Professional Documents
Culture Documents
Acidizing Treatments
Table of Contents
Section 1: Introduction and Safety
Overview............................................................................................................................................ 1-1
Safety .................................................................................................................................................1-2
Hydrogen Chloride (HCl) Acid Safety .........................................................................................1-2
Hydrogen Fluoride (HF) Acid Safety ........................................................................................... 1-3
Hydrogen Sulfide (H2S) Safety .................................................................................................... 1-4
Emergency-Spill Procedure for Acid............................................................................................ 1-5
Section 2: On-Site Quality Assurance Standards for Acidizing Treatments
Overview............................................................................................................................................ 2-1
Pre-Mobilization Preparation............................................................................................................. 2-1
Job Preparation .................................................................................................................................. 2-4
During-Job Requirements .................................................................................................................. 2-8
Post-Job Requirements ...................................................................................................................... 2-9
Section 3: Acidizing Treatment Laboratory Procedures
Overview............................................................................................................................................ 3-1
Sampling Chemicals/Water ............................................................................................................... 3-2
Measuring Temperature ..................................................................................................................... 3-3
Measuring Specific Gravity ............................................................................................................... 3-4
Measuring pH .................................................................................................................................... 3-5
Acid-Strength Test.............................................................................................................................3-6
Additive Solubility/Dispersibility Test............................................................................................ 3-10
Blend-Compatibility Test ................................................................................................................ 3-11
Emulsion Break Test........................................................................................................................ 3-13
Sludge Test ......................................................................................................................................3-15
March 2009
Table of Contents
ii
Table of Contents
March 2009
SECTION
Section
Preface
March 2009
1-1
Safety
Hydrogen Chloride (HCl) Acid Safety
Introduction
HCl acid can cause eye, skin, and respiratory burns, and it is harmful if swallowed.
Personal Protection Equipment (PPE)
Engineering Controls: Use in a well-ventilated area. Local exhaust ventilation should be used in
areas without good cross ventilation.
Skin Protection: Use full protective chemical-resistant clothing and rubber boots. (See Appendix
A).
Eye Protection: Wear chemical goggles and also a face shield if a splashing hazard exists.
Other Precautions: Eyewash fountains and safety showers must be easily accessible.
Note
See Appendix A for proper PPE selection. Select the PPE for the most stringent
chemical exposure situation.
Inhalation: If inhaled, remove victim to fresh air. If victim is not breathing, give artificial
respiration, preferably mouth-to-mouth. If breathing is difficult, give oxygen. Get medical
attention.
Skin: In case of contact, immediately flush skin with plenty of soap and water for at least 15
minutes. Get medical attention. Remove contaminated clothing. Clothes contaminated with
chemicals should be thoroughly washed before wearing them again.
Note
Eyes: In case of contact or suspected contact, immediately flush eyes with plenty of water for at
least 15 minutes. Keep a premixed solution of 1 tsp of soda (sodium bicarbonate) and 1 pt of water
to flush the eyes. Get medical attention immediately.
Note
1-2
When washing eyes, use a gentle flow of water when rinsing. A heavy stream of water
could damage the eyes. DO NOT use dry soda in the eyes.
Ingestion: Do not induce vomiting. Slowly dilute with 1 to 2 glasses of water or milk and seek
medical attention. Never give anything by mouth to an unconscious person.
March 2009
Engineering Controls: Use in a well-ventilated area. Local exhaust ventilation should be used in
areas without good cross ventilation.
Skin Protection: Use full protective chemical-resistant clothing and rubber boots. (See Appendix
A).
Eye Protection: Wear chemical goggles and also a face shield if a splashing hazard exists.
Other Precautions: Eyewash fountains and safety showers must be easily accessible. Calciumgluconate gel should be available on location.
Note
See Appendix A for proper PPE selection. Select the PPE for the most stringent
chemical exposure situation.
Skin: Skin contact with HF can cause severe burns. In case of contact, follow this procedure:
1. Remove the victim to a safe location. Use PPE when handling a contaminated victim.
2. Immediately flush the exposed skin with plenty of soap and water for at least 15 minutes. It is
critical to apply antidote as soon as possible.
3. Remove contaminated clothing while flushing exposed skin. Cut away clothing, if necessary,
to avoid injuring affected skin.
4. After adequate 15-minute rinsing, apply 2.5% calcium-gluconate gel to the skin gently and
freely. While wearing gloves, aggressively massage the gel into the affected area and continue
to reapply and massage until pain is entirely relieved. If medical assistance is delayed, apply gel
every 15 minutes until pain and/or redness disappear, or until the emergency rescue team
arrives. Get medical attention.
Note
Calcium gluconate is a topical gel used for treating HF-acid burns to the body. The
immediate use of calcium-gluconate gel can be extremely beneficial in reducing burn
damage to bone and deep tissue, and it can help relieve pain almost immediately.
Eyes: HF acid can cause severe eye burns, resulting in destruction or opacification of the cornea.
Blindness can result from severe or untreated exposures. Immediate first aid is necessary.
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1-3
Inhalation: HF acid produces pungent fumes on contact with air. These fumes can cause severe
problems if inhaled. If fumes are inhaled, remove the victim to fresh air. If the victim is not
breathing, give artificial respiration, preferably mouth-to-mouth. If breathing is difficult, give
oxygen. Get medical attention.
Ingestion: Do not induce vomiting. Slowly dilute with 1 to 2 glasses of water or milk and seek
medical attention. Never give anything by mouth to an unconscious person.
Important
Do not store samples of HF acid in glass jars/beakers. Always use plastic. Proper PPE
must be worn by all personnel when handling HF acid.
Other Precautions: Eyewash fountains and safety showers must be easily accessible.
Inhalation: If inhaled, quickly remove the victim to fresh air (rescuers must be careful). If the
victim is not breathing, give artificial respiration, preferably mouth-to-mouth. Get medical
attention.
Skin: In case of contact, immediately flush skin with plenty of soap and water for at least 15
minutes. Get medical attention. Remove contaminated clothing and thoroughly wash clothes before
reuse.
Eyes: In case of contact or suspected contact, immediately flush eyes with plenty of water for at
least 15 minutes and seek medical attention immediately after flushing.
1-4
March 2009
Warning
Important
The only way to determine the amount of H2S present is to test with an approved H2S
detector. Do not rely solely on sense of smell.
Note
After an acid spill is observed, the level of response required depends on the severity of the incident,
which should initially be assessed by the person discovering the spill and then communicated to the field
supervisor.
All acid spills have the potential to harm human health and the environment. Care should be taken at all
stages to ensure that:
Spill Management
When preparing the JSA, remember to consider these steps to follow in the event of spill on location:
1. The reporting procedure needs to be clearly identified, including emergency contact telephone
numbers and reporting to higher management. Also, be aware of the customer requirements.
2. Secure your own safety first. Inform all personnel in the area and evacuate nonessential persons
from the spill area.
3. Barricade the area with barrier tape to prevent traffic (people or equipment) from going through the
spill area.
4. If you are qualified and trained, assess the spill type (minor or major) by identifying the material
spilled (check the container label), and then approximate the quantity spilled.
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1-5
5. Check the label on the container and identify any hazardous properties of the chemical (hazard
symbol, risk phrases, and safety phrases). Make sure MSDS is available and refer to the MSDS for
details.
6. Identify appropriate PPE to protect you from exposure to the chemical and wear required PPE.
7. Contain and neutralize the spill.
a. Spill containment.
i. Stop the source of the spill by shutting valves or temporarily plugging any holes (if this
can be done safely).
ii. Prevent the spill from contaminating surface/water drains if they can be safely accessed.
iii. Use sand or soda ash/sodium bicarbonate to form a bund around the spill to limit it from
spreading before attempting to neutralize.
b. Spill neutralization.
i. Once the spill is contained, neutralize the spill using a reasonable quantity of soda
ash/sodium bicarbonate. Use the information in Table 1.1 as a guideline for the required
amount of agent needed to neutralize the acid.
Warning
1-6
March 2009
Sodium
Bicarbonate
(K-34
Breaker), lb
Calcium
Carbonate
(Limestone),
lb
122
193
115
245
388
231
369
584
348
494
783
466
620
983
586
748
1,186
706
7.5
942
1,492
889
1,007
1,596
951
1,139
1,805
1,075
10
1,271
2,015
1,200
11
1,405
2,227
1,327
12
1,540
2,441
1,454
13
1,676
2,657
1,582
14
1,814
2,874
1,712
15
1,952
3,094
1,843
16
2,092
3,316
1,975
17
2,233
3,539
2,108
% HCl Acid
Strength
ii. Ensure plenty of water is available to dilute acid remaining in tanks, to dilute spills, or
to flush lines of acid.
8. If any solid waste is left once the spill has been contained and neutralized, transfer the solid waste
to a suitable waste container. Clearly label the waste container with the identity of the spilled chemical and the appropriate hazard warning (e.g. corrosive).
9. Arrange for the collection and disposal of the waste through the person responsible for waste management.
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1-7
1-8
March 2009
SECTION
Section
12
Preface
Pre-Mobilization Preparation
Equipment Testing
Check all the equipment (acid tank, batch mixer, pump-tank lining, acid transport-trailer, etc.)
Inspect hoses carefully. Ensure that appropriate hose is being used for the job (usually Parker
Polyflex hose is used for acid jobs).
Tank Lining: Tank linings are essential when transporting corrosive chemicals, such as acid.
Linings increase the life of the tank and help to ensure the chemical's integrity. A brief
description of various tank linings is given below:
TNEMEC (vinyl ester coating) Lining: Contains Derakane resins (primer coat is Derakane
8084 and topcoat is Derakane 470). This lining is especially suited for HCl acid transport. It
is not compatible with solvents, such as xylene.
Note
These tanks should not be used for storing chemicals. They are only intended for
transporting of chemicals.
March 2009
2-1
Polyethylene: This lining is suitable for almost all chemicals that Halliburton pumps. However,
some chemicals (especially solvents, such as xylene) will permeate and absorb into the
polyethylene. This absorption does not degrade the liner, but will cause some swelling and
possibly contamination.
Natural Rubber: This lining should be used for tanks that are used only for storing
concentrations of HCl acid without additives.
Important
Note
If a natural-rubber-lined tank is left empty for more than one month, it should
be filled with a weak salt solution or purged with nitrogen. Air (ozone) will
prematurely deteriorate the liner.
Recommendations
Use the following reference to help determine the compatibility of a tank lining
with particular acid systems:
http://halworld.corp.halliburton.com/HES/HESMFG/HESMFG_Catalog/HE
SMFG_Catalog_content/HESMFG_Catalog_pe/PE1D2/Chemical%20Comp
atibility.asp
Raw-Acid Testing
The raw-acid supplier should provide acid that meets the Halliburton specifications given in Table 2.1.
The Halliburton field lab will not be able to cross-check all of the components listed in the table. At a
minimum, the density and raw-acid strength should be confirmed before a batch of acid is accepted. The
procedure for determining acid strength and specific gravity is provided in Section 3.
Raw-acid strength can also be checked before a blend is mixed.
2-2
March 2009
Note
Components
Maximum Allowable
Concentration, ppm
Sulfate
400
Iron
20
Fluorides
25
Sulfites
100
Arsenic
Copper
Organic chlorides
Acid suppliers must provide acid that meets these specifications. If the acid does not
meet these specifications, the supplier needs permission from Halliburton before
attempting to deliver.
Pre-Job Inventory
Before beginning a job, prepare a list of the chemicals/additives required for the job.
All of these chemicals/additives must be documented by strap reading, and the results should be
recorded on the Inventory QC Form in Appendix B.
March 2009
2-3
Job Preparation
General Mixing Guidelines
When mixing acid blends, the general guideline for the order of addition is as follows:
1. Water
2. Dispersant and/or mutual solvents
3. Corrosion inhibitor
4. Acid
5. Surfactant/ nonemulsifier/ antisludge agent
6. Iron-control additives
Important
Important
Mixing until the solution is homogeneous is essential after the addition of each
chemical. Failure to do so will not always result in a problem, but will certainly
improve the chances of a problem occurring. Note: "Roading" the acid is not
sufficient to ensure a uniform solution.
Important
Iron-control chemicals in water will invariably lead to precipitates; therefore, ironcontrol additives should be added after the addition of the acid.
It is recommended that iron-reducing agents (FDP-S769-05 and Fe-5A
iron-reducing agent) be added immediately before pumping downhole or on-the-fly.
These agents react with oxygen and become ineffective. Limit the contact with
entrained air or dissolved oxygen as much as possible.
Iron-chelating agents (Fe-2 buffering agent) or pH-control agents (Fe-1A) can be
added at any time during the process. Either could be added before the HCl acid is
added but after the corrosion inhibitor has been added to the water.
Important
Consult the appropriate Technology Bulletin for the order of addition for specific
intensifiers (such as HII-500M, HII-600, HII-124C, and HII-124T
corrosion-inhibitor intensifiers, etc.).
Note
The mixing procedures for gelled-acid and emulsified-acid systems are provided in
Section 4.
Note
The order of addition above should be followed in all cases unless blend-specific
mixing procedures have been developed or lab testing has determined alternative
requirements.
2-4
March 2009
Source-Water Analysis
Source water is tested to ensure that it is acceptable for use in an acidizing job. Source-water analysis
detects the presence of components that can alter fluid properties and, therefore, might affect the job. Test
source water for pH, iron, and sulphates.
As many factors are involved, it is not always possible to set a specific limit on each component. Table
2.2 lists maximum limits for few parameters. However, these limits should not replace sound chemical
or engineering principles.
Note
Amount
Iron (Fe)
10 ppm
Sulfate (SO4-2)
400 ppm
pH
5.0 to 10.0
Excess amounts of sulfate can cause scaling issues once the acid spends.
Excess amounts of iron can result in iron-hydroxide precipitation once the acid spends above a pH
of about 3.5.
Note
Note
March 2009
2-5
Seawater in Sandstones
Seawater cannot be used within any stage of an HF acidizing treatment (Sandstone 2000
acidizing service treatments), and it cannot be used as a non-acid pre-flush or over-flush fluid
because the sodium/potassium in the seawater can cause serious precipitation problems.
Seawater should not be used in any acid blend intended for use in a sandstone formation where the
precipitation of calcium sulfate would be unacceptable. Seawater contains about 2,700 ppm of
sulfate, which will almost completely precipitate as calcium sulfate as the acid spends on small
amounts of carbonate in the matrix. The total calcium sulfate being precipitated will only be about
30 lb/Mgal. So, if an acid wash uses 50gal/ft, then only 1.5 lb of precipitation will occur per foot of
interval. If this is too much for the customer, then seawater should not be used to prepare the acid.
Important
Water not conforming to guidelines must be tested for compatibility with the acid
blends and reservoir fluids. If necessary, a different water source should be
considered.
Fluid Testing
After-Blend Preparation
Blend-Acid Strength Test: This test is necessary to ensure that the strength of the acid blend is
correct before it is pumped downhole. Determine the blend-acid strength for a sample from each
acid tank.
Additive Solubility/Dispersibility Test: This test ensures that all of the additives in an acid blend
are compatible and there is no additive separation or precipitation.
Blend Compatibility Test: Blend compatibility testing determines the most effective combination
of additives and the concentration of those additives needed to help prevent incompatibilities with
formation, wellbore treatment, and workover fluids.
Emulsion Break Test: The emulsion break test determines the most effective surfactant and
necessary concentration of the surfactant to help prevent stable emulsions from forming between
the acid fluids and crude oil from the treated formation. Emulsion break tests should be run before
the job begins.
Sludge Test: This test ensures that the live-acid blends are compatible with the formation crude and
that no sludge is formed. This test determines if antisludging agents will be required in case of
sludge formation.
Note
For gelled-acid systems, test a sample from each tank for viscosity and pH.
For emulsified-acid systems, tests should be conducted to check the stability of the
emulsion at surface temperature and BHST.
2-6
March 2009
pH
Temperature
Acid strength
Specific gravity
Note
For gelled-acid systems, test a sample from each tank for viscosity and pH.
For emulsified-acid systems, check the stability of the emulsion.
Review all pre-job test results with the customer, the service supervisor, and the engineer. Conduct this
review before attending the health, safety, and environmental (HSE) safety meeting.
Note
Tubular Cleanup/Pickling
Before the treatment, the casing, tubing, and workstring should be completely free of rust, dirt, mill scale,
and any other fines-generating debris. Failure to clean the tubulars could lead to losses of reactive acidstimulation fluid because of spending in the pipe. A basic 15% HCl inhibited-acid is typically used to
pickle tubulars to help prevent carrying mill scale and/or precipitating iron hydroxides into the formation
with the main acid.
Tubular Cleanup Recommendations
Use xylene with 1% mutual solvent to remove any pipe dope or hydrocarbon deposits.
Dope Buster M pipe dope remover solvent and BaraScrub casing wash (Baroid product) can be
used to remove pipe dopes. Dope Buster M solvent is a direct replacement for xylene. Refer to the
technical bulletin for more information:
http://halworld.corp.halliburton.com/internal/PS/pe/contents/Best_Practices/web/
A_through_G/DopebusterM_Solvent.html
Use 15% HCl acid containing inhibitor, surfactants, and iron-control additives. This fluid system
can be used to help remove mill-scale (magnetite), rust, or scales from inside tubulars.
Note
The surfactants and iron-control additives can be omitted if the perforations have not
been shot before the pickling treatment.
Acid/tubing contact time should be 45 to 60 minutes for reasonable cleaning. (This is the total time
that the acid will be in contact with the pipe, not the time that it will be in contact with any particular
section of the pipe).
March 2009
2-7
The amount of fluid used depends on the tubular size. Table 2.3 lists the recommended volumes for
pickling a tubular with 15% HCl acid.
Table 2.3Recommended Volume for Pickling a Tubular with 15% HCl Acid
Size of Tubular,
in.
2 3/8
85
2 7/8
110
3 1/2
140
4 1/2
190
5 1/2
240
310
Important The listed volume is required to make sure that enough HCl is present to dissolve all
of the mill scale. The contact time is necessary to make sure that the acid has time to
dissolve the mill scale.
Note
These recommendations apply to carbon steel/standard steel and are not applicable
for exotic steel. For information on exotic steel, contact the Duncan Technology
Center (DTC).
During-Job Requirements
During the treatment, test for pH, specific gravity, and acid strength. Record all test results on the
During-Job QC form in Appendix B.
Note
2-8
For gelled-acid systems, test samples for viscosity and pH at regular intervals.
Real Time Monitoring: Rate, pressure, and density must be displayed and recorded during the job.
Note
Do not dispose of the samples collected during the job until the job has been
completed and approved by the customer.
Note
March 2009
Post-Job Requirements
Post-Job Neutralization
Once the job is completed, all equipment/tanks should be properly rinsed before moving them from
location to field camp. Sodium-carbonate/sodium-bicarbonate solution should be used to rinse
equipment/tanks, using the following procedure:
1. Neutralize the remaining acid in the tank using the appropriate quantity of soda ash/sodium
bicarbonate. Refer to the Table 1.1 for detailed information about the quantity required to neutralize
the acid.
2. After removing neutralized acid from the tank, add at least 10 bbl of water and 15 to 20 kg of sodium
carbonate to neutralize the tank. This should be done at the job location if possible. Drain rinsate as
per the requirements of the location.
3. If the tank is not rinsed on location, then on arrival at the field camp rinse the inside surfaces of the
tank with water and drain the tank in an approved location, as indicated by HSE personnel.
4. Leave drain valves open and rinse for 15 minutes.
5. Check the pH of the water; the pH of the drain water should be greater than 5 and less than 10. If it
is not, continue rinsing until the required pH range is observed.
6. Leave the drain valve and top hatch open.
Sampling Returns
The collection procedure is based on a percentage of total treating volume (TTV):
1. Collect five samples (every 5% of TTV until 25% recovery).
2. Collect five samples (every 10% of TTV until 75% recovery).
3. Collect six samples (every 25% of TTV until 200% recovery).
The cumulative water production and time of collection should be recorded for each sample
Post-Job Report
Immediately after completing the main treatment, compile treatment graphs and outputs and present them
to the customer with a job summary. The report should cover the following points:
Executive summary
Well information
Pumping schedule
Stage summary
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2-9
Appendix/attachments
2-10
March 2009
SECTION
Section
13
Preface
Always refer to Appendix A for proper PPE selection while handling any
chemical. Select the PPE for the most stringent chemical exposure situation.
March 2009
3-1
Sampling Chemicals/Water
Scope: To obtain samples for QC testing.
Required Equipment
PPE: Face shield, gloves (refer to Appendix A), coveralls (refer to Appendix A), safety glasses,
rubber boots, and a hard hat.
Labels
Permanent marker
Procedure
Use the following procedure to obtain a chemical sample for QC testing:
1. Determine whether one sample or a composite of several samples is required.
2. Label a clean, dry sample bottle with the following information:
Sample number/tank number
Chemical name
Date
3. Thoroughly agitate, aerate, or stir the liquid in the tank.
4. Collect sample using sampling device.
Note
3-2
Do not use samples from roll lines, manifolds, and hoses. They might not be
representative of the entire fluid volume.
March 2009
Measuring Temperature
Scope: To determine the temperature of the acid/fluid system.
Required Equipment
PPE: Face shield, gloves (refer to Appendix A), coveralls (refer to Appendix A), safety glasses,
rubber boots, and a hard hat
Thermometer
Procedure
1. Collect the sample.
2. Immediately after collecting the sample, insert a clean, dry, calibrated temperature probe in the fluid
sample without allowing the probe to touch the sample bottle.
3. After the reading is stabilized, note the temperature.
March 2009
3-3
Required Equipment
PPE: Face shield, gloves (heat-resistant gloves might be required; refer to Appendix A), coveralls
(refer to Appendix A), safety glasses, rubber boots, and a hard hat
Procedure
1. Place a sufficient volume of the sample in a transparent container so that a hydrometer can float
freely within the container without touching the sides.
2. Twirl the hydrometer in the sample, making sure it does not touch the sides of the container.
3. After the hydrometer stops twirling, read the scale to the nearest figure at the bottom of the meniscus and note the reading.
4. Clean the hydrometer.
3-4
March 2009
Measuring pH
Scope: To measure the pH of the acid system using a pH meter and pH paper.
Required Equipment
PPE: Face shield, gloves (refer to Appendix A), coveralls (refer to Appendix A), safety glasses,
rubber boots, and a hard hat
Portable pH meter
pH probe
Narrow-range pH paper
Buffers
ProcedureUsing pH Meter
1. Ensure that the probe is clean and has been pre-soaked according to the instructions for that probe.
2. Rinse the probe with deionized water.
3. Following the manufacturers' specifications, calibrate the probe and pH meter for two pH values
that span the expected pH range to be measured.
4. Place the probe into the fluid.
5. Allow the pH reading to stabilize and note the reading.
6. Rinse and clean the probe with deionized water.
7. Place the probe in the correct storage container.
ProcedureUsing pH Paper
1. Immerse the paper strip in the fluid sample until the color stabilizes.
2. Compare the color of the paper strip with the color chart and note the reading.
Note
March 2009
Samples that are cooler or have a higher ionic strength will delay reading times.
3-5
Acid-Strength Test
Scope: To determine the concentration of an acid system.
PPE: Face shield, gloves (refer to Appendix A), coveralls (refer to Appendix A), safety glasses,
rubber boots, and a hard hat.
Procedure
Before performing the acid-strength test, the following two solutions must be prepared:
Standard NaOH solution
Mixed indicator solution
3-6
March 2009
c.
Titrate the KHP mixture with the NaOH solution until the color changes.
d.
If desired, 0.200-N NaOH can be used instead of the solution standardized above.
0.200-N NaOH is inexpensive, already standardized, and readily available from
several suppliers of laboratory chemicals.
Do not allow the standard NaOH solution to contact air (replace the cap on the bottle
as soon as the solution has been removed). CO2 in the air will react with the NaOH,
lowering its activity. If the normality of the NaOH is suspect, re-standardize it against
KHP or discard it.
Caution
Use plastic flasks and pipettes when handling samples containing HF acid
because the HF acid will react with glass. Use extreme caution when handling
HF acid because it can penetrate the skin and react with the calcium in bones.
In large doses, exposure to HF acid can be fatal.
Important
March 2009
3-7
After preparing these two solutions, the main procedure for testing acid strength can begin.
Procedure for Acid Strength Test
1. Filter the acid sample that has a concentration to be determined through the Whatman filter paper.
2. Pipette a 1-mL aliquot of the filtered sample into each of the two Erlenmeyer flasks. The sample
size should increase to 3.00 mL or 5.00 mL if the acid content is suspected to be low.
3. Add 50 mL of deionized water to each Erlenmeyer flask.
4. Add 3 to 5 drops of mixed indicator solution to each Erlenmeyer flask and mix thoroughly by swirling the flask.
5. Titrate one sample quickly (do not attempt to be accurate to the drop) with the standardized NaOH
solution to determine the relative endpoint and relative amount of NaOH that will be needed to see
the color change from red to dark green.
6. Swirl the flask while titrating to ensure proper mixing of the NaOH with the acid sample. This is a
rough measurement that will be used to help make the second titration easier and more accurate.
Use the amount of NaOH required to change the color in this quick titration as a guideline for Step
7.
7. Using the solution in the second Erlenmeyer flask, titrate quickly up to 2 mL before the color
change is supposed to occur.
8. Add 0.2 mL to 0.5 mL slowly, swirling the flask as each drop is added.
9. As the endpoint is approached, add one drop at a time until the first color of green appears. This is
the endpoint.
10. Record this volume of NaOH to use in the acid strength calculations.
Calculations
Calculate the percent acid in the sample with one of the appropriate equations below:
Single Acid Calculations
To obtain the percentage of acid, use the appropriate acid-dilution table and find the acid concentration
corresponding to the measured normality. It might be necessary to interpolate if the measured normality
is not listed.
3-8
March 2009
Where:
mL NaOH = the volume of NaOH required to reach the endpoint.
N = the normality of the NaOH that was calculated when the NaOH was standardized.
mL sample = the volume of the acid sample pipetted into the Erlenmeyer flask.
Alternately, if the approximate concentrations are sufficient, the following calculations can be used
without the need for acid-dilution tables. These calculations do not give a true weight percent and will be
in error by a factor of the specific gravity. If specific gravity is known or can be determined, the answer
can be corrected to give weight percentage by dividing the answer by the specific gravity.
Where Parameter depends on the type of acid and is defined as follows for different acids:
HCl = 3.65
HF acid = 2
Sulphuric acid (H2SO4) = 4.9
Acetic acid (CH3COOH) = 6.01
Formic acid (HCOOH) = 4.6
Mixed Acid Calculations
This procedure cannot determine the exact composition of solutions that contain more than one acid.
However, the total acid normality can be obtained by titration and compared to the expected normality
for a particular mixed acid.
Example:
HCl acid normality (N): X
Formic acid normality (N): Y
Combined acid normality (N): X + Y
March 2009
3-9
PPE: Face shield, gloves (refer to Appendix A), coveralls (refer to Appendix A), safety glasses,
rubber boots, and a hard hat
Procedure
Note
1. Prepare two live-acid blends, one containing all the additives with 500 ppm of Fe3+ and one
containing all the additives without Fe3+.
2. Add 100 mL of the live-acid blend containing all additives without Fe3+ into the glass jar.
3. Add 100 mL of live-acid blend containing all additives with Fe3+ into the other glass jar.
4. Allow both jars to stand for 1 hour.
5. After 1 hour, observe and record any additive separation.
6. The acid blend is acceptable if no separation of additives occurs on the top, bottom, or sides of the
jar.
7. If the acid blend separates, perform one of the following steps:
3-10
a.
Add dispersant or mutual solvent to the blend. The exact amount and type can be determined by testing.
b.
Change additives or adjust the additive concentration. The extent of changes and
adjustments can be determined by testing.
March 2009
Blend-Compatibility Test
Scope: To find the most effective combination of additives needed to help prevent incompatibilities
between fluids.
PPE: Face shield, gloves (refer to Appendix A), coveralls (refer to Appendix A), safety glasses,
rubber boots, and a hard hat.
One stopwatch
Watch-Glass Testing
1. Use a syringe to transfer 5 mL of test fluid onto a watch glass. Add 5 mL of the acid blend to the
test fluid, drop-wise, using the Pasteur pipette.
2. Observe the mixture for 5 minutes, checking for effervescence or evolution of gas.
Note
If the watch glass indicates the evolution of gas, the blend-compatibility test
procedure using the closed-container test method might not be suitable. Contact your
lab supervisor to determine whether this type of testing is appropriate for your
specific situation.
Note
If the watch glass indicates the evolution of gas and the blend-compatibility test
procedure is still desired, the test should be performed by mixing the components in
an open container with a mechanical mixing device. After mixing, the contents should
be placed into a graduated cylinder and observed for separation.
Procedure
1. Place 50 mL of the acid blend into a 250-mL plastic bottle.
2. Add 50 mL of the formation/wellbore treatment/workover fluid to the plastic bottle.
3. Observe for any effervescence in the bottle. If evolution of gas or effervescence occurs, contact
your lab supervisor and determine whether the test should be performed by mechanical stirring.
4. Tightly seal the lid on the bottle, and then vigorously shake the jar by hand for 30 seconds.
March 2009
3-11
5. Slowly remove the lid to allow for the release of gas, and then transfer the contents to a 100-mL
graduated cylinder.
6. Allow the graduated cylinder to stand at ambient temperature or place the graduated cylinder in a
water bath set to the BHST or 180F, whichever is lower.
7. Observe the contents in the graduated cylinder for 5 and 10 minutes.
8. Perform one of the following steps:
a.
b.
If Fe3+ is a concern with the live acid blend, repeat the test with 1,000 ppm of Fe3+ added
to the live acid
Note
Important
3-12
March 2009
PPE: Face shield, gloves (refer to Appendix A), coveralls (refer to Appendix A), safety glasses,
rubber boots, and a hard hat
Syringes
Crude oil100 mL
Test fluid100 mL
Chemicalssurfactant
Procedure
Conduct this procedure with both live and spent acid.
1. Prepare the desired acid-treatment fluid. The volume of treatment fluid is determined by the test
amount.
2. Cool the fluid to ambient temperature.
3. For a blank test, add 50 mL of the acid fluid and 50 mL of the produced crude to one of the glass
bottles.
4. Tightly seal the jar.
5. Vigorously shake the jar for 30 seconds.
6. Record the break rate at time intervals of 1, 5, and 10 minutes.
7. If 100% separation does not occur at ambient temperature, place the emulsion test in a water bath
set to 200F or BHST, whichever is lower.
8. Record the break rate at time intervals of 1, 5, and 10 minutes.
9. To the second bottle, add 50 mL of the acid fluid. Add the appropriate surfactant volume to the acid
fluid. Consult the technology bulletin for the particular surfactant to determine the appropriate
volume. Concentration can be determined from field experience or prior testing knowledge. The
emulsion characteristics of the crude oil will dictate the required chemical concentration. As a
general rule, the surfactant concentration will probably range from 0.1 to 1.0%, depending on test
specifics. Thoroughly combine the surfactant with the acid.
10. Add 50 mL of the produced crude oil.
11. Tightly seal the bottle and repeat Steps 5 thru 8.
12. Observe the crude oil mixture in the water bath after 5- and 10-min intervals to determine if the
induced emulsion has 100% separation.
March 2009
3-13
Note
If 100% separation of the acid fluid and crude oil occurs in 10 minutes or less at
ambient temperature, the test is successful. These results recommend the surfactant
or surfactant mixtures and concentrations to use with the fluid
Important
3-14
March 2009
Sludge Test
Scope: To ensure that the live-acid blends are compatible with the formation crude and no sludge is
formed.
PPE: Face shield, gloves (refer to Appendix A), coveralls (refer to Appendix A), safety glasses,
rubber boots, and a hard hat
One stopwatch
One balance
Procedure
1. Prepare 50 mL of the desired live-acid blend.
2. Place the blend in a 4-oz glass jar.
3. Add 50 mL of the formation crude oil and tightly seal the jar.
4. Vigorously shake the jar by hand for 30 seconds.
5. Place the jar in a water bath heated to the BHST or 200F, whichever is lower.
Important Slightly unscrew the jar lid to prevent pressure build-up within the jar. Failure to
release the pressure during the heating stage can result in a sample loss or a broken jar.
6. After 30 minutes, remove the jar from the bath.
7. Pour the contents of the jar through a 100-mesh screen.
8. Observe any sludge adhering to the inside of the glass jar and on the screen.
9. Rinse the solids on the screen with kerosene.
March 2009
3-15
PPE: Face shield, gloves (refer to Appendix A), coveralls (refer to Appendix A), safety glasses,
rubber boots, and a hard hat.
One stopwatch
One balance
Procedure
1. Prepare 50 mL of the desired live-acid blend.
2. Place the blend in a 4-oz glass jar.
3. Add 50 mL of the formation crude oil and tightly seal the jar.
4. Vigorously shake the jar by hand for 30 seconds.
5. Place the jar in a water bath heated to the BHST or 200F, whichever is lower.
Important Slightly unscrew the jar lid to prevent pressure build-up within the jar. Failure to
release the pressure during the heating stage can result in a sample loss or a broken jar.
6. Weigh a Whatman No. 4 filter-paper disc.
7. Place the filter-paper disc inside the Buchner funnel.
8. Using a Filtervac seal, insert the Buchner funnel into the sidearm vacuum flask.
9. Using the vacuum hose, attach the sidearm vacuum flask to either the vacuum pump or faucet aspirator.
10. After 30 min, remove the jar from the bath.
11. Activate the vacuum.
12. Open the jar and pour the contents onto the pre-weighed filter-paper disc.
3-16
March 2009
March 2009
3-17
3-18
March 2009
SECTION
Section
14
Preface
Acid Systems
Carbonate 20/20 Acidizing Service ............................................................................................4-2
Sandstone 2000 Acidizing Service .............................................................................................4-20
March 2009
Acid Systems
4-1
Please consult the appropriate Technology Bulletins for more detailed information on
these acidizing systems.
Important
Ensure that all personnel handling the product read, understand, and follow the
precautions in the MSDS for each chemical. Summaries of the relevant points and
information on first-aid measures by different exposure routes are contained in each
product's MSDS.
The MSDS for components of this service can be found at the following URL
address: http://msds.corp.halliburton.com
4-2
Acid Systems
March 2009
Applications/Advantages
Used for horizontal wells in carbonate formations and for diversion in matrix acidizing.
Mixing Procedures
The ZCA system can be batch mixed or mixed on-the-fly, depending on the gelling agent that is used.
Note
If SGA-II or SGA-V gelling agents are used, the system can be run on-the-fly.
If SGA-III gelling agent is used, the system must be batch-mixed. Remember that
the crosslink is not apparent until the acid spends, so it is not present at surface or in
the tubulars.
Important
Always clean out the tubing before running this system. Otherwise, crosslinking
might be adversely affected.
Corrosion inhibitor
b.
c.
Important
When adding gelling agent to the acid, use as much shear as possible to help
prevent lumping and to ensure proper hydration, especially when using 28%
HCl.
March 2009
Acid Systems
4-3
Acids: Can cause eye and skin burns, and respiratory irritation. Can be harmful if swallowed.
Fercheck Ferric-Iron Inhibitor: Can cause eye, skin, and respiratory irritation. Airborne dust can
be explosive.
SGA-II, SGA-III, and SGA-IV Gelling Agents: Can cause headaches, dizziness, and other
central-nervous-system effects. Can be harmful if swallowed.
XL-1 Crosslinker: Can cause eye, skin, and respiratory burns and damage to internal organs. Can
be fatal if swallowed.
First Aid
Inhalation: If inhaled, remove victim from area to fresh air. If victim is not breathing, give artificial
respiration, preferably mouth-to-mouth. If breathing is difficult, give oxygen. Get medical
attention.
Skin: In case of contact, immediately flush skin with plenty of soap and water for at least 15
minutes. Get medical attention. Remove contaminated clothing and launder before reuse.
Eyes: In case of contact, or suspected contact, immediately flush eyes with plenty of water for at
least 15 minutes and get medical attention immediately after flushing.
Ingestion
Acids, BF-1 Buffering Agent, XL-1 Crosslinker: Do not induce vomiting. Slowly dilute with 1
to 2 glasses of water or milk and seek medical attention. Never give anything by mouth to an
unconscious person.
SGA-II, SGA-III and SGA-IV Gelling Agents: Get medical attention! If vomiting occurs, keep
head lower than hips to prevent aspiration.
Notes to Physician
SGA-III Gelling Agent: Activated charcoal or gastric lavage might be advisable for significant
ingestion.
XL-1 Crosslinker: If ingested, a stomach wash followed by saline catharsis and cenodyne is
recommended.
Spills
Environmental Precautionary Measures
4-4
Acid Systems
March 2009
Acid, Gelling Agents, and Buffer: Avoid contact with eyes, skin, or clothing. Avoid breathing
vapors. Wash hands after use. Launder contaminated clothing before reuse.
Exposure Controls
Engineering Controls
Use in a well-ventilated area. Local exhaust ventilation should be used in areas without good cross
ventilation.
March 2009
Acid Systems
4-5
Applications/Advantages
Allows extended reaction times, provides built-in iron control, and enhances the performance of
acid gelling agents.
Emulsion problems are less likely associated with this acid system because of reduced interfacial
tension.
Sludging problems are usually eliminated because of reduced H+ concentration compared to HClacid systems.
Subtract the volume of inhibitor, surfactant, and acid gelling agent from the water
volume
Important
Use the acid calcualtion spreadsheet to determine the required volume of each organic
acid:
http://halworld.corp.halliburton.com/internal/PS/pe/contents/Interactive_Tools/web/
Acid_Brine_Calculations.xls
4-6
Acid Systems
March 2009
HRA System: Can cause eye and skin burns, headaches, dizziness, and other central-nervoussystem effects. Can be harmful if swallowed. Combustible.
First Aid
Inhalation: If inhaled, remove victim from area to fresh air. If victim is not breathing, give artificial
respiration, preferably mouth-to-mouth. If breathing is difficult, give oxygen. Get medical
attention.
Skin: In case of contact, immediately flush skin with plenty of soap and water for at least 15
minutes. Get medical attention. Remove contaminated clothing and launder before reuse.
Eyes: In case of contact, or suspected contact, immediately flush eyes with plenty of water for at
least 15 minutes and get medical attention immediately after flushing.
Ingestion (Acids): Do not induce vomiting. Slowly dilute with 1 to 2 glasses of water or milk and
seek medical attention. Never give anything by mouth to an unconscious person.
Spills
Environmental Precautionary Measures
Avoid contact with eyes, skin, or clothing. Avoid breathing vapors. Wash hands after use. Launder
contaminated clothing before reuse.
Exposure Controls
Engineering Controls
Use in a well-ventilated area. Local exhaust ventilation should be used in areas without good cross
ventilation.
March 2009
Acid Systems
4-7
Applications/Advantages
Primarily used for acidizing carbonate reservoirs that contain asphaltenic crude.
Can be used in sour wells if sulfide scavenger is added and in sweet wells if ferric iron-control is
used.
Mixing Procedures
CCA system components are readily dispersible and easily mixed. Use the following procedure to mix
these components:
1. Add water to the tank, reducing the required volume by the additive volume to be used.
2. Add HAI-GE corrosion inhibitor. AS-10 antisludging agent, G-Sperse dispersant, and CCA-H2S
hydrogen-sulfide scavenger can also be added at this time or after the concentrated HCl acid has
been added.
3. Mix well, but avoid rolling the tank with air if FDP-S769-05 iron-reducing agent is used. It is an
oxygen scavenger, and air mixing will deplete its reduction capability.
Important Do not add FDP-S769-05 iron-reducing agent until the concentrated HCl has been
added.
Acids, FDP-S769-05 Iron-Reducing Agent: Can cause eye and skin burns. Can cause respiratory
irritation. Can be harmful if swallowed.
AS-10 Antisludging Agent: Repeated overexposure can cause liver and kidney effects.
4-8
Acid Systems
March 2009
G-Sperse Dispersant: Can cause eye, skin, and respiratory irritation. Can cause allergic skin
reactions and respiratory reactions. Can be absorbed through the skin. Can be harmful if swallowed.
First Aid
Inhalation
If inhaled, remove victim from area to fresh air. If victim is not breathing, give artificial respiration,
preferably mouth-to-mouth. If breathing is difficult, give oxygen. Get medical attention.
Skin
In case of contact, immediately flush skin with plenty of soap and water for at least 15 minutes. Get
medical attention. Remove contaminated clothing and launder before reuse.
Eyes
In case of contact, or suspected contact, immediately flush eyes with plenty of water for at least 15
minutes and get medical attention immediately after flushing.
Ingestion
G-Sperse Dispersant: Under normal conditions, first aid procedures are not required.
Notes to Physician
HAI-GE Corrosion Inhibitor: Probable mucosal damage can contraindicate the use of gastric
lavage.
Spills
Environmental Precautionary Measures
Isolate spills and stop leaks where safe. Contain spills with sand or other inert materials.
March 2009
Acid Systems
4-9
Handling Precaution
CCA-H2S Hydrogen-Sulfide Scavenger: Avoid contact with eyes, skin, or clothing. Avoid
creating or inhaling dust. Wash hands after use.
Acids, HAI-GE Corrosion Inhibitor, FDP-S769-05 Iron-Reducing Agent: Wash hands after
use. Launder contaminated clothing before reuse.
HAI-GE Corrosion Inhibitor, G-Sperse Dispersant: Do NOT consume food, drink, or tobacco
in contaminated areas. Ground and bond containers when transferring from one container to
another.
Exposure Controls
Engineering Controls
Use in a well-ventilated area. Local exhaust ventilation should be used in areas without good cross
ventilation.
HAI-GE Corrosion Inhibitor: When used in high concentrations, a supplied air respirator or a
self-contained breathing apparatus might be required.
4-10
Acid Systems
March 2009
Applications/Advantages
Can be used in low-pressure, liquid-sensitive wells that normally produce fines during acidizing.
Under matrix acidizing conditions, the FRA system can be used to divert in long horizontal
openhole sections.
Mixing Procedure
1. Add water to a recirculating mixer.
2. Add HAI-GE corrosion inhibitor or HAI-81M acid corrosion inhibitor.
3. Add non-emulsifier, if needed.
4. Add HCl acid.
5. Add SGA-I gelling agent and mix thoroughly by circulating the acid until all globules of gelling
agent disappear.
6. Place the mixture in a holding tank that is free of rust and organic contamination. The gelled-acid
system is sensitive to high concentrations of iron, oil, and other organic materials.
Important
Do not roll the mixture with air. Doing so can cause excessive foaming.
Note
March 2009
Acid Systems
4-11
Hazard Overview
Acids, SGA-I Gelling Agent: Can cause eye and skin burns and respiratory irritation. Can be
harmful if swallowed.
HAI-GE Corrosion Inhibitor: Can cause eye, skin, and respiratory burns, headaches, dizziness,
and other central-nervous-system effects. Can be absorbed through the skin. Can be harmful if
swallowed. Can cause allergic skin and respiratory reactions. Flammable.
HAI-81M Acid Corrosion Inhibitor: Can cause eye, skin, and respiratory irritation, headaches,
dizziness, and other central-nervous-system effects. Can be absorbed through the skin. Can be fatal
if swallowed. Can cause blindness. Flammable.
First Aid
Inhalation
If inhaled, remove victim from area to fresh air. If victim is not breathing, give artificial respiration,
preferably mouth-to-mouth. If breathing is difficult, give oxygen. Get medical attention.
Skin
In case of contact, immediately flush skin with plenty of soap and water for at least 15 minutes. Get
medical attention. Remove contaminated clothing and launder before reuse.
Eyes
In case of contact, or suspected contact, immediately flush eyes with plenty of water for at least 15
minutes and get medical attention immediately after flushing.
Ingestion
Acids, HAI-GE Corrosion Inhibitor, and SGA-I Gelling Agent: Do not induce vomiting. Slowly
dilute with 1 to 2 glasses of water or milk and seek medical attention. Never give anything by mouth
to an unconscious person.
HAI-81M Acid Corrosion Inhibitor: If swallowed, induce vomiting immediately by giving two
glasses of water and sticking fingers down throat; never give anything to an unconscious person.
Get medical attention.
Spills
Environmental Precautionary Measures
4-12
Acid Systems
March 2009
Isolate spills and stop leaks where safe. Contain spills with sand or other inert materials.
Acids:
1. Neutralize to pH of 6 to 8.
2. Scoop up and remove.
Handling Precautions
Acids, HAI-GE Corrosion Inhibitor: Avoid contact with eyes, skin, or clothing. Avoid breathing
vapors. Wash hands after use. Launder contaminated clothing before reuse.
HAI-GE Corrosion Inhibitor: Do NOT consume food, drink, or tobacco in contaminated areas.
Ground and bond containers when transferring from one container to another.
Exposure Controls
Engineering Controls
Use in a well-ventilated area. Local exhaust ventilation should be used in areas without good cross
ventilation.
When used in high concentrations, a supplied air respirator or a self-contained breathing apparatus
might be required.
March 2009
Acid Systems
4-13
Applications/Advantages
CEA service is used in carbonate-reservoir stimulation jobs that require retarded acid-reaction rates.
In fracture-acidizing applications, formations that produce heavy crude oils with high quantities of
asphaltenes tend to respond best to CEA service.
Mixing Procedure
CEA service can be batch-mixed or mixed continuously or semi-continuously.
Batch-Mixing Procedure
1. Place the hydrocarbon fluid in the emulsion tank and blend the appropriate quantity of AF-61 or
AF-70 emulsifier.
2. Add water to the acid tank, followed by corrosion inhibitor and the 20 or 22Be HCl acid.
3. Slowly add the acid blend to the hydrocarbon. When the fluids pass through the shearing device,
the emulsification process begins.
Important Always add the acid blend slowly. If the blend is added too quickly, the emulsion can
break out.
Note
The fluid must be passed through the shearing device several times before all of the
acid blend is added into the emulsion.
4-14
Acid Systems
March 2009
Acids: Can cause eye and skin burns and respiratory irritation. Can be harmful if swallowed.
Diesel, AF-61 Emulsifier: Can cause eye, skin, and respiratory burns, headaches, dizziness, and
other central-nervous-system effects. Can be absorbed through the skin. Can be harmful if
swallowed. Can cause skin and respiratory allergic reactions. Combustible.
HV-60 Intensifier Agent: Can cause eye, skin, and respiratory irritation.
First Aid
Inhalation
If inhaled, remove victim from area to fresh air. If victim is not breathing, give artificial respiration,
preferably mouth-to-mouth. If breathing is difficult, give oxygen. Get medical attention.
Skin
In case of contact, immediately flush skin with plenty of soap and water for at least 15 minutes. Get
medical attention. Remove contaminated clothing and launder before reuse.
Eyes
In case of contact, or suspected contact, immediately flush eyes with plenty of water for at least 15
minutes and get medical attention immediately after flushing.
Ingestion
Acids: Do not induce vomiting. Slowly dilute with 1 to 2 glasses of water or milk and seek medical
attention. Never give anything by mouth to an unconscious person.
Diesel, AF-61 Emulsifier: Get medical attention! If vomiting occurs, keep head lower than hips to
prevent aspiration.
HV-60 Intensifier Agent: Under normal conditions, first aid procedures are not required.
Spills
Environmental Precautionary Measures
Prevent from entering sewers, waterways, or low areas.
Procedure for Cleaning/Absorption
Isolate spills and stop leaks where safe. Contain spills with sand or other inert materials.
March 2009
Acid Systems
4-15
AF-61 Emulsifier:
1. Isolate spills and stop leaks where safe.
2. Contain spills with sand or other inert materials.
3. Scoop up and remove.
Handling Precautions
Acids: Avoid contact with eyes, skin, or clothing. Avoid breathing vapors. Wash hands after use.
Launder contaminated clothing before reuse.
G-Sperse Dispersant: Do NOT consume food, drink, or tobacco in contaminated areas. Ground
and bond containers when transferring from one container to another.
Personal Precautionary Measures: Use appropriate PPE. Avoid creating and breathing dust.
Exposure Controls
Engineering Controls
Use in a well-ventilated area. Local exhaust ventilation should be used in areas without good cross
ventilation.
HV-60 Intensifier Agent: When used in high concentrations, a supplied air respirator or
self-contained breathing apparatus might be required.
4-16
Acid Systems
March 2009
Application/Advantages
CSA service can be used to stimulate carbonate formations by fracture-acidizing or matrix-acidizing.
Note
Mixing Procedure
Follow the General Mixing Guidelines under Job Preparation on Page 2-4 for order of addition.
Note
The gelling agent should be added after the acid but before the surfactant.
Important
SGA-HT acid system gelling agent should be mixed at a high shear rate for at least
15 min to ensure it is fully hydrated before pumping downhole.
Warning
To avoid unpredictable reactions, do not batch mix SGA-HT acid system gelling
agent and SCA-130 sulfide-cracking inhibitor. Run one or both of these
components on-the-fly.
Acids: Can cause eye and skin burns and respiratory irritation. Can be harmful if swallowed.
SGA-HT Acid System Gelling Agent, SGA-II Acid Gelling Agent, and SGA-III Gelling
Agent: Can cause eye, skin, and respiratory irritation, headaches, dizziness, and other centralnervous-system effects. Can be harmful if swallowed.
March 2009
Acid Systems
4-17
First Aid
Inhalation
If inhaled, remove victim from area to fresh air. If victim is not breathing, give artificial respiration,
preferably mouth-to-mouth. If breathing is difficult, give oxygen. Get medical attention.
Skin
In case of contact, immediately flush skin with plenty of soap and water for at least 15 minutes. Get
medical attention. Remove contaminated clothing and launder before reuse.
Eyes
In case of contact, or suspected contact, immediately flush eyes with plenty of water for at least 15
minutes and get medical attention immediately after flushing.
Ingestion
Acids: Do not induce vomiting. Slowly dilute with 1 to 2 glasses of water or milk and seek medical
attention. Never give anything by mouth to an unconscious person.
SGA-HT Acid System Gelling Agent, SGA-II Acid Gelling Agent, and SGA-III Gelling
Agent: Get medical attention! If vomiting occurs, keep head lower than hips to prevent aspiration.
Acids, SGA-HT Acid System Gelling Agent, SGA-II Acid Gelling Agent, and SGA-III Gelling
Agent: Avoid contact with eyes, skin, or clothing. Avoid breathing vapors. Wash hands after use.
Launder contaminated clothing before reuse.
4-18
Acid Systems
March 2009
Exposure Controls
Engineering Controls
Use in a well-ventilated area. Local exhaust ventilation should be used in areas without good cross
ventilation.
SGA-HT Acid System Gelling Agent: When used in high concentrations, a supplied air
respirator or self-contained breathing apparatus might be required.
March 2009
Acid Systems
4-19
The mixing procedure for all these Sandstone 2000 service treatments should follow
the general mixing procedure, unless otherwise mentioned separately (i.e., water +
corrosion inhibitor + acid + surfactants). The detailed general-mixing guideline is
mentioned in Section 2 (On-Site Quality Assurance Standards for Acidizing).
Please consult the appropriate Technology Bulletins for more detailed information on
these acidizing systems.
Important
Ensure that all personnel handling the product read, understand, and follow the
precautions in the MSDS for each chemical. Summaries of the relevant points and
information on first-aid measures by different exposure routes are contained in each
product's MSDS.
The MSDS for components of this service can be found at the following URL
address: http://msds.corp.halliburton.com
4-20
Acid Systems
March 2009
Application/Advantages
This fluid system is compatible with a majority of formations and particularly designed for cases
where the formation mineralogy is unknown or uncertain. It should be used for acidizing most
sandstone formations.
Contains high HCl-HF acids ratio to provide compatibility with most formation mineralogies.
Aids in iron control, in most cases eliminating the need for other iron-control additives, such as
Fe-2 iron-sequestering agent (citric acid) and Fe-1A (acetic acid) agent. If Fe3+ must be reduced,
Ferchek ferric-iron inhibitor, Ferchek A reducing agent, or Ferchek SC iron-control system will
be required.
Note
This acid system should not be used in formations high in feldspars, particularly at
temperatures below 200F and in formations containing HCl-acid-sensitive minerals.
Acids, Ferchek SC Iron-Control System: Can cause eye and skin burns and respiratory irritation.
Can be harmful if swallowed.
PEN-88M and PEN-88 HT Surfactants: Can cause eye, skin, and respiratory irritation,
headaches, dizziness, and other central-nervous-system effects. Can be harmful if swallowed.
Combustible
March 2009
Acid Systems
4-21
Fe-2 Iron-Sequestering Agent: Can cause eye and respiratory irritation. Airborne dust can be
explosive.
Fercheck A Reducing Agent: Can cause skin and respiratory allergic reactions. Airborne dust
can be explosive.
First Aid
Inhalation
If inhaled, remove victim from area to fresh air. If victim is not breathing, give artificial respiration,
preferably mouth-to-mouth. If breathing is difficult, give oxygen. Get medical attention.
Skin
In case of contact, immediately flush skin with plenty of soap and water for at least 15 minutes. Get
medical attention. Remove contaminated clothing and launder before reuse.
Eyes
In case of contact, or suspected contact, immediately flush eyes with plenty of water for at least 15
minutes and get medical attention immediately after flushing.
Ingestion
Do not induce vomiting. Slowly dilute with 1 to 2 glasses of water or milk and seek medical
attention. Never give anything by mouth to an unconscious person.
Spills
Environmental Precautionary Measures
4-22
Acid Systems
March 2009
Exposure Controls
Engineering Controls
Use in a well-ventilated area. Local exhaust ventilation should be used in areas without good cross
ventilation.
Ferchek SC, PEN-88 HT: In high concentrations, supplied air respirator or a self-contained
breathing apparatus may be required.
March 2009
Acid Systems
4-23
Application/Advantages
1. Retarded reaction with sand and silica to promote deep damage removal and improve compatibility
with feldspar-containing formations.
2. It is primarily used for formations containing significant kaolinite and/or illite.
3. It can also be effective in formations that are HCl-acid-sensitive.
4. Deeper penetration of live HF acid into the formation.
5. Clay stabilizer to control fines migration during and following the treatment.
Acids and Alchek Agent: Can cause eye and skin burns and respiratory irritation. Can be harmful
if swallowed.
PEN-88M and PEM-88 HT Surfactants: Can cause headaches, dizziness, and other centralnervous-system effects. Combustible.
First Aid
Inhalation
4-24
If inhaled, remove victim from area to fresh air. If victim is not breathing, give artificial respiration,
preferably mouth-to-mouth. If breathing is difficult, give oxygen. Get medical attention.
Acid Systems
March 2009
Skin
In case of contact, immediately flush skin with plenty of soap and water for at least 15 minutes. Get
medical attention. Remove contaminated clothing and launder before reuse.
Eyes
In case of contact, or suspected contact, immediately flush eyes with plenty of water for at least 15
minutes and get medical attention immediately after flushing.
Ingestion
Do not induce vomiting. Slowly dilute with 1 to 2 glasses of water or milk and seek medical
attention. Never give anything by mouth to an unconscious person.
Spills
Environmental Precautionary Measures
Exposure Controls
Engineering Controls
Use in a well-ventilated area. Local exhaust ventilation should be used in areas without good cross
ventilation.
March 2009
Acid Systems
4-25
K-Spar Acid
Introduction
K-Spar acid is designed for treating formations containing significant sodium feldspar, potassium
feldspar, or illite. K-Spar acid is a blend of 9% HCl acid and 1% HF acid that contains Fe-1A (acetic acid)
to control aluminum scaling and iron precipitation, Pen-88M/Pen-88 HT surfactant as a penetrating
agent, and Cla-Sta FS compound as a clay- and fines-control additive.
Application/Advantages
It should be used where the formation contains K-Spar acid and/or illite as the dominant mineral
(Overall content 10%)
Since the fluorosilicates are less soluble at lower temperature, K-Spar acid should be used in most
formations containing significant sodium feldspars at temperatures below 175F.
Contains clay stabilizer to control fines migration during and following the treatment.
Note
Acids, Ferchek SC: May cause eye and skin burns. May cause respiratory irritation. May be harmful
if swallowed.
Cla-Sta FS Compound, Cla-Sta XP Clay-Stabilizing Agent: Can cause eye, skin, and respiratory
irritation. Can be harmful if swallowed.
PEN-88M and PEN-88 HT Surfactants: Can cause eye, skin, and respiratory irritation,
headaches, dizziness, and other central-nervous-system effects. Can be harmful if swallowed.
Combustible
4-26
Acid Systems
March 2009
First Aid
Inhalation
If inhaled, remove victim from area to fresh air. If victim is not breathing, give artificial respiration,
preferably mouth-to-mouth. If breathing is difficult, give oxygen. Get medical attention.
Skin
In case of contact, immediately flush skin with plenty of soap and water for at least 15 minutes. Get
medical attention. Remove contaminated clothing and launder before reuse.
Eyes
In case of contact, or suspected contact, immediately flush eyes with plenty of water for at least 15
minutes and get medical attention immediately after flushing.
Ingestion
Do not induce vomiting. Slowly dilute with 1 to 2 glasses of water or milk and seek medical
attention. Never give anything by mouth to an unconscious person.
Spills
Environmental Precautionary Measures
Exposure Controls
Engineering Controls
Use in a well-ventilated area. Local exhaust ventilation should be used in areas without good cross
ventilation.
K-Spar Acid, PEN-88 HT Surfactant: When used in high concentrations, a supplied air respirator
or self-contained breathing apparatus might be required.
March 2009
Acid Systems
4-27
Application/Advantages
Compatible with HCl-sensitive minerals (for example, chlorite, zeolites, and other clays at
temperatures above their HCl-decomposition temperature).
Can be used at higher temperatures than HCl-based fluids without decomposing clays or zeolites or
having high corrosion rates. This system is much easier to inhibit to prevent excessive corrosion.
Avoids secondary precipitation observed with formic-HF acid and acetic-HF acid.
Typically, this acid system will not cause sludging with crude oils.
Note
Acids: Can cause eye and skin burns. Can cause respiratory irritation. Can be harmful if swallowed.
PEN-88M Surfactant, PEM-88 HT Surfactant: Can cause eye, skin, and respiratory irritation,
headaches, dizziness, and other central-nervous-system effects. Can be harmful if swallowed.
Combustible.
4-28
Acid Systems
March 2009
Volcanic Acid System II, AF: Can cause eye, skin, and respiratory irritation. Can damage
bones. Can be harmful if swallowed.
Fe-2 Iron-Sequestering Agent: Can cause eye, skin, and respiratory irritation. Airborne dust
can be explosive.
First Aid
Inhalation
If inhaled, remove victim from area to fresh air. If victim is not breathing, give artificial respiration,
preferably mouth-to-mouth. If breathing is difficult, give oxygen. Get medical attention.
Skin
In case of contact, immediately flush skin with plenty of soap and water for at least 15 minutes. Get
medical attention. Remove contaminated clothing and launder before reuse.
Eyes
In case of contact, or suspected contact, immediately flush eyes with plenty of water for at least 15
minutes and get medical attention immediately after flushing.
Ingestion
Spills
Environmental Precautionary Measures
March 2009
Acid Systems
4-29
Exposure Controls
Engineering Controls
Use in a well-ventilated area. Local exhaust ventilation should be used in areas without good cross
ventilation.
4-30
Acid Systems
March 2009
Application/Advantages
This acid system is recommended for use only where the formation is 100% quartz and contains no
clay minerals.
Used for removal of silica scale from the wellbore in areas where silica scale can form (geothermal
wells or steam flooding).
Note
Acids: Can cause eye and skin burns. Can be harmful if swallowed.
First Aid
Inhalation
If inhaled, remove victim from area to fresh air. If victim is not breathing, give artificial respiration,
preferably mouth-to-mouth. If breathing is difficult, give oxygen. Get medical attention.
Skin
In case of contact, immediately flush skin with plenty of soap and water for at least 15 minutes. Get
medical attention. Remove contaminated clothing and launder before reuse.
HF Acid: While wearing protective gloves, apply 2.5% calcium-gluconate gel at burn site, rubbing
continuously.
Eyes
In case of contact, or suspected contact, immediately flush eyes with plenty of water for at least 15
minutes and get medical attention immediately after flushing.
HF Acid: If available, apply 1 to 2 drops of 0.5% pontocaine hydrochloride into open eye. Irrigate
with 1.0% calcium gluconate in normal saline for 1 to 2 hours.
March 2009
Acid Systems
4-31
Ingestion (Acids)
Do not induce vomiting. Slowly dilute with 1 to 2 glasses of water or milk and seek medical
attention. Never give anything by mouth to an unconscious person.
Spills
Environmental Precautionary Measures
Avoid contact with eyes, skin, or clothing. Avoid breathing vapors. Wash hands after use. Launder
contaminated clothing before reuse.
Exposure Controls
Engineering Controls
4-32
Use in a well-ventilated area. Local exhaust ventilation should be used in areas without good cross
ventilation.
Acid Systems
March 2009
SECTION
Appx
1
A
Preface
March 2009
A-1
A-2
March 2009
Face shield
Dust, Mist
Fume Respirator
HEPA
AF Additive
CG
AF-61 Emulsifier
CG
OV
NEO/NIT
OV/AG
OV/AG
OV/AG/P
F
AF-70 Emulsifier
Tyvek
Coverall
Chemical
Goggles
BUT
Atmosphere
Supplying
Respirator
Apron
ABF Additive
Product Name
Chemical
Cartridge
Respirator
Gloves
Comments
Possible
CG
CG
CG
CG
CG
NEO
CG/VIT/
BUT/ NEO
OV
OV/AG
OV/AG
Possible
OV/AG/P
F
OV/AG/P
F
Neoprene coated apron or
clothing is required
Supplied air respirator might
be required
95%
Possible
CG
Cla-Sta FS Compound
CG
OV/AG/P
F
CG
OV/PF
CG
OV/AG/P
F
CG
OV/AG
Rubber boots
CG
OV/AG
Rubber boots
Cla-Sta XP Clay-Stabilizing
Agent
Clayfix Clay-Control Material
(Liquid)
Carbonate Emulsion Acid
(CEA) Service
Carbonate Completion Acid
(CCA) System
Rubber boots
Engineering controls
required
CG
NIT
CG
CG/NIT/
NEO/PVC
OV/AG
95%
X
CG
CG
CG
WG
Ferchek SC Iron-Control
Process
CG
AG
CG
CG
G-Sperse Dispersant
CG
Rubber boots
OV
95%
AG
OV/AG
Rubber boots
95%
95%
95%
AG
Rubber boots
OV/AG
Rubber boots
OV/AG
Possible
CG
OV/AG
Possible
CG
OV/AG
Possible
CG
OV/AG
Possible
CG
OV/AG
Possible
CG
OV/AG
Possible
CG
OV/AG
Possible
Possible
CG
HII-124B Corrosion-Inhibitor
Intensifier
CG
CG
HII-124F Corrosion-Inhibitor
Intensifier
CG
CG
CG
HEPA
95%
OV/PF
CG
OV/AG
Rubber boots
CG
OV/AG
Rubber boots
WG
CG
AG
Rubber boots
CG
AG
Rubber boots
K-Spar Acid
CG
AG
Possible
HII-500M Corrosion-Inhibitor
Intensifier
HII-600 Corrosion Inhibitor
Intensifier
OV/AG
Possible
AG
Rubber boots
Solid, safety glasses or
goggles; engineering
controls required
95%
95%
Possible
NEO/NIT/
VIT
OV
Possible
CG
OV/AG
Possible
PEN-88 HT Surfactant
CG
OV
Possible
PEN-88M Surfactant
CG
OV
AG
Sandstone Acid
CG
VIT/NIT/N
EO
Rubber boots
SCA-130 Sulfide-Cracking
Inhibitor
SGA-HT Acid System Gelling
Agent (Flocculent)
CG
OV
PVC/OR
OV
Possible
BUT
CG
OV/AG/P
F
OV
CG
OV
CG
OV/PF
possible
CG
OV/AG
SP Breaker Agent
BUT
CG
CG
XL-1 Crosslinker
Zonal Coverage Acid (ZCA)
System
CG
CG
Rubber boots
95%
Rubber boots
Solid, dust-proof goggles
95%
OV/AG
AG/PF
AG
Abbreviations:
CHEMICAL CARTRIDGE RESPIRATORS
AG = Acid gas
OV = Organic vapor
PF = Particulate pre-filter (N95)
HEPA = High-efficiency particulate air
95% = 95% dust/mist
Rubber boots
Rubber boots
Rubber boots
SECTION
Appx
1
B
Preface
March 2009
B-1
B-2
March 2009
Well No:
Depth:
Date:
Acid System:
On-Site Inventory Form
Chemical Information
Expiration Date
Lot No. / Supplier
Name
Fluid on Location:
Tank No.
1
2
3
4
5
Total, gal:
Starting Volume, gal
Required
Ending, gal:
Ending Volume, gal
Used
Total used:
Used Volume, gal
Well No:
Depth:
Date:
Acid System:
Tank No.
1
Well No:
Depth:
Date:
Acid System:
NaOH, mL
SG
Temp, F/C
Corrected SG
Acid Conc.
Additives Information:
Additive Name
Visual Inspection:
Remarks:
gal/Mgal
lb/Mgal
Volume, mL
Well No:
Depth:
Date:
Acid System:
Concentrations
Chemicals/
Additives
Concentrations
Tank No.:
Sample Location:
Concentrations
Chemicals/
Additives
Concentrations
Tank No.:
Sample Location:
Concentrations
Chemicals/
Additives
Concentrations
Tank No.:
Sample Location:
Well No:
Depth:
Date:
Acid System:
Stage
Number
Time,
min
Type of Acid:
Stage Volume,
gal
Temperature,
F/C
Viscosity,
cp @ 300 RPM
NaOH,
mL
SG
Acid Conc.
Well No:
Depth:
Date:
Acid System:
Time,
min
Gel
Loading
Viscosity,
cp at 300 RPM
Gel
Loading
SECTION
Appx
1
C
Preface
March 2009
C-1
C-2
March 2009
Well No:
Depth:
Date:
Acid System:
Yes
No
Remarks
Well No:
Depth:
Date:
Acid System:
Yes
No
Remarks
SECTION
Appx
1
D
Preface
March 2009
D-1
D-2
March 2009
Type of Request: