begin to come out of
____________________.
4. The pour point is the ____________________ when oil can no longer ____________________.
5. Factors affecting paraffin deposition are:
__________________________________________________________________
__________________________________________________________________
__________________________________________________________________
__________________________________________________________________
__________________________________________________________________
6. ______ True ______ False It is impossible to cause paraffin deposition during a stimulation job.
7. Paraffin removal is accomplished by:
__________________________________________________________________
__________________________________________________________________
__________________________________________________________________
8. Parachek® 160 inhibitor is an effective blend of chemicals that may be classed as

____________________ ____________________.
9. ____________________ can be used to help dissolve asphaltenes when added to Paragon and
____________________ can be used to prevent asphaltene precipitation.

Unit I: Scale Removal and Prevention

The deposition of scaling material from brines
produced with oil has been a serious problem for Scale Type
Chemical
Mineral Name
many years. Compounds such as calcium Formula
sulfate, calcium carbonate and barium sulfate Water Soluble Deposits
have been found in many wells. These deposits Sodium
may exist in injection wells, producing wells and NaCl Halite (salt)
Chloride
waste disposal wells. Acid Soluble Deposits
Calcium
CaCO3 Calcite
Scale Effects Carbonate
Iron Carbonate FeCO3 Soderite
The effects that scales caused by brine Iron Sulfide FeS Trolite
production have on a well depend largely on the Iron Oxide Fe3O4 Magnetite
type of scale in the system. Scales may restrict
and completely choke off production in the Fe2O3 Hematite
tubing, flow lines, or tubing perforations either Magnesium
Mg(OH)2 Brucite
at the formation face or in the perforations. Hydroxide
Scales have been suspected of depositing in Acid Insoluble Deposits
fractures or in the formation some distance from Calcium Sulfate CaSO4 2H2O Gypsum
the well bore.
Calcium Sulfate CaSO4 Anhydrite
Scale not only restricts production, but also
Barium Sulfate BaSO4 Barite
causes inefficiency and production equipment
failure. Since many older fields have entered Strontium
SrSO4 Celestite
into enhanced recovery stages, scaling problems Sulfate
can have an even greater impact on waterflood Barium
operations. Strontium BaSr(SO4)2
Sulfate
One of the most important factors in dealing
Table 8.5 - Oilwell Scale Deposits
with scaling problems is to have an accurate
identification of the material being deposited.
There are essentially two methods used in the
laboratory for the identification of scales. One
involves the use of an instrumental method (x- Types of Scale
ray diffraction). The other uses chemical
methods. Scales can roughly be divided into three classes:
• water soluble
• acid soluble
• acid insoluble
These are based on the ability of water or
hydrochloric acid to dissolve the scale. This is a
simplified division (see Table 8.5) because many
times pure calcium sulfate or pure calcium
carbonate is not deposited. The scale deposit is

usually a mixture of one or more of the major

scales plus corrosion products, solidified oil,
silicates, paraffin, etc. However, separation into
water soluble, acid soluble or acid insoluble is
adequate for field analysis.
Scale Formation
Prior to production, well fluids remain in a
static, undisturbed state. Scale deposits occur as
a result of disturbing this equilibrium. When
production is started, a pressure drop occurs near
the well bore. This pressure change allows
dissolved gases to come out of solution. Since
changes destroy the state of equilibrium, Figure 8.8 - Heavy Scale Deposits
deposits can form. For example, calcium
carbonate scale can occur as a result of a
pressure drop at the well bore. Calcium
carbonate does not exist in the formation brine
as calcium and carbonate ions, but as calcium
Scale Form
and bicarbonate ions. A change in pressure
allows carbon dioxide (CO2) to escape from The Physical form of a scale deposit is
solution. Calcium carbonate scale can then be dependent upon the manner in which it was
formed. deposited. Scale does not form spontaneously.
Instead, it occurs in stages. Scale molecules
Scale deposits may also occur as the result of form clusters over a period of time. As these
mixing incompatible waters. Waters from clusters grow, they become too heavy to remain
different zones may become mixed in the well suspended in solution. They precipitate or
bore, or injection water may mix with formation become deposits. The final crystal form of the
water. In water injection wells, brines from scale may resemble popcorn and be either soft
several sources may be combined and cause and fluffy or very hard and dense. The hard,
compatibility problems which could form scale. dense scales occur as the result of slow growth.
The incompatibility of mixed brines results The soft, fluffy scales are often deposited
when one water contains a high concentration of rapidly. Most inorganic scales appear in one of
calcium or barium and the other water contains a three forms:
high concentration of sulfate or bicarbonate ions
in solution. As these waters mix, deposition can • thin scales or popcorn like
occur because the final solution becomes • laminated deposits
saturated with calcium sulfate, barium sulfate, or
calcium carbonate. These deposits may be • crystalline deposits
found on the rods, tubing or flow lines. The thin type scales are normally the most
Corrosion and microbial reaction products can permeable and easily removed. The laminated
result in deposition of various iron scales such as or crystalline scale forms are less permeable and
iron oxides and iron sulfide. Sulfate reducing harder to remove.
bacteria are a source of hydrogen sulfide which Factors such as pressure drops, temperature, and
can precipitate iron that is in solution, or the the mixing of water can result in severe scale
hydrogen sulfide can react with steel. Iron in problems. However, the formation of scale is
solution can also be precipitated if oxygen is usually a situation with several possible causes.
introduced into a system. Iron oxide (rust) can As changes in the equilibrium occur, interaction
form on metal surfaces when oxygen is present.

of these changes with other conditions downhole particular scale deposit takes can significantly
can result in deposits. The final form that a affect efforts to remove the scale.
Figure 8.9 - Flowchart for field identification of scale
Acid Soluble Scale Removal Regular Inhibited Acid
Acid soluble scales are: Regular inhibited acid solution is normally 15 %

hydrochloric acid that contains corrosion
• Calcium Carbonate
inhibitor. It is the basic acid for preparing
• Iron Carbonate penetrating and non-emulsifying acid. It is not
normally used for scale removal.
• Iron Sulfide
• Iron Oxides
Penetrating Acid
• Iron Hydroxide.
One or more of the following solutions can Penetrating acid solution is regular inhibited
remove these acid soluble scales. acid that has 1 ½ gallons of Pen-5 or Pen-88 per
1000 gallons. Pen-5 and Pen-88 are surfactants

that lower the surface tension of the acid during the course of the acidizing treatment, iron
solution to approximately 25 dynes/cm. salts and oxides that were put into solution as
Lowering the surface tension increases the iron chlorides may form insoluble iron
acid’s ability to contact the scale. hydroxides. These iron compounds can deposit
near the well bore and cause even lower
A penetrating acid solution can be successfully
injectivity than before the treatment.
used on scales containing only a small amount
of iron if it does not form an emulsion with the The pH control is based on the action of a weak
formation fluids. When treating surface acid that reacts much more slowly on the
pipelines, gathering lines, or other systems limestone scale and other acid soluble materials
where the solution will not enter the formation, than the hydrochloric acid reacts. While the pH
penetrating acid can be used for all acid soluble remains low (less than 3), the iron will not
scale. Under cold conditions, increasing the precipitate.
concentration of the hydrochloric acid will
increase the reaction rate. With most iron
scales, it is usually best to use at least 20 percent Multiple Service Acid (MSA)
hydrochloric acid.
MSA contains a 10 percent concentration of
acetic acid. MSA’s greatest attribute in scale
Non-Emulsifying Acid (NE) removal treatment is that it will not damage
chrome-plated parts or alloy steels found in
Non-emulsifying acid solution is regular downhole pumping. Calcium carbonate scales
inhibited acid that has one or more of the non- are readily dissolved by MSA.
emulsifying chemicals added. Non-emulsifying
acid can also have Pen-5 or Pen-88 added to the
solution to help obtain the desired wetting Paragon Acid Dispersion (PAD)
properties.
The non-emulsifying chemicals are added to Paragon Acid Dispersion (PAD) is a mixture
help prevent the formation of emulsions between that contains Paragon (an aromatic solvent),
the treating solution and the formation fluids. acid, and a surfactant. The acid phase may be
Non-emulsifying acid, like penetrating acid, is prepared from a number of acid solutions and
used when the scale is primarily calcium selection of the acid phase depends on the
carbonate and the iron concentration is low. conditions involved. In scale removal
applications, the aromatic Paragon portion of the
dispersion is effective in removing paraffin,
Fe Acid congealed oil and other organic deposits. This
allows the acid to contact the scale and react
more completely. PAD has been injected as the
Fe acid contains hydrochloric acid along with a
first stage for degreasing and removing acid
blend of sequestering agents and a pH control
soluble material prior to a Gypsol or Liquid
agent. During scale removal, the sequestering
Scale Disintegrator job for the removal of acid
agent contained in Fe Acid prevents the
insoluble gypsum.
precipitation of the iron by forming a complex
with the iron and keeping it in solution. Fe Acid
is most suited for the removal of iron
compounds from disposal and injection wells.
These deposits normally occur near the well
bore and gradually block the permeability.
Hydrochloric acid will dissolve iron scales and
cause a temporary increase in injectivity.
However, as the acid spends on the formation

Type of Scale
Gal 15% HCL/ lb Scale/ gal Before placing the Gypsol, the wellbore should
cu ft of Scale of 15% HCL be degreased with kerosene containing Hyflo IV
CaCO3 (Calcium 95 1.84 or with DopeBuster M. After pumping off the
Carbonate) kerosene, the acid reactive scales and corrosion
Fe2O3 (Iron Oxide) 318 0.98 products should be removed with Fe Acid or
MSA. PAD made with Fe Acid or MSA can
FeS (Iron Sulfide) 180 1.62
also be used to degrease the well bore to remove
FeCO3 (Siderite) 111 2.13 the acid reactive materials present. The acid-
Fe3O4 423 0.74 containing solution should be completely
pumped off before placing the Gypsol. The
Table 8.6- Volume of scale dissolved in 15% converted gypsum can then be removed by
HCL dumping or pumping inhibited hydrochloric acid
or MSA. If the scale is extremely thick,
successive treatments may be necessary with
Acid Insoluble Scale Removal Gypsol followed by acid.
Acid insoluble scales are:

• Calcium Sulfate
Liquid Scale Disintegrator
• Barium Sulfate Liquid Scale Disintegrator or LSD, is an organic
• Strontium Sulfate solution that is designed specifically for the
removal of calcium sulfate scales, gypsum and
• Barium-Strontium Sulfate. anhydrite. LSD reacts with gypsum to form a
Two general types of conversion agents have precipitate that won’t adhere to gypsum but
historically been used for scale removal; Gypsol forms a water dispersible sludge. The
and hydroxide solutions. Since then, research precipitate has a tendency to slough away from
has developed a number of additional scale the surface of the gypsum and increases the
removal chemicals that can be used. penetration of the solvent. Also, since the
precipitate does not adhere tightly and is readily
dispersible in water, an acid stage may not be
GYPSOL needed to remove the sludge. If it becomes
necessary to remove the LSD precipitate with
acid, it is soluble at 1.2 pounds per gallon of
Gypsol gypsum converter is a water solution
15% hydrochloric acid.
containing one-half pound of OG-1 and one-half
pound of OG-2 per gallon of solution. A Laboratory and field tests have shown that most
surfactant, Pen-5, is also added at one gallon per gypsum deposits can be removed with LSD in
1000 gallons of the solution. 24 to 48 hours. Also, LSD is more effective
than Gypsol for removing gypsum scale. A
With Gypsol, gypsum (CaSO4∗2H20) is
degreasing step with Paragon or a PAD solution
converted to acid soluble calcium carbonate.
with Fe Acid as the acid phase is preferable prior
Gypsol is inexpensive and has been successfully
to the scale removal treatment. The degreasing
used in many wells. However, the converting
step should be circulated for 12 to 24 hours
properties of Gypsol are severely retarded when
before being pumped off. The LSD solution is
encountering dense, laminated gypsum scale.
then dumped in the annulus. If the scale deposit
Because of this lack of penetration, repeated
is present in fractures some distance from the
application may be necessary.
well bore, a soaking period prior to circulating is
Gypsol works only with gypsum deposits. recommended. If the scale deposit is considered
Gypsol is normally placed in contact with the restricted to the well bore, circulation can be
scale for 24 to 48 hours and allowed to convert started immediately after dumping. Since the
gypsum to an acid soluble calcium carbonate. scale deposit may be oil wet, the addition of a

suitable surfactant would allow better wetting 7.0

and contact.
6.0
NOTE: Emulsion tests should be conducted
5.0
with the LSD and non-emulsifiers added just as
they would be with an acid treatment. Wells on 4.0
gas lift or flowing wells must have the “spot and
3.0
soak” technique applied.
2.0
LSD can be used at concentrations ranging from
10-50%. Concentrations and volumes used are 1.0
determined by the amount of scale present
downhole. Figure 8.10 gives the theoretical 0 10 20 30 40 50
amount of gypsum removed by various CONCENTRATION OF LSD (WT%)
concentrations of LSD in pounds per gallon. Figure 8.10 - Theoretical Amount of

Note that these are theoretical values and Gypsum Removed by Various
represent the maximum amount of gypsum that Concentrations of LSD (per gallon)
can be removed. For instance, LSD-300 and
LSD-500 solutions will theoretically remove
4.35 and 7.0 pounds of gypsum per gallon, In cases as serious as the one mentioned,
respectively. However, laboratory tests circulating the LSD solution through the interval
conducted with field scale samples have shown would be more practical. The volume and
that LSD-300 and LSD-500 solutions will concentration of LSD treating solution necessary
remove only 2-3 and 3-5 pounds of gypsum per to circulate would depend upon the length of the
gallon in 24 to 48 hours under static test interval, tubing volume, and fluid level in the
conditions. annulus. The treatment time would depend on
The best method in determining the most the particular scale deposit, but 24-48 hours of
effective and economical concentration of LSD circulation should be enough. Longer
for a gypsum removal treatment is to conduct circulating times may be necessary in extremely
disintegration rate tests with scale from the well. difficult cases. Dilution with well fluids may
However, this is not always possible under field slow the disintegration rate.
conditions. Equations are in this unit for determining the
Success or failure of a scale removal treatment cubic feet of scale present on the inside and
often depends upon having sufficient volumes outside of various pipe sizes. The number of
and concentrations of chemicals. For example, pounds of gypsum present per linear foot may be
if a 2 in. I.D. pipe has scale 0.5 in. thick, it calculated by multiplying 144 x cubic foot of
would contain 0.016 cubic feet of gypsum per gypsum present per linear foot. A cubic foot of
linear foot of pipe. Gypsum weighs 144 pounds gypsum weighs approximately 144 pounds.
per cubic foot so each linear foot of pipe would
contain 2.3 pounds of gypsum. A pipe with a 2 BaSO4lvent
in. I.D. containing 0.5 in. thick scale has a
capacity of 0.0449 gallon per linear foot. BaSO4lvent, pronounced (bay-solvent), is a
Calculations show 0.0449 gallon of LSD will solution specifically designed to remove barium
theoretically remove 0.314 pounds of gypsum. sulfate and strontium sulfate scales from
So, as many as 5-10 treatments may be required injection wells, disposal wells, gas wells, or
to remove the scale if a spot and soak technique producing wells. BaSO4lvent solution is a one
is used. stage solvent; it does not require an additional
acid stage for the removal of the scale. The use
of BaSO4lvent solution can minimize or
eliminate costly and time-consuming pulling

operations and physical descaling of pumps and Equations for Determining

tubing. Deposits in perforations, SSSV, and gas-
lift valves can be removed with BaSO4lvent
Volume of Scale Present
solution. By using BaSO4lvent, operators can
more effectively remove NORM (naturally Often, if a simple calcium carbonate scale is to
occurring radioactive material) scale without be removed, the problem is finding how much
exposure to its hazards and eliminate the costly 15% hydrocholoric acid is needed. It is possible
disposal of these materials. to use too little acid and fail to effectively
stimulate the well. For example, more than 90
BaSO4lvent solution can be applied neat or cubic feet of calcium carbonate scale have been
diluted to a 50% concentration consisting of found in some injection wells. For this quantity
freshwater, seawater, or low-hardness brines. of scale, a treatment of at least 8,550 gallons of
Higher temperatures increase the performance 15% hydrochloric acid should be used. A
and reaction rate of BaSO4lvent solution. Any smaller amount of acid may not improve
means of agitation, such as circulation or injectivity and may even decrease it because of
periodical pumping of the material back and sloughing of the deposit.
forth through scaled perforations, will reduce the
time required for scale removal. Formation The following equations give the scale quantities
squeezes are effective for removing scale from in cubic feet for deposits of various thicknesses
the near-wellbore area. Soak and shut-in times on the inside and outside of different pipe sizes.
of 8 to 48 hours are recommended. The actual By measuring the thickness of scale, finding the
time required can vary depending on the severity length of the scaled interval over which scale is
of the deposit. Before the solvent is used in deposited, and knowing the pipe size, the
downhole well applications, well fluids should amount of scale present can be determined. The
be pumped off or displaced to minimize necessary volume of acid or scale removal
interference with the dissolving process at the solution such as LSD can then be calculated.
problem contact point. Equation 1 is for the calculation of scale volume
When the deposition of barium sulfate or on the outside of tubular goods.
strontium sulfate has been diagnosed, the most (1) V = 0.0218 t (D1 + t)
practical solution to the problem is to eliminate
the causes. For instance, barium sulfate is most Equation 2 is for the calculation of scale volume
often formed as a result of high-barium content on the inside of tubular goods.
injection water being mixed with water that (2) V = 0.0218 t (D2 – t)
contains an excess of sulfates. By isolating
these waters, the problem could be eliminated. Where
If the cause cannot be eliminated, the next most V = volume of scale in cubic
practical approach is to treat the injection water feet/linear feet.
or produced water with a scale inhibitor such as
LP-55 to help prevent the deposition of the D1 = pipe O.D. in inches
scale. D2 = pipe I.D. in inches
t = scale thickness in inches
Hydra Jet
Table 8.6 gives the theoretical quantity of 15%
HCL necessary to remove one cubic foot of
A sand laden acid or water wash pumped
various types of scale and the pounds of scale
through a properly designed jetting device will
removed by one gallon of 15% HCL.
remove all types of scale that are not subject to
chemical means of removal. Hydra Jet is Example
especially valuable in open hole injection wells.
Determine the quantity of 15% HCL necessary
Special tools are available for use in removing
to remove an iron sulfide scale having an
scale from tubing or casing.

average thickness of 3/8 inch from the outside of producing wells. The chemicals used in the
1000 feet of pipe having 3-inch O.D. Scalechek® service are three types: solid
Scalechek SCP-2 and HT and liquid Scalechek®
Solution
LP-55.
First, use equation 1 to calculate the quantity of
SCP-2 is designed to minimize the formation of
scale per linear foot.
scale in producing wells. The chemical nature
V = 0.0218 t (D1 + t) of the material allows formation water to pass
V = 0.0218 × 3/8 in. (3in. + 3/8 in.) over the polyphosphate with only a small
quantity being dissolved. This low
Change 3/8 in. to a decimal and solve for V: concentration stabilizes the scale-forming
V = 0.0218 × 0.375 × (3 + 0.375) tendency and minimizes scale deposits. SCP-2
is suitable for use in wells having bottom hole
V = 0.0275906 cubic foot per temperatures up to 200°F.
linear foot
Scalechek® treatments with SCP-2 can be
Now multiply this volume of scale times the performed with fracturing treatments by mixing
length of pipe to be cleaned to determine the the material with the first 75 % of the propping
total volume of scale to be removed. This would agent. Scale forming water flows over or filters
be: through the granular bed at formation
temperature and pressure and releases a low
ft 3
Scale Volume = 1000 ft × 0.0275906 concentration of polyphosphates. Most scales
ft such as calcium carbonate, calcium sulfate, and
= 27.5906 ft of iron sulfide scale
3
barium sulfate can successfully be controlled.
The quantity of 15% HCL necessary to remove Oil or water base solutions should be used to
iron sulfide is given in Table 8.3. Multiply the carry the SCP-2. Acids tend to cause the rapid
total volume of scale times the quantity of acid decomposition of all polyphosphates and should
necessary to remove one cubic foot of scale and not be used as a placement medium. This does
the total acid requirement is determined not mean that acid cannot be used as a
breakdown fluid, providing that an oil or water
spacer is used prior to placing the SCP-2. Wells
gallons 15% HCL which have had polyphosphates placed in them
Acid Volume = 180 3
× 27.5906 ft 3 should not be treated with acid.
ft
= 4966.308 gallons
Scalecheck® HT
Scale Inhibition
Scalechek® HT is a solid scale inhibitor
Scale removal treatments may be expensive, and designed to be placed in a fracturing treatment.
the deposition of scale might result in decreased It is placed along with the proppant as a method
production. Therefore, it is often more of inhibiting the formation of scale.
economical to prevent scale deposition before it Incompatibility between scale inhibitors and
occurs. A number of materials and techniques fracturing fluids has long been an inherent
are available to help prevent scale deposition. problem in stimulation treatments. This
incompatibility results in long or no crosslink
times due to the binding of the phosphate,
Scalechek® Scale Prevention phosphonate, or acrylic acid molecule with
Service crosslinkers such as CL-11, 18, 23, 24, and 29.
Scalechek® HT has been coated to prevent
interference with crosslinked fracturing fluids.
Scalechek® service is a process for preventing This encapsulation controls the flash release of
the deposition of scale in injection, disposal and inhibitor which affects crosslink time. The high

concentrations (flash release) of inhibitor these kinds of uses, the final concentration of
observed in produced water following squeeze LP-55 in the treated water should be 5-20 ppm
treatments are not likely to occur with (parts per million).
Scalechek® HT. This leaves a higher percentage
of Scalechek® HT in the formation to control
scale compared to squeezed inhibitors. Calchek Service
Scalechek® HT is effective in controlling calcite
(calcium carbonate (CaCO3)), gypsum (calcium Carbonate or sulfate scaling, after acidizing
sulfate (CaSO4 · 2H2O)), and barite (barium limestone formations, has been observed in areas
sulfate (BaSO4)) scales. Scalechek® HT is where the formation water contains large
effective in preventing Naturally Occurring amounts of bicarbonates or sulfates. It has been
Radioactive Material (NORM) scale that is often found that 0.1% LP-55 in the acid will help
associated with barium sulfate scale formation. prevent this secondary scaling.
Scalechek® HT is effective for temperatures of Many oil operators routinely run remedial acid
100°F and above; it has been evaluated up to treatments on their wells and follow with
275°F. inhibitor squeezes after cleaning up the treating
LP-55 is a liquid scale inhibitor containing no fluids. With the Calchek service, the producers
polyphosphates. It is used to help prevent the are able to stimulate their wells with the same
deposition of calcium carbonate, calcium sulfate, treatment at reduced cost.
and barium sulfate scales in producing and Adding LP-55 at a concentration of 0.1% will:
injection wells. It is a water soluble organic
compound that acts as a crystal poison by • aid in preventing secondary scaling
altering the structure of the particles and • aid in well cleanup
preventing growth after a crystal nucleus has
formed. • provide scale protection for short periods of
time
LP-55 is recommended only as a scale
preventer, not a scale removal compound. If long-term scale protection is desired, the LP-
Consequently, it should be used after some 55 concentration should be increased to 0.5 to
effective descaling treatment has been applied. 0.1% of the treating volume. The shut-in time
for the treating slug should be increased to allow
The most popular method of placing LP-55 in a complete spending of the acid.
well is with the Chemical Placement Technique
(CPT). The CPT nomograph (Figure 8.2) is The Calchek service treatment is intended for
used to determine the volume of water in which application in either limestone or dolomite
to mix LP-55. This is based on production rate formations.
and desired recovery time. The volume of LP-
55 to be used is then based on the expected total
water production over the recovery time. For Protex-All Inhibitor
example, if the recovery time is six months, and
the production total is 5480 bbls, the required Protex-All is a blend of LP-55 and a surface-
volume can be calculated. LP-55 is used at a active agent that forms a slowly soluble complex
concentration of 0.002 gal/bbl gives 11 gallons when placed in contact with an aqueous fluid.
of LP-55. If the CPT nomograph shows that This complex appears to have very high
4,000 gallons of water should be used, then adhesive properties on tubular goods and on
eleven gallons would be added to 4,000 gallons sandstone and limestone formations. Protex-All
of water for placement. LP-55 can be diluted provides long term protection against gypsum,
with water and lubricated down the annulus of calcium carbonate, and barium sulfate scales.
wells or through small tubing strings to treat The following types of treatments have been
water downhole. It can also be metered into performed in the field:
water going into injection or disposal wells. In

• dumping 1-5 gallons of Protex-All down the length and height of the fracture is required.
annulus and overflushing with water The effective permeability of the formation must
also be known so that the fluid loss coefficient
• placing Protex-All at a concentration of 1 can be calculated. The effective permeability
gallon/1000 in an acid or aqueous fracturing should include both matrix and fracture
fluid permeability, which is more important in
• placing 1-5 gallons of Protex-All in water limestones and dolomites rather than in
displacing this dispersion into the formation sandstones.
Protex-All is only very slightly soluble in If fracture dimensions are not available from
aqueous fluids, but is readily dispersible at low frac plans or effective permeability from logs is
concentrations. not available, then reasonable values must be
assumed. These will probably vary from one
Notice that Protex-All should be added to the area to another depending on depth, type of
aqueous carrying fluid on a continuous basis. formation, etc.
Mixing Protex-All in high concentrations with
water or an aqueous fluid will result in a mass Calculations and field evaluations indicate the
precipitation of the complex. Once this complex following treatment suggestions:
adheres to steel, it is difficult to remove. • Effective treatments can be obtained in both
propped and natural or acidized fractures.
Chemical Placement Technique • Treatments can be performed on previously
(CPT) fractured wells or along with fracturing jobs.
• Injection rates should be maintained at 1
CPT is a method of placing chemical solutions BPM or lower while placing the chemical
having high fluid loss properties into producing solutions.
formations to achieve slow feed-back with the
produced fluids. This technique can provide • No fluid loss additives should ever be
long term control of scale and paraffin incorporated into the chemical solutions.
deposition by using solutions of Scalechek LP- • The well should be left shut in for several
55 or Parachek. Emulsion breakers, corrosion hours to permit pressure to dissipate.
inhibitors, foaming agents, bactericides and
alcohols can also be placed for slow feed back. • Recovery times of 6 months to 15 months
have been achieved using LP-55 in water at
The placement of chemical solutions must be a concentration of 10 gallons/1000 gallons.
done in formations that contain natural fractures,
induced fractures that are propped, or along with It is possible to place two or more treating
a fracturing treatment. This is necessary since chemicals into a formation together. However,
the slow return of the chemicals is a result of the this requires careful selection to avoid
pressure drop profile or flow patterns that exist incompatibility. Chemicals that are highly
in a fractured formation. Injection into an adsorbed on formation rock require increased
unfractured formation will result in a fairly rapid treating levels to be effective (such as some
return of the chemicals. emulsion breakers and corrosion inhibitors).
Adsorption will not completely inactivate the
Equations have been developed which permit materials. In fact, it will probably increase the
calculation of total feed back time and also the recovery time but decrease the concentration
initial concentration of chemical being returned being returned. With corrosion inhibitors in
in the produced fluids. In order to use the sandstone formations, as much as 50% of the
equations, there are a number of things that must chemical injected in the initial treatment may
be known or assumed about the formation. never be recovered. However, on subsequent
First, the equations were developed for flow in a treatments nearly 100% will be recovered.
vertical fracture system. Knowledge of the

Figure 8.11 – CPT Nomograph

Unit I Quiz
Fill in the blanks with one or more words or select the correct answer(s) to check your progress in
Unit I.
1. Scale deposits can be found in ____________________ ____________________,
____________________, ____________________, and ____________________
____________________ .
2. Scales are classified as ____________________ ___________________, ____________________

____________________, or ____________________ ____________________.
3. Most scales appear as
______________________________________________
______________________________________________
______________________________________________
4. Which of the following fluids can be used to remove acid soluble scales? (check all that apply)
_____a) Regular Acid
_____b) Penetrating Acid
_____c) Diesel
_____d) NE Acid
_____e) Fe Acid
_____f) Xylene
_____g) MSA
_____h) Water
_____i) PAD
5. ____________________, ____________________ ____________________,

____________________ and ____________________ are chemical methods of removing acid
insoluble scales.
6. Scale formation can be inhibited with:
_____a) Scalechek LP-55 additive
_____b) SCP-2

_____c) Calchek service
_____d) Protex-All inhibitor
_____e) All of the above

Unit J: Placement Aids

During stimulation operations it is sometimes
necessary to divert the stimulation fluid. Selection of Bridging Agent
Diverting materials should bridge effectively
and be easily removed. Temporary Bridging
Agents are solids used to divert treating fluids in
Well Conditions
stimulation operations and to protect producing
zones during workover operations.
A series of temporary bridging agents have been
developed for diverting operations involving a
Temporary Bridging Agents variety of well conditions and a wide range of
temperatures. The selection of the bridging
agent and concentration is based on:
The effectiveness of a Temporary Bridging
Agent is dependent on its particle size • formation fluids contacted
distribution. TBA-110, the first water soluble,
graded (specifically sized), temporary bridging • feet of formation
agent was introduced in 1969. Early in 1970, • formation temperature
TBA-350, the first oil soluble, graded,
temporary bridging agent was introduced. The • physical properties of the formation
bridging efficiency of these graded materials • type of well completion
was readily apparent in the field when pressure
charts were studied. • placement technique
Because of the efficiency of TBA-110 (TBA-
350 is now obsolete), TLC-80, with a particle
Melting Point
size distribution to help prevent caking and to
divert effectively, has also been added to the A bridging agent should be selected that has a
inventory. softening point high enough that it does not
soften before the diverting operation has been
The graded bridging agents contain particles completed. In most treating operations, the
ranging from about 0.25 inch to 0.002 inch in treating fluid preceding the diverting material
diameter. The larger particles bridge on the cools the formation. Effective diversion may be
zone. The smaller particles successively bridge accomplished when the normal bottom hole
on larger particles until a bridge is built that has temperatures exceed the melting point of the
very little permeability. Pressure increases are bridging agent.
then sufficient to register on pressure recording
charts and show effective diversion.
Solubility
Bridging agents previously used that were
ungraded (TLC-W3, TLC-15) bridged A bridging agent should be soluble in the
effectively and probably slowed down the flow produced or injected fluid if possible. Oil
of treating fluid into the bridged zone slightly. soluble bridging agents are not used in water
However, the slow down was not enough to injection and disposal wells. Water soluble
show a pressure increase on pressure recording bridging agents should not be used in oil wells
charts and gas wells that are not making water unless
an overflush of water is used to dissolve the
agents. Otherwise, a cleanup operation should
be planned with dilute acid or brine. Some

materials will sublime (go from solid to vapor) increases the overall effectiveness of the
in gas wells at the bottom hole temperature and diverting process.
can be removed without a solvent.
Carrier Fluid
Well Completion Type
The carrier fluid is an important consideration in
The type of well completion should be diverting. It should have its specific gravity and
considered along with the physical properties of viscosity adjusted to maintain a uniform
the formation. If the formation to be bridged is dispersion of the bridging agent. The carrier
fairly homogeneous and free of vugs or fluid may be gelled or emulsified. Laboratory
fractures, consider bridging agents that are tests show that gel type carrier fluids are less
composed of smaller particles. These particles difficult for the bridging agent to hold in place
should not bridge on perforations or fractures, than emulsions. The strongest bridge is
but instead will bridge on the formation and fill probably achieved with carrier fluids having the
perforations and channeled areas behind the minimum viscosity for maintaining a uniform
casing. Such bridging agents are Matriseal O dispersion of the bridging agent. The lower
and Matriseal OWG. viscosity lets the carrier fluid continue to flow
through the bridge for a slightly longer time and
If the zone contains vugs, fractures or is
deposit more solids for a stronger, less
composed of coarse sand or gravel that will be
permeable bridge. The tail end of the carrier
difficult to bridge, a bridging agent such as
fluid should then have maximum pumpable
TLC-80, TBA-110 or FRAX-160 wax should be
viscosity so that it will not flow through the
considered. Since bridging may be achieved on
bridge and will act as a blanket. This would be
the perforations or on the formation, placement
the ideal method of application but would be
techniques must be considered.
difficult to achieve. The most practical option
would be to compromise between maximum
Placement Techniques pumpable viscosity and the viscosity necessary
to keep the bridging agent uniformly dispersed.
When the graded bridging agents (TLC-80,
TBA-110) are used, special techniques must be Concentration of Bridging
used if they are to pass the perforations and
bridge on the formation. Low concentrations of Agent
bridging agent should be used per gallon of the
carrier fluid, which must be viscous enough to The type of well completion and previous well
maintain a uniform dispersion of the solids. treatment history will help determine the
Larger volumes of carrier fluid are then quantity of solids required to form a bridge.
necessary to transport sufficient bridging agent Erosion of perforations and presence of voids,
through the perforation. vugs, and fractures are also important factors.
If you desire to bridge on perforations, a high The best volumes of both carrier fluid and
concentration of bridging agent is required in a bridging agent vary widely from area to area.
carrier fluid which has as low a viscosity as However, a general rule seems to be to use at
possible and can still transport the bridging least twice the volume of the casing covering the
agent to the perforation. interval for carrier fluid. The quantity of solids
should depend on type of diversion being
Decreasing the pump rate when the diverting attempted.
material approaches the zone is considered one
of the most important steps in correct placement Open hole completions in fractured or vuggy
techniques. This allows an initial bridge to be limestone may require 2-4 pounds of TBA-110
accomplished more easily and quickly and per gallon of carrier fluid. An open hole

completion in a highly permeable formation, zone. The data presented for bridging in open
free of fractures and vugs, may be bridged and hole, highly permeable, or lost circulation zones
sealed with 4-6 pounds of TBA-110 per square were obtained using the BB Bed test. The zones
foot of open hole surface area. Bridging on 3/8 were considered unfractured and non-vugular.
inch perforations may be achieved with ½ to 2
pounds of TBA-110/gallon of carrier fluid. The
higher concentrations will bridge more quickly, Particle Size Distribution
have less loss of carrier fluid to the formation,
and form a stronger bridge. Effectiveness of a bridging agent is dependent
The bulk density of the solids is also a factor in on its particle size distribution. The efficiency
determining the concentration to use. TLC-80 is of various bridging agents is compared in Table
used at about one-half the TBA-110 8.7. The data were obtained at 76°F using water
concentration. All TLC-80 materials available gelled with 100 pounds of WG-6 per 1000
will not bridge on a 3/8 inch perforation. gallons. The specific gravity of the water was
adjusted to maintain a uniform dispersion of the
Specific data on bridging agent concentrations bridging agent. Bridging agents were used at a
are listed in each bridging agent bulletin. The concentration of 28 pounds per gallon. The
data on the perforations were obtained without carrier fluid containing the bridging agent was
formation, or other materials surrounding the displaced with kerosene using a constant pump
casing, and would simulate bridging on rate of two BPM. The maximum pressure was
perforations in a highly fractured or vugular recorded.
Pressure Held (psi)

Fracture Width 0.10 0.13 0.16 0.20 0.24 0.32 0.40
TBA-110 1000 1000 1000 1000 1000 385 No bridge
+
TLC-15S (graded) 1000 680 685 635 485 No bridge No bridge
+
Unibeads* 340 290 234 129 65 40 No bridge
TLC-80** (Velsicol Coarse) 0 0 No bridge No bridge No bridge No bridge No bridge
Table 8.7 - Bridging Agent Efficiency
*A 1:1 blend of Unibead Buttons and Unibead Wide Range material was used.
**These materials bridged fracture widths shown to have 0 pressure buildup but did not seal. Field operations at higher pump
rates than can be achieved in the laboratory have shown that these materials will achieve some fluid control. However, they are
not expected to be nearly as effective as TBA-110, TLC-15S, TBA-350, or the 1:1 blend of Unibead materials.
+ Obsolete
Open-hole completions in fractured or vuggy • disperses readily in aqueous treating fluids

limestone may require 2-4 pounds per gallon of
carrier fluid. Bridging on perforations can be • aids in maintaining a uniform dispersion of
achieved at 0.5-2.0 pounds per gallon. the polymer
• leaves the sandstone formation water-wet
® The oil-soluble polymer is readily soluble in
MATRISEAL O
most crude oils, kerosene, diesel, and Paragon
(aromatic solvents). Its particle size has been
Matriseal® O is used for diverting treating fluids
controlled so that it passes through 20-40 mesh
in wells that have been completed with sand
sand (permeability of about 121 darcies) and
packs behind slotted liners or sand screens. It is
bridges and seals on Oklahoma #1 sand
a finely ground, oil-soluble polymer slurried in a
(permeability of about 9 darcies). Musol® A,
carrier fluid. The carrier fluid has been carefully
solvent, included in a treating placement fluid
selected to provide a pourable slurry which:
with Matriseal® O softens the Matriseal® O

diverter particles. The softened particles stick aqueous treating fluid a white precipitate forms
together and do not divert effectively. that functions as a fluid-loss additive for
diverting. The slow solubility of this precipitate
Matriseal® O diverter, compatible with LoSurf-
in water, oil, and gas enables it to divert
259 and LoSurf-300, are the preferred non-
effectively and still have good cleanup
emulsifiers for sandstone acidizing. Matriseal®
properties for all applications.
O can be dispersed in HF acid treating fluid.
The acid flows through the liner and sand pack Musol® A solvent should not be included in
and penetrates the formation. The resin carrier fluids with Matriseal® OWG. The
component of Matriseal O filters out on the face dissolution rate of Matriseal® OWG increases to
of the formation and diverts acid into areas of the extent that it will not be effective.
the formation having lower permeability.
Progressive diversion occurs and eventually
distributes acid over the zone. Temporary Bridging Agents in
The oil soluble polymer is readily soluble in Conjunction with Temblok
most crude oils and will be removed when Diverting Materials
contacted by produced crude oil. However, at
times it may be desirable to spot a hydrocarbon Temblok agents are a series of viscous fluid type
solvent (kerosene, diesel or Paragon) over the diverting materials available in several varieties
zone for rapid removal of the polymer present. to meet differing application requirements for
stimulation and work-over operations. Due to
their viscous consistency, Temblok materials
Matriseal® OWG Diverter resist flow into the formation matrix. Where
vugular or fractured zones are encountered,
Matriseal® OWG is a universal diverting granular agents such as the Temporary Bridging
material that may be used in treating or Agents may be incorporated into the Temblok
completion fluids for injection, disposal, oil and diverting materials to assist in bridging and
gas wells. Matriseal® OWG diverter has unique sealing the zone. The Bridging Agent must be
properties. It is a water clear liquid that may be insoluble in the Temblok material selected.
metered into the stream on large volume treating Table 8.8 describes the properties of various
operations, or it may be dispersed readily in the Temblok materials and compatible Temporary
treating solution when batch mixing. When Bridging Agents.
MATRISEAL® OWG is dispersed in the
Temblok Type Fluid Temblok Time and TBA additives that can be used
Temperature Stability if needed
1 180-350°F
80 Tough Water Gel TBA-110
0.2 to over 30 days
2 200-350°F
90 Tough Water Gel TBA-110, TLC-80, FRAX-160
2 to over 30 days
80-200°F
100 Tough Water Gel TBA-110, TLC-80, FRAX-160
over 30 days
Table 8.8 - Temblok/TBA Properties
1.
Should be prepared with saturated salt water for greatest 2.
Do not use Calcium brines.
stability, and to prevent dissolution of TBA-110.

Unit J Quiz
Fill in the blanks with one or more words or circle the correct answer(s) to check your progress in
Unit J.
1. The effectiveness of a Temporary Bridging Agent is dependent on its ____________________
____________________ ____________________.
2. Bridging agent type and concentration is dependent upon:
_____a) formation fluids
_____b) temperature
_____c) formation interval
_____d) type of formation
_____e) all of the above
3. When the graded bridging agents (TLC-80, TBA-110) are used, special techniques must be used if
they are to pass the perforations and bridge on the formation. ________________ concentrations of
bridging agent should be used per gallon of the carrier fluid.
4. If you desire to bridge on perforations, a ________________ concentration of bridging agent is

required in a carrier fluid which has as ________________ a viscosity as possible and can still
____________________ the bridging agent.
5. Musol® A solvent should not be included in carrier fluids with ____________________ or

____________________ because of dissolving problems.

Unit K: Job Calculations

Three common job types are:
1. Spotting to the end of the tubing or 2 3/8-in. 4.7 Tubing
packer
2. Balanced acid spot 4 1/2-in. 11.6 Casing
3. Flushing and overflushing

We shall go through an example of each.
Calculations for Spotting Acid

to the End of Tubing or Packer
In most wells, it is desirable to place as little Top of Acid
fluid on the formation as possible. Many
chemical placement designs call for the
chemical to be spotted to the end of the treating
tubing by circulating. To spot the acid or
chemical, first find the total capacity of the
tubing using the Red Book:
⎛ ft ⎞
Tubing Capacity = Depth (ft) × ⎜⎜ factor ⎟⎟
⎝ gal ⎠ Tubing Depth 6,500 ft
Then, subtract the amount of acid from the total

tubing capacity:
Flush Volume = Tubing Depth - Feet of Acid Spotted
Example:
Figure 8.12 – Acid Spotting Example
How much 2% KCL water is needed to spot 250
gal 15% HCL to the bottom of the tubing?
Solution:
gal
Tubing Capacity = 6500 ft × 0.1624 (RedBook )
ft
= 1055.6 gal
Flush Vol = 1055.6 gal − 250 gal
= 805.6 gal

2 3/8-in. 4.7 Tubing

Calculations for Balanced Acid
Spot 4 1/2-in. 11.6 Casing
Spotting a balanced acid pill may be necessary

for acid soaking and perforating applications.
The equal height (balanced height) of the acid
can be determined with the equation:
Gallons of acid to be spotted
Height =
⎛ gal gal ⎞
⎜ factor(tubing) + factor(annulus) ⎟
⎝ ft ft ⎠
To find the volume of displacement:
Feet of Tubing to Flush
= Tubing Length - Feet of Acid Spotted
Flush Volume
gal Top of Acid
= Feet of Tubing to Flush × factor(tubing)
ft
Tubing Depth 6,500 ft
Note: The ability to spotting a balance acid pill
is based on the assumption that the well fluid
and the acid are the same weight.
Example:
Find the displacement volume necessary to spot

a balance acid pill of 250 gal. Figure 8.13
Solution:
250 gal
Acid Height =
⎛ gal gal ⎞
⎜⎜ 0.4227 + 0.1624 ⎟
⎝ ft ft ⎟⎠
= 427.28 ft
Flush Height = 6500 ft - 427.28 ft = 6072.72 ft
gal
Flush Volume = 6072.7 ft × 0.1624 = 986 gal
ft

Calculations for Flush and 2 3/8- in. 4.7 Tubin g

OverFlush
4 1 /2- in. 11 .6 Casing
It is a standard practice to flush more than the
volume of tubing after pumping acid. This
ensures that:
• any acid that is not spent can continue to
penetrate the formation
• there is no live acid in the tubing to
cause corrosion
• any secondary precipitates that could
form from the acid reaction are
displaced as far into the formation as
possible
Acid flush volume calculations are done from
the bottom of the perforations or open hole
section. So:
Vol to Pump = Tubing Volume Tubing Depth 6,500 ft

+ Casing Volume to the Bottom Perf
+ Overflush Volume Top Perf 6,700 ft
Example: Bot tom Perf 6,8 00 f t
Calculate the volume needed to overflush an

acid job by 1 barrel per foot of perforations. Figure 8.14
Solution:
gal
Tubing Vol = 6500 ft × 0.1624 = 1005.60 gal
ft
gal
Casing Vol = 300 ft × 0.6528 = 195.84 gal
ft
bbl 42 gal
Overflush = 1 × × 100 ft
ft of perfs bbl
= 4200 gal
Vol to Pump = 1005.6 gal + 195.84 gal + 4200 gal
= 5401.44 gal

Unit Quiz K:
1. Well Information:
Casing – 5.5, 23 lb/ft L-55 to 10,200 ft
Tubing – 2-7/8”, 6.5 lb/ft N-80 with a packer set at 9,850 ft
Perforations – 10,030 – 10, 050 ft
Calculate the displacement necessary to spot 2000 gallons of 10% FE acid to the end of the tubing.
2. Well Information:
Casing – 5-1/2”, 15.5 lb/ft N-80 to 9,500 ft
Tubing – 2-7/8” 6.5 lb/ft N-80 to 8,500 ft
Perforations – 8,500 – 8,550
Assumption: Hole is full of a uniform weight of fluid.
Calculate the volume of flush necessary to set a balanced spot of acid at the top of the perforations.

Self-Check Test for Section 8: Chemical Stimulation

Mark the single best answer to the following questions.
1. ______ True ______ False The major acids used in chemical stimulation are HCL and HF.
2. ______ True ______ False Commercially available HCL can be 20 °Be or 22 °Be.
3. ____________________________ acid is the only acid that will not damage chrome.
4. Check what procedures to observe when working with acid.
_____a. wear goggles
_____b. have sodium bicarbonate available
_____c. wash eyes with strong water jet
_____d. smoke around acid tanks
_____e. add acid to water
5. If you have 22°Be acid, how much acid and water are required for 750 gallons of 7% HCL?
__________ gal acid
__________ gal water
6. ______ True ______ False Inhibitors decrease the corrosion rate of acid on steel pipe.
7. ______ True ______ False Halliburton corrosion inhibitors will protect metals other than steel,
such as aluminum and magnesium.
8. ______ True ______ False Matrix acidizing is done at rates and pressures below fracturing
pressure.
9. Emulsion break tests are run with ___________________ ___________________ and
____________________ _______________________. Complete separation of oil and acid in
_____________________ to _____________________ minutes is desirable.
10. ______ True ______ False HF Acid is used to dissolve limestone out of a sandstone formation.
11. ______ True ______ False HF Acid’s rate of spending is constant; it never changes.
12. The major retarded HF system Halliburton offers is:
_____a. Sandstone Acid
_____b. FE
_____c. ClaySol
_____d. ClayFix
_____e. Fines Control Acid
13. ______ True ______ False HF Acid can react with limestone to form an insoluble precipitate.
14. ______ True ______ False Spent HF Acid can react with sodium and potassium to form more
HF acid.
15. Damage to a formation results when invasion of which of the following occurs?

a. ______ Clay
b. ______ Whole mud
c. ______ Filtrate
d. ______ All of the above
16. ______ True ______ False If the formation is limestone, mud damage can be removed with HCL
or HF.
17. The cloud point of an oil is __________________________________________________.
18. The pour point of an oil is ___________________________________________________.
19. Paraffin can be removed ____________________, ______________________, and with
____________________.
20. Scales are classified as __________________ _________________ or _______________
________________.
21. List three methods of removing acid insoluble scales.
________________________________________________
________________________________________________
________________________________________________
22. What are two products used for scale inhibition?
______________________
______________________
23. ______ True ______ False Particle size determines how effective TBA agents are.
24. ______ True ______ False TBA products should be insoluble in formation fluids.
25. TBA agents can be placed using
a. ______ acids
b. ______ emulsions
c. ______ gels
d. ______ Temblok
e. ______ all of the above

Answer Key
Items from Unit A Quiz
1. hydrochloric, hydrofluoric, organic
2. damage removal / matrix / fracture
3. 20 / 31.45
4. sandstone
5. Formic / acetic
6. acetic
Items from Unit B Quiz

1. Goggles
2. sodium bicarbonate
3. skin / eyes
4. hydrogen gas
5. water / acid
6. dust mask
Items from Unit C Quiz

1. 1843
2. 2050 / gallons / water / 6620 / carbon dioxide
3. 1020
4. 288 acid / 712 gal water
Items from Unit D Quiz

1. temperature, time of contact, type of acid, pressure, type of steel, ratio of volume of acid to exposed
steel surface area.
2. Ff.)
3. HII 124 / HHII 500
4. Ff.)
5. 0.05
6. Organic
Items from Unit E

1. skin

2. fracturing
3. collapse / coning / scaling
4. fracture acidizing
5. preflushes / cool
6. F
7. b
8. c
9. sustained – production acidizing
Items from Unit F

1. a, c
2. e
3. physical and chemical composition of the formation, temperature, surface area of rock exposed to a
particular volume of acid, concentration of excess hydrochloric acid
4. Clayfix
5. hydrocarbons / invasion / emulsions
6. Fines Removal Acid
Items from Unit G Quiz

1. filtrate / clay / whole mud
2. Acid / Mud flush
3. F
4. Oil External Emulsions / True Oil Base
5. N-Ver-Sperse A / N-Ver-Sperse O
Items from Unit H Quiz

1. T
2. F
3. temperature / solution
4. temperature / flow
5. The alternate coating of the pipe and draining of the oil, The presence of only a film of oil in contact
with the pipe while the well is flowing oil through water zones, Rough pipe surface, Electrical charger
on various materials in the crude oil, Temperature drop
6. F
7. Mechanical equipment, Solvents which dissolve the deposits, Heat, which melts the wax and reduces
it to a liquid so that it can be easily removed
8. Crystal modifiers
9. Targon II / Tarchek

Items from Unit I Quiz

1. Flow liner / tubing / perforations / formation face
2. water soluble / acid soluble / acid insoluble
3. Thin sealer or popcorn like laminated deposits crystalline deposits
4. a, b, d, e, g, i
5. GYPSOL, Liquid Scale Disintegrator, BaSo4lvent
6. e
Items from Unit J Quiz

1. particle size distribution
2. e.)
3. formation
4. high / low / transport
5. Matriseal OWG / Matriseal O
Items from Unit K Quiz

gal
Tubing Capacity = 9850 ft × .2431 = 2394.54 gal
1. ft
Flush Volume = 2394.54 gal - 2000 gal = 394.54 gal
gal gal
factor for 2 - 7/8" tubing = 0.2431
ft ft
gal gal
factor for 5 - 7/8" casing = 0.6625
ft ft
2. 500 gal
Acid Height = = 552.12 ft
⎛ gal gal ⎞
⎜ 0.2431 + 0.6625 ⎟
⎝ ft ft ⎠
gal
Flush Vol = (8500 ft - 552.12 ft ) × 0.2431 = 1932.13 gal
ft

Self Check Test

1. T
2. T
3. Acetic
4. a, b, e
5. 175 acid / 825 water
6. T
7. F
8. T
9. produced fluid / treating solution / ten / fifteen
10. F
11. F
12. e
13. T
14. F
15. d
16. F
17. the cloud point is the temperature where paraffin begins to come out of solution.
18. Pour point is the temperature where oil will not flow when tilted to a horizontal position
19. mechanically /, solvents which dissolve paraffin, / heat which melts the way and reduces it to a liquid
20. water soluble /, acid soluble /, acid insoluble
21. GypsolYPSOOL, Liquid Sacle Disintegrator, BaSO4lvent
22. SCP-2 / Scalecheck, LP-55
23. T
24. F
25. e

Section 8 - Chemical Stimulation

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Section 8 - Chemical Stimulation

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© 2005, Halliburton 8•1 Stimulation I

Formation Conditioning....................................................................................................................... 8-26

© 2005, Halliburton 8•2 Stimulation I

Scalechek® Scale Prevention Service................................................................................................... 8-53

© 2005, Halliburton 8•3 Stimulation I

Use for Section notes…

© 2005, Halliburton 8•4 Stimulation I

© 2005, Halliburton 8•5 Stimulation I

Unit A: Types of Acids

© 2005, Halliburton 8•6 Stimulation I

3. Commercially available hydrochloric acid is standardized at __________ °Be or __________%.

5. Two organic acids commonly used are ____________________ and ____________________.

© 2005, Halliburton 8•7 Stimulation I

© 2005, Halliburton 8•8 Stimulation I

4. The possible presence of ____________________ ____________________ is one reason smoking is

6. Wear a ____________________ ____________________ when handling powders.

© 2005, Halliburton 8•9 Stimulation I

Unit C: Reactions of Hydrochloric Acid

© 2005, Halliburton 8 • 10 Stimulation I

Gals 22°Be Acid & Gals 20°Be

© 2005, Halliburton 8 • 11 Stimulation I

© 2005, Halliburton 8 • 12 Stimulation I

Unit D: Corrosion Inhibitors

© 2005, Halliburton 8 • 13 Stimulation I

MSA Inhibitors procedures for MSA-II inhibitor are the same as

© 2005, Halliburton 8 • 14 Stimulation I

2. ______ True ______ False Inhibitors will stop corrosion.

3. Above 275° F, secondary components such as ____________________ and ____________________

6. MSA Inhibitor is required when you use ____________________ acids.

Now, look up the suggested answers in the Answer Key.

© 2005, Halliburton 8 • 15 Stimulation I

Unit E: Carbonate Acidizing

Matrix Acidizing WELLBORE

© 2005, Halliburton 8 • 16 Stimulation I

help ensure that a greater percentage of the Fracture Acidizing

© 2005, Halliburton 8 • 17 Stimulation I

Figure 8.3 - Acid Treatment Decision Flowchart

© 2005, Halliburton 8 • 18 Stimulation I

© 2005, Halliburton 8 • 19 Stimulation I

Carbonate Stimulation Acid Zonal Coverage Acid

© 2005, Halliburton 8 • 20 Stimulation I

Carbonate Emulsion Acid Hot Rock Acid

Fines Recovery Acid (FRA) is an energized acid Additional Reference

© 2005, Halliburton 8 • 21 Stimulation I

SUPRA FLC (Fluid-Loss Control)

SUPRA FLC controls acid fluid-loss in induced

© 2005, Halliburton 8 • 22 Stimulation I

Figure 8.6 - Fracture-Acidizing Process

© 2005, Halliburton 8 • 23 Stimulation I

5. One method of obtaining slower reaction rates is to use water _____________________ to

_____ a) Carbonate Stimulation Acid

_____ b) Carbonate Completion Acid

_____c) Zonal Coverage Acid

_____d) Carbonate Emulsion Acid

8. Which acid system uses a crosslinked gel to control leakoff?

_____a) Carbonate Stimulation Acid

_____b) Carbonate Completion Acid

_____c) Zonal Coverage Acid

_____d) Carbonate Emulsion Acid

9. What does SUPRA stand for?

Now, look up the suggested answers in the Answer Key.

© 2005, Halliburton 8 • 24 Stimulation I

Unit F: Sandstone Acidizing

3. Commercially available hydrochloric acid is standardized at °Be or %.

5. Two organic acids commonly used are and .

4. The possible presence of is one reason smoking is

6. Wear a when handling powders.

2. True False Inhibitors will stop corrosion.

3. Above 275° F, secondary components such as and