Acidizing Treatments

Quality Assurance for Acidizing Treatments

Part No. 101765409

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All information contained in this publication is confidential and proprietary property of Halliburton Energy Services, Inc. Any reproduction or use of these instructions, drawings, or photographs without the express written permission of an officer of Halliburton is forbidden. © 2009 Halliburton All Rights Reserved. Printed in the United States of America. Part No. 101765409




























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




























Section 4: Acid Systems Carbnate 20/20™ Acidizing Service....... Service.............................. ............................................ ............................................ ............................................ ....................... .. 4-2 Zonal Covera Coverage™ ge™ Acid (ZCA) System ....... ................ .................. .................. ................. ................. ................. ................ ................ ................ ............ .... 4-3 Hot Rock™ Acid (HRA) (HRA)........................ ........................ ...................... .............................................. ........................ ...................... ........................................ .................. 4-6 Carbonate Carbona te Completi Completion™ on™ Acid (CCA) System ......... ................ ............... ................ ................. .................. ................. ................ ................ .......... .. 4-8 Fines Recovery™ Acid System................ System..................................... ............................................ ............................................ ...................................... ................. 4-11 Carbonate Emulsion™ Acid (CEA) Service .................... ........................................ ........................................ ...................................... .................. 4-14 Carbonate Stimulation™ Acid (CSA) Service Service.................... ........................................ .......................................... ................................... ............. 4-17 Sandstone 2000™ Acidizing Service. Service...................... ......................................... ............................................ ........................ .................... ............................ ........ 4-20 Sandstonee Complet Sandston Completion™ ion™ Acid System ......... ................. ................. .................. .................. .................. .................. .................. .................. ............... ...... 4-21 Fines Control™ Acid System........... System.................................. ............................................ ............................................. ........................ ..................... ....................... 4-24 K-Spar™ Acid Acid......................... ......................... ......................... ...................... ................................................ .......................... ...................... .......................... .... 4-26 Volcanic™ Acid System ................... ........................................... ........................ ..................... ............................................ ............................................ ..................... 4-28 Silica Scale™ Acid System. System...................... .......................................... ............................................ ........................................... ...................................... .................. 4-31

Appendix A: Hazardous Material and PPE Selection Matrix Appendix B: Acidizing On-Site QC Example Forms Appendix C: Acidizing Equipment Check Example Forms Appendix D: Change Request Form



























SECTION Section

1

Preface

Introduction and Safety Overview This document is intended to provide a global standard set of procedures for performing acidizing jobs. The Th e objective is to improve the t he execution of designs design s being pumped down dow n the well, to increase productivity, to have consistency in the methods used by Halliburton at different locations, and to provide top-quality service to our customers. Quality control (QC) is the process of ensuring that the materials and equipment meet specifications and are delivered in proper condition at the well site. It is also important to ensure that the fluids prepared on location have similar properties to the fluids selected on the basis of the initial laboratory tests and to the parameters used in the design. Failure to carry out these quality-control checks can result in the treatment not being pumped exactly as designed. By implementing standard operating procedures for pre-job testing, during-job testing, real-time monitoring, and post-job reporting, along with appropriate safety precautions, Halliburton can help create a consistent, stable, safe, and environmentally acceptable work place. Providing all field personnel with quality assurance and QC guidelines for acidizing operations can help ensure that the customer receives exactly what the job proposal stipulates.




























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 Controls: Use in a well-ventilated area. Local exhaust ventilation should be used in areas without good cross ventilation.

•

A to select appropriate gloves. Hand Protection: See Protection: See Appendix A to

•

Skin Protection: Use Protection: Use full protective chemical-resistant clothing and rubber boots. (See Appendix A).

•

Eye Protection: Wear Protection: Wear chemical goggles and also a face shield if a splashing hazard exists.

•

A to select appropriate respiratory protection (respirator). Respiratory Protection: See Protection: See Appendix A to

•

Other Precautions: Eyewash Precautions: Eyewash fountains and safety showers must be easily accessible. Note

See Appendix A A for proper PPE selection. Select the PPE for the most stringent chemical exposure situation.

First Aid Measures •

Inhalation: If inhaled, remove victim to fresh air. If victim is not breathing, give artificial Inhalation: If 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 Skin: In minutes. Get medical attention. Remove contaminated clothing. Clothes contaminated with chemicals should be thoroughly washed before wearing them again. Note No te

•

Appl Ap ply y sod sodiu iumm-bi bica carb rbon onat atee so solu luti tion on at bu burn rn si site te,, rub rubbi bing ng co cont ntin inuo uous usly ly..

Eyes: In case of contact or suspected contact, immediately flush eyes with plenty of water for at Eyes: In 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 No te

When wa When wash shin ing g eye eyes, s, us usee a ge gent ntle le fl flow ow of wa wate terr whe when n rin rinsi sing ng.. A hea heavy vy st stre ream am of wa wate terr could damage the eyes. DO NOT use dry soda in the eyes.






























Hydrogen Fluoride (HF) Acid Safety Introduction HF acid is an extremely hazardous liquid. It can cause severe skin and eye irritation or deep-seated, slow-to-heal burns (the acid penetrates the skin and attacks the bones). In certain cases, exposure can prove fatal. For any major exposure to HF, immediate paramedic assistance is necessary.

PPE •

Engineering Controls: Use Controls: Use in a well-ventilated area. Local exhaust ventilation should be used in areas without good cross ventilation.

•

A to select appropriate gloves. Hand Protection: See Protection: See Appendix A to

•

Skin Protection: Use Protection: Use full protective chemical-resistant clothing and rubber boots. (See Appendix A).

•

Eye Protection: Wear Protection: Wear chemical goggles and also a face shield if a splashing hazard exists.

•

A to select appropriate respiratory protection (respirator). Respiratory Protection: See Protection: See Appendix A to

•

Other Precautions: Eyewash Precautions: Eyewash fountains and safety showers must be easily accessible. Calciumgluconate gel should be available on location. Note

See Appendix A A for proper PPE selection. Select the PPE for the most stringent chemical exposure situation.

First Aid Measures •

Skin: Skin contact with HF can cause severe burns. In case of contact, follow this procedure: Skin: Skin 1. Remove the victim victim to a safe safe location. location. Use Use PPE when when handling a contaminated contaminated victim. 2. Immediately Immediately flush the exposed exposed skin with with plenty of of soap and and water for at least 15 minutes. It It is critical to apply antidote as soon as possible.




























In case of contact or suspected contact, follow this procedure: 1. Imm Immedia ediatel tely y flush eyes eyes with plenty plenty of of water water for at least least 15 minutes minutes.. 2. Irrigate the eye repeat repeatedly edly with 500 to 1000 1000 mL of a 1% calcium calcium gluconate gluconate solution solution (mix calcium gluconate with water) applied through a syringe. 3. Get med medical ical atte attentio ntion n as as soon soon as as possib possible. le. 

Inhalation: HF acid produces pungent fumes on contact with air. These fumes can cause severe Inhalation: HF 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 Ingestion: Do medical attention. Never give anything by mouth to an unconscious person.

Important

Do not store samples of HF acid in glass jars/beakers. A lways use plastic. Proper PPE must be worn by all personnel when handling HF acid.

Hydrogen Sulfide (H 2 S) Safety Introduction Hydrogen sulfide (H2S) is a highly toxic, colorless gas, heavier than air, with the odor of rotten eggs. It is an irritating gas with a pungent odor that forms explosive mixtures with air. The maximum allowable concentration in an 8-hour day is 10 ppm of air (0.001% concentration of the gas). Death can occur rapidly with exposure to 600 ppm (0.05% H2S).

PPE •

Respiratory Protection: Positive-pressure Protection: Positive-pressure self-contained breathing apparatus.

•

Hand Protection: Impervious Protection: Impervious rubber gloves.




























Warning

Exposure to H2S can be deadly. Avoid unnecessary risks. Be aware of the concentration of gas present before doing any work.

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

Always be prepared for H2S when treating limestone or dolomite formations.

Emergency-Spill Procedure for Acid Introduction An emergency-spill procedure is required to provide guidance on the appropriate course of action to be taken in the event of an acid spill. It is important to ensure that the risk relating to the spill of any substance is effectively assessed and managed to help protect personnel and the environment. This can be achieved by ensuring that the job safety analysis (JSA) documents contain the proper procedures for the appropriate response in the event of an acid leak: •

Minor Min or lea leaks ks fro from m hose hoses/c s/conn onnect ection ionss

•

Major Ma jor le leaks aks fr from om aci acid d stor storag agee tank tankss

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: •

Pers Pe rsonn onnel el do do not pla place ce the themse mselve lvess at risk risk

•

Damage Dama ge to the envi environm ronment ent is minim minimize ized d and and contro controlled lled




























5. Check the the label on the the container container and identify identify any any hazardous hazardous properties properties of the chemica chemicall (hazard (hazard symbol, risk phrases, and safety phrases). Make sure MSDS is available and refer to the MSDS for details. 6. Identif Identify y appropriate appropriate PPE to protect you from exposure exposure to the chemical chemical and wear wear required required PPE. PPE. 7. Con Contai tain n and neut neutra raliz lizee the spi spill. ll. a. Spill containment. i. Stop the source source of the the spill by shutting shutting valves valves or temporarily temporarily plugging plugging any holes holes (if this this can be done safely). ii. Prevent the spill spill from contaminating contaminating surface/wate surface/waterr drains if they can be safely safely accessed. accessed. iii. Use sand or soda ash/sodium bicarbonate bicarbonate to form a bund around the spill spill to limit it from spreading before attempting to neutralize. b. Spill neutralization. i. Once the spill is contained contained,, neutralize neutralize the spill using using a reasonable reasonable quantity quantity of soda ash/sodium bicarbonate. Use the information in Table 1.1 as 1.1 as a guideline for the required amount of agent needed to neutralize the acid. Warning Warnin g

Significant heat will be generated Significant generated as the the acid is being being neutrali neutralized. zed. Spontaneo Spontaneous us combustion (fire) can occur during neutralization if materials are added quickly. Allow time for heat to dissipate.




























Table 1.1—Amount of Agent Required to Neutralize Acid Neutralizing Agent for 1,000 gal of Acid Sodium Carbonate (Soda Ash or K-35™ Buffering Agent), lb

Sodium Bicarbonate (K-34™ Breaker), lb

Calcium Carbonate (Limestone), lb

1

1 22

193

115

2

2 45

388

231

3

3 69

584

348

4

4 94

783

466

5

6 20

983

586

6

7 48

1,186

706

7.5

9 42

1,492

889

8

1,007

1,596

951

9

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

% HCl Acid Strength
























































SECTION Section

1 2

Preface

On-Site Quality Assurance Standards for Acidizing Treatments Overview This section presents a summary of the tests to be performed before, during, and after the job. The detailed procedures and format to be used to record the data and results are given in Section 3 and Appendix B and B and Appendix C. C.

Pre-Mobilization Preparation




























– Polyethylene: This Polyethylene: This lining is suitable for almost all chemicals that Halliburton pumps. How ever, 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 Rubber: This lining should be used for tanks that are used only for storing concentrations of HCl acid without additives. Important

Natural rubber will fail if solvents or acids containing a small amount of solvents (xylene or toluene) are stored in the tank. Also, small amounts of organic-based liquids, such as acetic acid and formic acid, will cause the liner to fail.

Note No te

If a na natu turral al-r -rub ubbe berr-li line ned d ta tank nk is le left ft emp mpty ty for mo more re th thaan on onee mo mont nth, h, it sh shou ould ld be filled with a weak salt solution or purged with nitrogen. Air (ozone) will prematurely deteriorate the liner.

Recommendations •

Whenever When ever possi possible, ble, insp inspect ect tank lini lining ng befor beforee use. use.

•

Avoid Avo id using using che chemica micals ls incom incompati patible ble with the lini lining. ng.




























Table 2.1—Specifications for Raw/Stock Acid Components

Maximum Allowable Concentration, ppm

Sulfate

400

Iron

20

Fluorides

25

Sulfites

100

Arsenic

1

Copper

1

Total other heavy metals

5

Organic chlorides

5

Organics (benzene, surfactants etc.)

1

Free chlorine and bromine

1




























Job Preparation General Mixing Guidelines When mixing acid blends, the general guideline for the order of addition is as follows: 1. Water 2. Disp Dispers ersant ant and/ and/or or mutu mutual al solv solvents ents 3. Co Corr rros osio ion n inh inhib ibit itor or 4. Acid 5. Sur Surfac factant tant// nonemuls nonemulsifie ifier/ r/ antislu antisludge dge agent agent 6. Ir Iron on-c -cont ontrol rol ad addit ditive ivess Important

Always add water first.

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.






























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 2.2 lists maximum limits for few parameters. However, these limits should not replace sound chemical or engineering principles. Not otee

Lab te Lab test stin ing g is reco com mmende ded d to confi firrm th thaat ther eree are no com omp pati tib bilit ity y pro rob ble lem ms between the water and acid.




























Seawater in Sandstones 

Seawater cannot Seawater cannot be used within within any stage of an HF acidizing acidizing treatme treatment nt (Sandstone (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 Seawater should not be be used in any acid blend blend intended intended for use in a sandstone sandstone formation 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 50g al/ft, then only 1.5 lb of precipitation precipit ation will occur per foot of interval. If this is too much for the customer, then seawater should not be used to prepare the acid.




























On the Day of Treatment Before pumping downhole, collect samples from each acid tank and test them for the following parameters: 

pH

•

Temperature

•

Acid strength

•

Spec Sp eciific grav aviity

Note

For ge gelled-acid sy systems, te test a sample fr from ea each ta tank fo for vi viscosity an and pH pH.




























•

Monitor Moni tor pH of the ret returns urns for futu future re acid acid trea treatmen tments. ts.

•

The amo amount unt of fluid fluid used depe depends nds on the the tubul tubular ar size size.. Table 2.3 lists 2.3 lists the recommended volumes for pickling a tubular with 15% HCl acid.

Table 2.3—Recommended Volume for Pickling a Tubular with 15% HCl Acid Size of Tubular, in.

Volume of Acid, gal per 1,000 ft of Tubular

2 3/8

85

2 7/8

110

3 1/2

140




























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 Neutralize the remaining remaining acid acid in the tank tank using the appropri appropriate ate quantity quantity of soda ash/sodium bicarbonate. Refer to the Table 1.1 for 1.1 for detailed information about the quantity required to neutralize the acid. 2. After removing removing neutralized neutralized acid acid from the tank, tank, add at least least 10 bbl of water water and 15 to 20 kg of sodium sodium






























•

Perf Pe rform orman ance ce highlig highlights hts/op /oper erat ation ional al issues issues – Job summary



























SECTION Section

Preface




























Sampling Chemicals/Water Scope: To obtain samples for QC testing.




























Measuring Temperature Scope: To determine the temperature of the acid/fluid system.




























Measuring Specific Gravity Scope: To measure the specific gravity of an acid/fluid sample.




































































































































































































































































































































































































































































































































































































































































































































































































•

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, inhaled, remove remove victim victim from area to to fresh air. If If victim victim is not breathing breathing,, give artifici artificial al respiration, respiration, preferably mouth-to-mouth. If breathing is difficult, give oxygen. Get medical attention.

Skin •

In case case of contact, immediat immediately ely flush flush skin with with plenty of soap and water water for at least least 15 minutes. minutes. Get Get medical attention. Remove contaminated clothing and launder before reuse.

Eyes •

In case of contact, contact, or suspected suspected contact, contact, immediate immediately ly flush eyes eyes with plenty plenty of water water for for at least least 15 minutes and get medical attention immediately after flushing.

Ingestion •

Do not induce vomiting. Slowly dilute with with 1 to to 2 glasses glasses of of water water or milk and and seek seek medical medical attention. Never give anything by mouth to an unconscious person.

Spills Environmental Precautionary Measures •

Prevent Pre vent from ente enterin ring g sewers sewers,, waterw waterways, ays, or low low areas. areas.

Procedure for Cleaning/Absorption 1. Isolate spills and and stop leaks leaks where safe. Contain Contain spills spills with sand sand or other other inert inert materials. materials. 2. Ne Neutr utral alize ize to pH of 6 to to 8. 8. 3. Sc Scoo oop p up up and and re remo move ve..

Handling Precautions •

Acids, Ferchek A Reducing Agent, Ferchek ® SC Iron-Control System, PEN-88 HT™ Avoid contact with eyes, skin, or clothing. Avoid breathing vapors. Wash hands after Surfactant: Avoid Surfactant: use. Launder contaminated clothing before reuse.

•

Fe-2 Iron-Sequestering Agent: Avoid Agent: Avoid creating or inhaling dust.

•

PEN-88M Surfactant: Do Surfactant: Do not consume food, drink, or tobacco in contaminated areas.




























Exposure Controls Engineering Controls •

Use in a well-ventila well-ventilated ted area. area. Local exhaust ventilatio ventilation n should be used used in areas areas without without good good cross ventilation.

•

Ferchek SC, PEN-88 HT: HT : In high concentrations, supplied air respirator or a self-contained breathing apparatus may be required.




























Fines Control™ Acid System Introduction Fines Control acid system is a retarded HF-acid system designed for treating sandston e formations. Fines Control acid 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 stabilizer. Note

If ca carbonates ex exceed 5% 5%, Al Alchek™ agent should be be used in in pl place of FE FE-1A. If permeability is less than 30 md, Cla-Sta ® XP clay-stabilizing agent should be used instead of Cla-Sta FS compound.

Application/Advantages 1. Retarded Retarded reaction with sand and and silica to promote promote deep deep damage removal removal and and improve compatibi compatibility lity with feldspar-containing formations. 2. It is primarily primarily used for formati formations ons containing containing significant significant kaolinite kaolinite and/or and/or illite. illite. 3. It can can also be effective effective in formations formations that that are are HCl-acid-se HCl-acid-sensitive. nsitive. 4. Dee Deeper per penetr penetrati ation on of live live HF acid acid into the the formati formation. on. 5. Clay stabilizer stabilizer to control control fines fines migration migration during during and following the treatment. treatment.

Health and Safety Precautions Potential Chemicals Involved: Fines Involved: Fines Control acid, HF acid, FE-1A, PEN-88M surfactant, PEN-88 HT surfactant, Cla-Sta FS compound, Cla-Sta XP clay-stabilizing agent, Alchek agent.

Hazard Overview •

Acids and Alchek Agent: Can Agent: Can cause eye and skin burns and respiratory irritation. Can be harmful if swallowed.

•

Cla-Sta FS Compound, Cla-Sta XP Clay-Stabilizing Agent, PEN-88M Surfactant, PEN-88 HT Surfactant: Can cause eye, skin, and respiratory irritation. Can be harmful if swallowed.

•

PEN-88M and PEM-88 HT Surfactants: Can Surfactants: Can cause headaches, dizziness, and other centralnervous-system effects. Combustible.

•

FE-1A: Reacts violently with water.




























Skin •

In case of contact, contact, immediately immediately flush skin skin with plenty plenty of soap and water for for at least 15 minutes. Get medical attention. Remove contaminated clothing and launder before reuse.

Eyes •

In case of contact, contact, or suspected suspected contact, contact, immediate immediately ly flush eyes eyes with plenty of water for for at least least 15 minutes and get medical attention immediately after flushing.

Ingestion •

Do not induce vomiting. Slowly dilute with with 1 to 2 glasses glasses of water water or milk and and seek seek medical medical attention. Never give anything by mouth to an unconscious person.


Prevent Pre vent from ente entering ring sew sewers, ers, wat waterwa erways, ys, or low low areas. areas.

Procedure for Cleaning/Absorptio Cleaning/Absorption n 1. Isolate spills and and stop leaks leaks where safe. Contain spills spills with sand sand or other other inert inert materials. materials. 2. Ne Neutr utral alize ize to pH of 6 to to 8. 8. 3. Sc Scoo oop p up up and and re remo move ve..


Acids, Cla-Sta® Compound Additive, Cla-Sta ® XP Clay-Stabilizing Agent, PEN-88 HT™ Surfactant: Avoid contact with eyes, skin, or clothing. Avoid breathing vapors. Wash hands after use. Launder contaminated clothing before reuse.

•

PEN-88M Surfactant: Do Surfactant: Do not consume food, drink, or tobacco in contaminated areas.


Use in a well-ventila well-ventilated ted area. area. Local exhaust ventilati ventilation on should be used used in areas areas without without good good cross ventilation.

•

PEN-88 HT Surfactant: When used in high concentrations, a supplied air respirator or self-contained breathing apparatus might be required.




























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 should be used where where the the formation formation contains contains K-Spar K-Spar acid and/or and/or illite illite as the dominant dominant mineral mineral (Overall content ≥ 10%)

•

Since the fluorosilica fluorosilicates tes are are less soluble at at lower tempera temperature, ture, K-Spar acid should should be used in most formations containing significant sodium feldspars at temperatures below 175°F.

•

Contain Con tainss Fe-1A Fe-1A for iron contr control ol and pre prevent venting ing alumin aluminum um scalin scaling. g.

•

Contains clay stabilize stabilizerr to control fines migration during and following following the treatment. treatment.

Note

If ca carbonates ex exceed 5% 5%, Al Alchek ™ agent sh should be be used in instead of FE FE-1A. If permeability is less than 30 md, Cla-Sta ® XP clay-stabilizing agent should be used instead of Cla-Sta FS compound.

Health and Safety Precautions Potential Chemicals Involved: K-Spar Involved: K-Spar acid, HCl acid, HF acid, FE-1A, PEN-88M surfactant, PEN-88 HT surfactant, Cla-Sta FS compound, Cla-Sta XP clay-stabilizing agent, and Alchek agent.

Hazard Overview •

Acids, Ferchek Ferchek SC: May May cause eye and and skin burns. burns. May May cause respir respiratory atory irritation. irritation. May be harmful if swallowed.

•

Cla-Sta FS Compound, Cla-Sta XP Clay-Stabilizi Clay-Stabilizing ng Agent: Can 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

•

Alchek Agent: Can Agent: Can cause eye, skin, and respiratory burns. FE-1A: Reacts violently with water.































If inhaled, inhaled, remove remove victim victim from area to to fresh air. If victim is is not breathing, breathing, give give artificial artificial respira respiration, tion, preferably mouth-to-mouth. If breathing is difficult, give oxygen. Get medical attention.

Skin •

In case of contact, contact, immediately immediately flush skin skin with plenty plenty of soap and water for for at least 15 minutes. Get medical attention. Remove contaminated clothing and launder before reuse.

Eyes •


Ingestion •

Do not induc inducee vomiting vomiting.. Slowly Slowly dilute dilute with with 1 to 2 glasses glasses of water water or milk and and seek seek medical medical attention. Never give anything by mouth to an unconscious person.


Prevent Pre vent from ente entering ring sew sewers, ers, wat waterw erways, ays, or low low areas. areas.

Procedure for Cleaning/Absorption 1. Isolate spills and and stop leaks leaks where safe. Contain spills spills with sand sand or other other inert inert materials. materials. 2. Ne Neutr utral alize ize to pH of 6 to to 8. 8. 3. Sc Scoo oop p up up and and re remo move ve..


Acid, Cla-Sta ® Compound Additive, Cla-Sta ® XP Clay-Stabilizing Agent, PEN-88 HT™ Avoid contact with eyes, skin, or clothing. Avoid breathing vapors. Wash hands after Surfactant: Avoid Surfactant: use. Launder contaminated clothing before reuse.




























Volcanic™ Acid System Introduction Volcanic acid system is an organic-HF-acid acidizing-blend developed to replace acetic-HF-acid and formic-HF-acid fluids. Two formulations of Volcanic acid system have been developed—Volcanic acid system I and Volcanic acid system II. Volcanic acid system I contains citric acid (Fe-2™ iron-sequestering agent), ABF (AF cannot be used as the fluoride source because it has the potential for secondary precipitation, which cannot be avoided with this formulation), NH4Cl (Clayfix™ clay-control material), and Pen-88M/Pen-88 HT™ surfactant. Volcanic acid system II is based on Alchek™ agent and can be prepared with either ABF or AF.


Compatible with HCl-sens Compatible HCl-sensitive itive minerals minerals (for example, example, chlorite chlorite,, zeolites, zeolites, and and other clays at temperatures above their HCl-decomposition temperature).

•

Can be be used at higher higher temperatur temperatures es than HCl-base HCl-based d fluids without decomposing decomposing clays or or zeolites zeolites or having high corrosion rates. This system is much easier to inhibit to prevent excessive corrosion.

•

Avoids Avoi ds seconda secondary ry precipi precipitati tation on observed observed with with formic-HF formic-HF acid acid and aceticacetic-HF HF acid. acid.

•

Contains NH4Cl to prevent swelling of water-sensitive clays.

•

Typical Typi cally, ly, this this acid acid system system will will not cause cause slud sludging ging with with crude crude oils. oils.

Not otee

MSAA-III™ cor orro rosi sion on--inh nhiibi bito torr sho hou uld be us useed with bot oth h Vol olccani nicc acid sy sysste tem ms.

Health and Safety Precautions Potential Chemicals Involved: Volcanic Involved: Volcanic acid systems I or II, ABF (solid), Fe-2 iron-sequ estering agent, AF, Alchek agent, AF-61™ emulsifier, PEN-88M surfactant, PEN-88 HT surfactant, Clayfix clay-control material.




























•

Volcanic™ Acid System II, AF: Can AF: Can cause eye, skin, and respiratory irritation. Can damage bones. Can be harmful if swallowed.

•

Fe-2™ Iron-Sequestering Agent: Can Agent: Can cause eye, skin, and respiratory irritation. Airborne dust can be explosive.


If inhaled, inhaled, remove remove victim victim from area to to fresh air. If victim is is not breathing, breathing, give give artificial artificial respirat respiration, ion, preferably mouth-to-mouth. If breathing is difficult, give oxygen. Get medical attention.

Skin •

In case of contact, contact, immediately immediately flush skin skin with plenty plenty of soap and water for at least 15 minutes. Get medical attention. Remove contaminated clothing and launder before reuse.

Eyes •


Ingestion •

Acids, PEN-88M Surfactant, PEN-88 HT™ Surfactant, Clayfix™ Clay-Control Material, ABF, AF, Fe-2 Iron-Sequestering Agent, Alchek™ Agent: Do not induce vomiting. Slowly dilute with 1 to 2 glasses of water or milk and seek medical attent ion. Never give anything by mouth to an unconscious person.


Prevent Pre vent from ente entering ring sew sewers, ers, wat waterw erways, ays, or low low areas areas..

Procedure for Cleaning/Absorption 1. Isolate spills and and stop leaks leaks where safe. Contain spills spills with sand sand or other other inert inert materials. materials.





























Use in a well-ventilate well-ventilated d area. area. Local exhaust ventilati ventilation on should be used in areas areas without good cross cross ventilation.

•

PEN-88 HT™ Surfactant: When used in high concentrations, a supplied air respirator or self-contained breathing apparatus might be required.

•

Fe-2™ Iron-Sequestering Agent: A Agent: A 95% dust/mist respirator is required.




























Silica Scale™ Acid System Introduction Silica Scale acid system is the old, regular HF acid or mud acid (12% HCl acid-3% HF acid).


This acid acid system system is recomme recommended nded for use only where the formation formation is 100% quartz and contains contains no clay minerals.

•

Used for remova removall of silica silica scale from the wellbore in areas areas where silica scale scale can can form (geother (geothermal mal wells or steam flooding).

Not otee

This acid sy sysste tem m is no nott to to be be us used ed in no norm rmal al--for orm mati tio on HF HF-acid idiizin ing g tr trea eatm tmeents ts.. Hig High h HF-acid concentrations would result in secondary precipitation near the wellbore.

Health and Safety Precautions Potential Chemicals Involved: Silica Involved: Silica Scale acid system, HCl acid, HF acid.

Hazard Overview •

Can cause eye and skin burns. Can be harmful if swallowed. Acids: Can Acids:

•

Silica Scale Acid System: Can damage bones.

First Aid Inhalation • Skin

If inhaled, inhaled, remove remove victim victim from area to to fresh fresh air. If victim victim is not breathi breathing, ng, give artifici artificial al respiration, respiration, preferably mouth-to-mouth. If breathing is difficult, give oxygen. Get medical attention.






























Ingestion (Acids) •

Do not induce induce vomit vomiting. ing. Slowl Slowly y dilute dilute with 1 to 2 glass glasses es of water water or milk milk and and seek seek medical medical attention. Never give anything by mouth to an unconscious person.


Prevent Pre vent fro from m enteri entering ng sewers sewers,, water waterways ways,, or low area areas. s.

Procedure for Cleaning/Absorption 1. Isolate spills and and stop leaks leaks where safe. Contain Contain spills spills with sand sand or other other inert materia materials. ls. 2. Neutral Neutralize ize with with lime slurry, slurry, limestone, limestone, or soda ash. Neutralize Neutralize to pH of 6 to 8. 3. Sc Scoo oop p up up and and re remo move ve..

Handling Precautions (Acids) •

Avoid contact contact with with eyes, eyes, skin, or clothing. clothing. Avoid Avoid breathing breathing vapors. vapors. Wash hands after after use. use. Launder Launder contaminated clothing before reuse.

Exposure Controls Engineering Controls



























SECTION Appx

1 A

Preface

Hazardous Material and PPE Selection Matrix Appendix A contains a copy of the Hazardous Material and PPE Selection matrix.






















































Hazardous Material and Personal Protective Equipment (PPE) Selection Matrix Emergency Phone Number: (281) 575-5000

Product Name

s e v o l G

n o r p A

l a s e c l i m g e g h o G C

d l e i h s e c a F

r o t a t r s i i p M s , e t s R u e D m u F

l e r o a c g t a i d r i i r m p e t r s h a e C C R

BUT

X

X

X

AF Ad di ti ve

CG

X

X

X

AF-61™ Emu lsif ls if ier

CG

X

X

X

OV

NEO/NIT

X

X

X

OV/AG

X

X

OV/AG OV/AG/P F

HEPA

CG

AS-5™ An ti-Slu ti -Slu dg in g Ag ent

CG

X

X

X


CG

X

X

X


CG

X

X

X

AS-10 An ti -Slu dg in g Ag ent

CG

X

X

X

AS-11a An ti -Slu dg in g Ag ent

NEO

X

X

X

AS-11e An ti -Slu dg in g Ag ent

CG/VIT/ BUT/ NEO

X

X

X

OV

X

X

OV/AG

®

Cla-Sta FS Compound

CG

OV/AG

Clayfix™ Clay-Contr Clay-Contr ol Material

X

Wear a face shield if splashing hazard exists. Rubber boots

Supplied air respirator might be required if methanol released

Possible

OV/AG/P F OV/AG/P F Neoprene coated apron or clothing is required Supplied air respirator might be required

95%

CG

X

X

X

OV/AG/P F

CG

X

X

X

OV/PF

CG

X

X

X

®

Cla-Sta XP Clay-Stabili Clay-Stabili zing Agent Ag ent

Comments

Self-contained breathing apparatus might be required.

Possible

Alch Al ch ek™ Ag ent (Scale In hi bi to r)

BF-1™ Buffering Agent

l l k a r e e v v y o T C

Solid, safety glasses or goggles

ABF Add itiv it ive e

AF-70 Emu lsif ls ifier ier

e r g r e n o h i t y a r p l s p i p o p s m u e t S R A

OV/AG/P

Possible X

Rubber boots Engineering controls required



























Carbonate Stimulation™ Acid (CSA) Service

CG

CCA-H2S Hydrogen Sulfide Scavenger

NIT

Diesel No. 2 FDP-S769-05 (Iron-Reducing Agent Ag ent ) FE-1A Acidizing Compound (Additive) FE-2™ FE-2™ Iron-Sequestering Iron-Sequestering Agent

CG CG/NIT/ NEO/PVC

X

X

X

X

CG

X

X

CG

X

X

®

WG

OV/AG

X

X

Rubber boots Solid, safety glasses or goggles

95% X

CG

Ferchek Ferric-Iron Ferric-Iron Inhibitor

X

X

®

Ferchek A Redu cing ci ng Agen t

X

OV 95%

AG

X

Wear a face shield if splashing hazard exists.

OV/AG

X

Rubber boots

95%


95%

Solid, dust-proof goggles

95%


®

Ferchek SC Iron-Control Process

CG

X

X

AG

Fines Control™ Iron-Oxide Removal And Surface-Passivator Service

CG

X

X

Fines Recovery™ Iron-Oxide Removal And Surface-Passivator Service

CG

X

G-Sperse G-Sperse Disp ersant

CG

HAI-GE Corrosion Inhibitor

X

Rubber boots, supplied air respirator might be required

AG

X

Rubber boots

X

OV/AG

X

Rubber boots

X

X

OV/AG Possible

CG

X

X

OV/AG

Possible

X

Rubber boots, supplied air respirator might be required

HAI-81M HAI-81M™ ™ Acid Corr osion Inhibitor

CG

X

X

OV/AG

Possible

X

Rubber boots, supplied air respirator might be required if methanol released

HAI-85M HAI-85M™ ™ Acid Corr osion Inhibitor

CG

X

X

OV/AG

Possible

X

HAI-202 Corrosion Inhibitor

CG

X

X

OV/AG

Possible

X

HAI-303 Corrosion Inhibitor

CG

X

X

OV/AG

Possible

X

Possible

Respirator might be required

Rubber boots, supplied air respirator might be required Rubber boots, supplied air respirator might be required Supplied air respirator might be required if methanol is





























HAI-OS Corrosion Inhibitor

CG

HII-12 HII-124B™ 4B™ Corro Corro sion-Inhib itor Intensifier

CG

HII-12 HII-124C™ 4C™ Inhib Inhib itor Intensifier

CG

HII-12 HII-124F™ 4F™ Corro Corro sion -Inhibitor Intensifier

CG

HII-12 HII-124T 4T Corr Corr osion Inhibit or Intensifier

CG

X

X

X

X

HEPA

X

X

X

95%

X

X

X

X

X

CG

X

X

X

OV/PF

CG

X

X

OV/AG

X

Rubber boots

Hot Rock™ Acid (HRA) (HRA) System (Solvent/Acid)

CG

X

X

OV/AG

X

Rubber boots

HV-60™ HV-60™ Intensifier Ag ent

WG

Hydrochloric (HCl) Acid

CG

X

X

AG

X

Rubber boots

Hydrofluoric (HF) Acid

CG

X

X

AG

X

Rubber boots

HII-50 HII-500M™ 0M™ Corro Corro sion-Inhib itor Intensifier HII-600 Corrosion Inhibitor Intensifier

OV/AG

AG

Possible

X

Rubber boots, supplied air respirator might be required if methanol is released Solid, safety glasses or goggles Solid, safety glasses or goggles

X

X

Rubber boots Solid, safety glasses or goggles; engineering controls required

95%

Solid, safety glasses or goggles, respirator might be required

95% Possible



























SCA-130 SCA-130™ ™ Sulfide-Cracking Inhibitor

CG

X

X

X

OV

PVC/OR

X

X

X

OV Possible

X

X

®

SGA-HT Acid System Gelling Agent Ag ent (Flo ccul cc ul ent ) SGA-I SGA-I Gellin Gellin g Agent

BUT

SGA-II™ SGA-II™ Acid Acid Gelling Agent

CG

X

X

X

OV/AG/P F OV

SGA-III™ Gelling Agent

CG

X

X

X

OV

SGA-V™ SGA-V™ Gellin Gellin g Ag ent

CG

X

X

X

OV/PF possible

Silica Scale™ Acid System (Solvent/Acid)

CG

X

X

OV/AG

SP™ Breaker Breaker Ag ent

BUT

X

Volcanic™ Acid System I (Solvent/Acid)

CG

Volcanic™ Acid System II (Solvent/Acid)

CG

XL-1™ Crossli nker Zonal Coverage™ Acid (ZCA)

CG CG

X

X

Respirator might be required X

Rubber boots

Respirator might be required X

95%

Rubber boots Solid, dust-proof goggles

X

X

95%

X

X

OV/AG

X

X

AG/PF

X

X

AG

X

Rubber boots Rubber boots

X

Rubber boots



























SECTION Appx

1 B

Preface

Acidizing On-Site QC Example Forms






















































Halliburton Energy Services Acidizing Production Enhancement Customer: Formation: Ticket No.:

Well No: Depth:

Date: Acid System: On-Site On-Site Inventor y Form

Name

Chemical Chemical Information Expir ation Date Lot No. / Suppl ier

Required

Chemical Chemical Amount s on Location Befor e Aft er

Used






























Well No: Depth:

Date: Acid System:

On-Site On-Site Water Water Analysis An alysis Record Record Form Parameters

Tank No. 1

2

3

4

5

6

7

8




























Well No: Depth:

Date: Acid System:

Pre-Job Pre-Job Acid Check Check Sheet Sheet Acid Ac id Tank

NaOH, NaOH, mL

SG

Temp, °F/°C

Corrected Corr ected SG

Acid Ac id Conc. Co nc.




























Well No: Depth:

Date: Acid System:

Pre-Job Gel Check Sheet Chemicals/ Ad di ti ves

Concentrations

Chemicals/ Ad di ti ves

Concentrations

Tank No.:

Sample Location:




























Well No: Depth:

During-Job Check Sheet For Acid Treatment Type of Acid :

Date: Acid System:




























Well No: Depth:

Date: Acid System:

During-Job Gel Gel QC Testin Testin g

Stage

Time, min

Gel

pH

Base Gel Data Temperature,

Viscosity,

Gel

Cross lin ked Gel Data Data Temperature, pH

Viscosity,













































































































































































Acidizing Treatments

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