JET_Manual_10_v2_0_OnlinePDF_4221679_01.pdf

Version 2.0

JET Manual 10

Acid Storage, Handling, Transportation, and

Mixing

JET Manual 10 Acid Storage,Handling, Transportation, andMixingReference: InTouch content ID# 4221679Version: 2.0Release Date: 04-Jun-2013EDMS UID: 1656413344Produced: 04-Jun-2013 16:13:09Owner: WIS T&D, WS T&DAuthor: InTouch-CTS, InTouch-OSP,

InTouch-Stimulation, PPC-SET

Private JET 10, JET Manual 10, WS Training &Development, Acid Storage, Acid Handling , AcidTransportation, Acid Equ ipment, Mixing, Spil lsand Disposal, Acid

Copyright 2013 Schlumberger, Unpublished Work. All rights reserved.

JET Manual 10 / Legal Information

Legal Information

Copyright 2013 Schlumberger, Unpublished Work. All rights reserved.

This work contains the confidential and proprietary trade secrets of Schlumbergerand may not be copied or stored in an information retrieval system, transferred,used, distributed, translated or retransmitted in any form or by any means,electronic or mechanical, in whole or in part, without the express writtenpermission of the copyright owner.

Trademarks & Service marks

Schlumberger, the Schlumberger logotype, and other words or symbols usedto identify the products and services described herein are either trademarks,trade names or service marks of Schlumberger and its licensors, or are theproperty of their respective owners. These marks may not be copied, imitatedor used, in whole or in part, without the express prior written permission ofSchlumberger. In addition, covers, page headers, custom graphics, icons, andother design elements may be service marks, trademarks, and/or trade dressof Schlumberger, and may not be copied, imitated, or used, in whole or in part,without the express prior written permission of Schlumberger.

A complete list of Schlumberger marks may be viewed at the SchlumbergerOilfield Services Marks page: http://markslist.slb.com

Marks of Schlumberger include but may not be limited to CemCADE*,DeepSTIM*, i-District*, i-Handbook*.

PrivateCopyright 2013 Schlumberger, Unpublished Work. All rights reserved.W

IST&D,W

ST&D\InTouch-CTS,InTouch-OSP,InTouch-Stimulation,PPC-SET\InTouchcontentID#4221679\2.0\ReleaseDate:04-Jun-2013\EDMSUID:1656413344\Produced:04-Jun-201316:13:09

JET Manual 10 / Document Control

Document ControlOwner: WIS T&D, WS T&D

Author: InTouch-CTS, InTouch-OSP, InTouch-Stimulation, PPC-SET

Reviewer: Steve Davies

Approver: InTouch-Stimulation

Contact InformationName: WIS T&D, WS T&DLDAP Alias: WS-PPC-TechCom

Revision HistoryVersion Date Description Prepared by

2.0 04-Jun-2013 Revised the manual to include the latest acidstorage, handling, transportation, and mixinginformation. Converted the manual fromInDesign to XML format in EDMS.

Author: Deepa Jain (WIST&D), Muhamad Arifin(InTouch-CTS), Jeff Beckel(InTouch-OSP), Steve Davies(InTouch-Stimulation), DennisJohnson (PPC-SET), JocelynCampitelli (PPC-TechCom)

1.0 31-Jan-2007 First version of the manual. Author: WS Training &Development


IST&D,WST&D\InTouch-CTS,InTouch-OSP,InTouch-Stimulation,PPC-SET\InTouchcontentID#4221679\2.0\ReleaseDate:04-Jun-2013\EDMSUID:1656413344\Produced:04-Jun-201316:13:09

JET Manual 10 / Regulatory Compliance

Regulatory Compliance

Waste managementIMPORTANT INFORMATION FOR CORRECT DISPOSAL OF THE EQUIPMENTThis symbol means that the equipment cannot be discarded in a rubbish-bin. Atits end of life, the equipment and/or its components must be treated, followingSchlumberger Environmental procedures, in compliance with Schlumberger QHSEPolicy and applicable laws and regulations on waste management.



JET Manual 10 / Foreword

ForewordNew releases of this document supersede any other version. The most currentversion of the document is in www.InTouchSupport.com.

If you have a printed copy, check the "Release Date" against the content inInTouch to be sure you have the most current version.

This document is OBSOLETE when printed.



vi JET Manual 10 / Table of Contents vi

Table of Contents

Regulatory Compliance __________________________________________ iv

Foreword _________________________________________________________ v

1 Introduction ____________________________________________________ 1-11.1 Learning Objectives __________________________________________ 1-21.2 Safety Warning ______________________________________________ 1-2

2 Acid Properties and Hazards ___________________________________ 2-12.1 Definition of an Acid __________________________________________ 2-12.2 Applications _________________________________________________ 2-22.3 Acid Properties ______________________________________________ 2-2

3 Use of Acids in the Oilfield _____________________________________ 3-13.1 Current Oilfield Acid Applications ______________________________ 3-13.2 Historical Background ________________________________________ 3-23.3 Acid System Selection _______________________________________ 3-33.4 Description of Acids Used in the Oilfield _______________________ 3-53.5 Acid Additives _______________________________________________ 3-8

4 Safety Considerations __________________________________________ 4-14.1 Safety Standards ____________________________________________ 4-14.2 Responsibilities ______________________________________________ 4-24.3 Personal Protective Equipment _______________________________ 4-34.4 Hazard Communication Documents ___________________________ 4-74.5 Transportation ______________________________________________ 4-14

5 Acid Supply ____________________________________________________ 5-15.1 Acid Supply Packaging _______________________________________ 5-15.2 Material Specifications _______________________________________ 5-35.3 Procedure to Receive Acid at the District ______________________ 5-35.4 Inventory Control ____________________________________________ 5-4

6 Acid Storage ___________________________________________________ 6-16.1 Safety Equipment ___________________________________________ 6-116.2 Acid Storage Tanks _________________________________________ 6-186.3 Fume Scrubber _____________________________________________ 6-246.4 Water Storage ______________________________________________ 6-276.5 Acid Mix/Transfer Tank ______________________________________ 6-286.6 Liquid Additive System ______________________________________ 6-30



vii JET Manual 10 / Table of Contents vii

6.7 Dry Additive System ________________________________________ 6-316.8 Pipe Work, Valves, and Fittings ______________________________ 6-316.9 Acid Transfer _______________________________________________ 6-326.10 Liquid Additive Pumps _______________________________________ 6-396.11 Transfer Hoses and Connections ____________________________ 6-40

7 Acid Transport Equipment _____________________________________ 7-17.1 Mobile Acid Transporter ______________________________________ 7-17.2 Acid Transport Tanks _________________________________________ 7-3

8 Acid Tank and Transport Equipment Maintenance ______________ 8-18.1 Tank Maintenance ___________________________________________ 8-28.2 Trailer and Tractor ___________________________________________ 8-78.3 Additional Testing and Inspection _____________________________ 8-98.4 Acid Plant Housekeeping and Maintenance ____________________ 8-9

9 Acid Mixing Procedures and Calculations ______________________ 9-19.1 HCl-Specific Calculations _____________________________________ 9-19.2 Acetic Acid __________________________________________________ 9-39.3 Mud Acid ____________________________________________________ 9-49.4 Clay Acid ____________________________________________________ 9-59.5 Other Acids __________________________________________________ 9-59.6 AcidMIX Formulator __________________________________________ 9-5

10 Operating Requirements and Procedures _____________________ 10-1

11 Acid Spills and Disposal ______________________________________ 11-111.1 Reporting ___________________________________________________ 11-211.2 Spill Prevention and Control Plan ____________________________ 11-311.3 MSDSs _____________________________________________________ 11-411.4 Spill Kits ____________________________________________________ 11-411.5 Disposal ____________________________________________________ 11-5

12 Matrix Key Service Quality Requirements _____________________ 12-1

13 Check Your Understanding ____________________________________ 13-1



viii JET Manual 10 / List of Figures viii

List of Figures

2-1 Measuring Specific Gravity with a Hydrometer (Read at the Bottom of theMeniscus)_________________________________________________________ 2-3

2-2 pH Scale__________________________________________________________ 2-42-3 pH Meter__________________________________________________________ 2-53-1 Pumping Acid in the Old Days ______________________________________ 3-23-2 Limestone_________________________________________________________ 3-43-3 Sandstone ________________________________________________________ 3-44-1 Goggles __________________________________________________________ 4-44-2 Face Shield _______________________________________________________ 4-44-3 Protective Suit_____________________________________________________ 4-54-4 Respirator_________________________________________________________ 4-64-5 Breathing Mask____________________________________________________ 4-64-6 US Chemical Label for 15% HCI___________________________________ 4-104-7 EU Chemical Label for 33% HCI___________________________________ 4-114-8 Canadian Chemical Label for 15% HCI_____________________________ 4-124-9 Fire Diamond NFPA 704 __________________________________________ 4-134-10 Transport Placards _______________________________________________ 4-144-11 ADR TREM Card for 15% HCl_____________________________________ 4-155-1 Commercial Acid Transporter_______________________________________ 5-15-2 Acid Railcar in Kazakhstan _________________________________________ 5-15-3 Acid Tote Tank (IBC) _______________________________________________ 5-25-4 220-Liter Acid Drums ______________________________________________ 5-26-1 Acid Storage Tanks at a Schlumberger Location _____________________ 6-16-2 Fume Scrubber with Electric Water Pump ___________________________ 6-26-3 Acid and Water Storage Tanks______________________________________ 6-26-4 Wilden Transfer Pumps and Acid Mix Tank __________________________ 6-26-5 Acid Mixing Tank with Electric Paddle _______________________________ 6-26-6 Liquid Additive Storage Tanks and Pumps___________________________ 6-26-7 Acid Loading Area with Loading Arm/Hose __________________________ 6-26-8 Acid Storage Tanks and Loading Area ______________________________ 6-36-9 Control Panel for Acid Plant ________________________________________ 6-36-10 Liquid Additive Storage Tanks and Fume Scrubbers__________________ 6-36-11 Liquid Additive Storage Totes, Fume Scrubbers and Loading Arm_____ 6-36-12 20,000 galUS Acid Storage Tanks with Suction and Filler-Up Lines____ 6-46-13 Rear of Acid Storage Tanks ________________________________________ 6-46-14 Acid Valve and Suction on Acid Storage Tanks ______________________ 6-46-15 Restricted Access to Acid Plant_____________________________________ 6-46-16 General View of Acid Storage Tanks, Water Supply Tank, and Fume Scrubber

(with Lagged Point) ________________________________________________ 6-56-17 Acid Storage Tanks, Piping, and Walkway (Notice Secondary Containment

Wall)______________________________________________________________ 6-56-18 Eye Wash Station (Notice Lagging for Cold Weather) ________________ 6-56-19 Acid Plant with Acid Railcar to be Offloaded _________________________ 6-56-20 Acid Bulk Plant Tank _______________________________________________ 6-6



ix JET Manual 10 / List of Figures ix

6-21 Manifolding Between Acid Tanks____________________________________ 6-66-22 2 x 30,000-galUS Rubber Lined Acid Tanks and Fume Scrubber with

Secondary Containment and Warning Signs_________________________ 6-66-23 Safety Shower and Equipment at Loading Point _____________________ 6-66-24 Acid Transfer Pumps_______________________________________________ 6-66-25 Acid Bulk Plant ____________________________________________________ 6-76-26 Acid Storage Plant_________________________________________________ 6-76-27 Bakersfield, California, Acid Bulk Plant ______________________________ 6-76-28 Loading Acid, Villahemosa, Mexico (View 1)_________________________ 6-76-29 Loading Acid, Villahemosa, Mexico (View 2)_________________________ 6-76-30 Galaxie Stimulation Vessel _________________________________________ 6-86-31 BIGORANGE 25 Stimulation Vessel ________________________________ 6-86-32 DeepSTIM Stimulation Vessel ______________________________________ 6-96-33 DeepSTIM III Stimulation Vessel____________________________________ 6-96-34 DeepSTIM Acid Storage __________________________________________ 6-106-35 BIGORANGE XVIII (North Sea)____________________________________ 6-106-36 BIGORANGE XVIII Liquid Additive Storage and Pumps _____________ 6-106-37 BIGORANGE XVIII _______________________________________________ 6-116-38 Revetment Area Before the Installation of Acid Tanks _______________ 6-126-39 Protective Lining Laid in Acid Tank Area, View 1 ____________________ 6-136-40 Protective Lining Laid in Acid Tank Area, View 2 ____________________ 6-136-41 Safety Signs on Acid Tank_________________________________________ 6-146-42 Safety Shower and Eye Wash Station______________________________ 6-156-43 Typical Mobile Spill Kit ____________________________________________ 6-176-44 Spill Kit Contents _________________________________________________ 6-176-45 12,000 galUS HDXLPE Acid Storage Tank _________________________ 6-196-46 Schematic of Acid Tank ___________________________________________ 6-206-47 15,000 galUS Rubber-Lined Acid Tank _____________________________ 6-216-48 6,000 galUS Butyl-Lined Acid Tank ________________________________ 6-216-49 Acid Fume Scrubber ______________________________________________ 6-246-50 Schematic of Acid Fume Scrubber _________________________________ 6-256-51 Marsh Pump Used for Fume Scrubber _____________________________ 6-266-52 Fume Scrubber Absorption Efficiency ______________________________ 6-276-53 Acid Mix Tank ____________________________________________________ 6-296-54 Liquid Additive Tank (TuffTank II) __________________________________ 6-306-55 Dry Powder Mixer Schematic______________________________________ 6-316-56 Delasco Pump (SUS-239)_________________________________________ 6-336-57 Delasco Pump Schematic _________________________________________ 6-346-58 Wilden Pump (SUS-271), Example of Chugger Pump _______________ 6-356-59 Wilden Pump Schematic __________________________________________ 6-366-60 Ramparts Acid Centrifugal Pump __________________________________ 6-376-61 March Series-10 Centrifugal Pump_________________________________ 6-386-62 Liquid Additive Skid (SUS-533) ____________________________________ 6-396-63 2-in WECO Figure 206 Union______________________________________ 6-416-64 Hose for Wilden and Delasco Pumps ______________________________ 6-426-65 4-in Orange Hose Covers on Discharge Lines ______________________ 6-427-1 STF-151 Acid Transporter__________________________________________ 7-17-2 STF-144 Acid Transporter__________________________________________ 7-2



x JET Manual 10 / List of Figures x

7-3 1,000 galUS Acid Transport Tank (SSS-111) ________________________ 7-47-4 2,000 galUS Acid Transport Tank (SSS-121) ________________________ 7-47-5 Containerized Acid Transport Tank__________________________________ 7-57-6 Top Hatch of SSS-111 Acid Tank with Safety Devices ________________ 7-68-1 Crack in Weld on Bottom Suction of a Transport Trailer ______________ 8-38-2 Blister in Rubber Lining Wrongly Used to Transport Solvents _________ 8-68-3 Check the Tractor _________________________________________________ 8-88-4 Prejob Check of Trailer_____________________________________________ 8-89-1 AcidMIX Formulator Input Screen 1 _________________________________ 9-69-2 AcidMIX Formulator Input Screen 2 _________________________________ 9-611-1 Acid Spill_________________________________________________________ 11-111-2 Acid Spill from 55-galUS Drums ___________________________________ 11-111-3 Acid Spill Exercise in Kazakhstan__________________________________ 11-312-1 Matrix Key Service Quality Requirements __________________________ 12-2



xi JET Manual 10 / List of Tables xi

List of Tables

3-1 Properties of Common Acids Used by Schlumberger_________________ 3-54-1 Approved PPE for Handling Different Acid Types ____________________ 4-38-1 Acid Plant Housekeeping and Maintenance Checklist, Page 1 _______ 8-108-2 Acid Plant Housekeeping and Maintenance Checklist, Page 2 _______ 8-118-3 Acid Plant Housekeeping and Maintenance Checklist, Page 3 _______ 8-129-1 Acetic Acid Preparation ____________________________________________ 9-39-2 AcidMIX Formulator Calculation Output _____________________________ 9-711-1 Spill Response Measures on MSDS for 15% HCl ___________________ 11-411-2 Disposal Considerations for 15% HCl from MSDS __________________ 11-5



1-i JET Manual 10 / Introduction 1-i

1 Introduction

1.1 Learning Objectives ____________________________________________ 1-21.2 Safety Warning _________________________________________________ 1-2


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1-1 JET Manual 10 / Introduction 1-1

1 IntroductionJET 10, JET Manual 10, WS Training & Development,Acid Storage, Acid Handling, Acid Transportation, AcidEquipment, Mixing, Spills and Disposal, Acid

This job execution training (JET) manual introduces the storage, handling,mixing, and transportation of the acids used by Schlumberger Well Services (WS)and Well Intervention Services (WIS) in matrix and acid-fracturing treatmentsand other acid-pumping services provided to clients.

This manual discusses how acid mixing and storage systems work, describesthe major components used, reviews their proper operation, and addressesimportant safety and maintenance issues.

NoteHydrochloric acid (HCl) is by far the most common acid used by Schlumberger,and unless otherwise stated, will be the acid of reference throughout this JETmanual.

Other acids used are hydrofluoric acid (HF), acetic acid (CH3CO2H), formicacid (HCO2H), or mixtures of acids.

Because Schlumberger has locations all over the world, acid storage tanks andrelated equipment, transfer pumps, and transport tankers are procured from avariety of sources. For this reason, operating and maintenance procedures aredifferent depending on the location.

However, some basic facts do not change. It is important for the equipmentoperator (EO) to understand and do the following:

Handle acid and acid materials with extreme caution. They are hazardousproducts.

Ensure that the correct personal protective equipment (PPE) are availableand wear the correct PPE at all times.

Be up to date on the required safety training and certification in standardsand procedures. This applies to all personnel.

Review all material safety data sheets (MSDSs) for all materials beforehandling.

Perform a risk assessment before any operation.


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1-2 JET Manual 10 / Introduction 1-2

Ensure that all equipment associated with the handling, storage, transport,transfer, mixing, and pumping of any acid or acid materials are wellmaintained and in good operating condition. In addition, ensure that theStandard Equipment Maintenance (STEM) program is well documented andfollowed.

Document all procedures for the operation of any equipment and processesrelating to the storage, handling, mixing, transportation, and pumping ofacids. All personnel must be competent.

NoteThe EO has a significant impact both on the HSE performance and theprofitability of the operation through the application of best practices related tothe storage, handling, and transportation of acids.

1.1 Learning ObjectivesUpon completion of this manual, you will be able to

describe the safe working practices required when working with acids

explain the principles of acid storage

identify the various types of bulk storage tanks, transfer pumps, fumescrubbers and transport tanks.

describe the operational guidelines for district acid plants and acid plantequipment on location

describe maintenance and procedures for acid storage and transport tanks.

1.2 Safety WarningProper supervision is required during hands-on training. Request assistancefrom your supervisor if you are unfamiliar with or uncomfortable with the properoperation of any equipment or chemical.

All personnel involved with the operation of acid equipment and transfer unitsmust understand the dangers involved when dealing with the materials andequipment, along with all applicable Schlumberger, WS, and WIS safetystandards. Follow proper procedures before working with equipment, acids,and acid additives, e.g., job safety analyses (JSAs) and Hazards Assessmentand Risk Controls (HARCs).



2-i JET Manual 10 / Acid Properties and Hazards 2-i

2 Acid Properties and Hazards

2.1 Definition of an Acid ___________________________________________ 2-12.2 Applications ___________________________________________________ 2-22.3 Acid Properties ________________________________________________ 2-2

2.3.1 Hydrochloric Acid Strength ___________________________________ 2-22.3.2 pH Scale ____________________________________________________ 2-4


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2-1 JET Manual 10 / Acid Properties and Hazards 2-1

2 Acid Properties and HazardsJET 10, JET Manual 10, WS Training & Development,Acid Storage, Acid Handling, Acid Transportation, AcidEquipment, Mixing, Spills and Disposal, Acid

This section describes the properties and dangers of acids.

2.1 Definition of an AcidAn acid is any chemical compound that, when dissolved in water, contributeshydrogen ions (H+) to a solution, resulting in a pH of less than seven.

For example: HCl in water ionizes to hydrogen and chloride ions:

HCl H+ + Cl-

Hence an aqueous solution of HCl is acidic.

The word acid comes from the Latin acidus meaning sour. Acids have thefollowing chemical and physical properties:

reactivity: Acids react with metals, oxides, hydroxides, or carbonates to formsalts and other products.

electrical conductivity: Acids are electrolytes.

touch: Acids produce a stinging feeling, particularly strong acids.

Acids are hazardous materials capable of doing harm. The handling, storage,transportation, and mixing of all acids must be done with extreme care.




2.2 ApplicationsThe wide range of properties of acids makes them very useful in many differentindustrial applications. Acids are used in the steel processing, water treatment,paper, leather, brewing, cosmetics, pharmaceutical, chemical manufacturing(production of inorganic salts, pesticides, catalysts, and plastics), metalextraction and producing, and food-producing industries.

In the oilfield, hydrochloric acid (HCl), organic acids (e.g., acetic, formic, and citricacid) and hydrofluoric acids are used for a variety of purposes. Their properties,reactivity, and reactions with various compounds is controlled with additives.

The demand for acids in the oil and gas industry is increasing worldwide. In1999, the demand for hydrochloric acid (also known as muriatic acid) in the USexceeded 6,500,000 metric tons. One percent of this demand was for use in oilwell stimulation. According to the Chemical Economics Handbook (CEH), in2009, 12% of all North American HCl demand was for use in oil well stimulation.According to IHS, in 2012, US contribution to world consumption of HCl stands ataround 24% HCl, obtained from about 80 suppliers around the world.

2.3 Acid PropertiesAcid has specific properties that are important to understand to be able to handleit safely.

2.3.1 Hydrochloric Acid StrengthHydrochloric acid (HCl) is a solution of hydrogen chloride gas in water. Thestrength of the acid depends on how much hydrogen chloride gas is dissolved ina given quantity of water. Maximum concentration of commercial grade HCl isabout 36% by weight.

This is then diluted to lower concentrations (in the 5 to 28% HCl range) by theaddition of water.


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For Quality Assurance/Quality Control (QA/QC), the following tests are requiredfor acid strength:

1. Specific gravity test by hydrometer (Specific Gravity Method)

2. Acid content test by titration with Sodium Hydroxide (Titration Method)

3. Chloride content test by titration with Silver Nitrate (Chloride Content)

These three laboratory tests are required to determine hydrochloric acidconcentration in acid concentrate. All three tests confirm the strength of the acid,while the third test also verifies that the acid is HCl and only HCl.

The most common method of measuring the concentration of dissolved gas isby determining the specific gravity of the acid solution. The lower the specificgravity is, the lower the concentration of acid is. The specific gravity reading isthen converted into a percentage HCl by weight.

A hydrometer is used to measure the specific gravity (and thus the strength) ofHCl solutions. A sample of the HCl is placed in a graduated cylinder so that itfloats freely (refer to Figure 2-1). Any floating oil must be removed from thesurface of the acid and the hydrometer must be cleaned. The point on thehydrometer scale at the surface of the liquid indicates the specific gravity.

Figure 2-1: Measuring Specific Gravity with a Hydrometer (Read atthe Bottom of the Meniscus)




Acid strength is also measured using the Baume scale, where 1.0 Baume units =1.0069 specific gravity.

The specific gravity is affected by temperature; therefore, it is also necessaryto measure the temperature of the acid at the same time. Corrections are thenmade to convert the readings back to the reference temperature of 60 degF(16 degC).

Refer to Section 3 of the Matrix Materials Manual (MMM), InTouch content ID#4013354, for more information about hydrochloric acid. Refer to the Key ServiceQuality Testing Requirements Matrix, InTouch content ID# 3051128, for moreinformation about the QA/QC tests to check acid strength.

2.3.2 pH ScaleThe pH scale (Figure 2-2) is a measure of the relative acidity or alkalinity of asolution. A change of one pH unit means a 10x change in the acidity or alkalinityof the solution. For example, a change from pH 5 to pH 2 means an increase inacidity of 1,000x.

Figure 2-2: pH Scale

Water is a neutral liquid with a pH of 7 (green). Acidic solutions have a pH ofless than 7, and the lower the number, the stronger the acid. The opposite ofan acid is a base. Base or alkaline solutions have a pH of over 7. The higherthe pH, the stronger the alkali.

Testing the pH helps to quickly identify fluids and to check if an acid has beenneutralized. The pH of a fluid can be measured using

red litmus paper: the paper turns red when touched by an acid.

chemical indicators: color changes in chemicals, such as cobalt chloride,Congo red, methyl orange, phenolphthalein, and turmeric, are used tomeasure different ranges of pH.


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electronic pH meter (Figure 2-3): a probe containing an acidic aqueoussolution encased in a special glass membrane allows the migration ofhydrogen ions (H+). If the water has a pH different from that of the solutionwithin the probe, an electric potential results that registers on the meter.

Figure 2-3: pH Meter



3-i JET Manual 10 / Use of Acids in the Oilfield 3-i

3 Use of Acids in the Oilfield

3.1 Current Oilfield Acid Applications ______________________________ 3-13.2 Historical Background _________________________________________ 3-23.3 Acid System Selection _________________________________________ 3-33.4 Description of Acids Used in the Oilfield _______________________ 3-5

3.4.1 Hydrochloric Acid ____________________________________________ 3-73.4.2 Hydrofluoric Acid _____________________________________________ 3-73.4.3 Mud Acid ____________________________________________________ 3-73.4.4 Clay Acid ____________________________________________________ 3-73.4.5 Acetic Acid __________________________________________________ 3-83.4.6 Formic Acid _________________________________________________ 3-83.4.7 Other Acid Systems __________________________________________ 3-83.5 Acid Additives _________________________________________________ 3-8

3.5.1 Inhibitors and Inhibitor Aids ___________________________________ 3-93.5.2 Surfactants __________________________________________________ 3-93.5.3 Foaming Agents ____________________________________________ 3-103.5.4 Mutual Solvents _____________________________________________ 3-103.5.5 Antisludge Agents ___________________________________________ 3-103.5.6 Nonemulsifying Agents ______________________________________ 3-113.5.7 Iron-Control Agents _________________________________________ 3-113.5.8 Specialty Additives __________________________________________ 3-11


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3-1 JET Manual 10 / Use of Acids in the Oilfield 3-1

3 Use of Acids in the OilfieldJET 10, JET Manual 10, WS Training & Development,Acid Storage, Acid Handling, Acid Transportation, AcidEquipment, Mixing, Spills and Disposal, Acid

The choice of different acids used in the oil industry is based on

their reactivity with different reservoir rocks and damage type

by-products formed when they react

properties of the reservoir, reservoir fluids, and well tubulars.

3.1 Current Oilfield Acid ApplicationsAcids are used in the oilfield to

stimulate wells to improve well production

wellbore cleanup: The wellbore is filled, washed, and allowed to soakwith acid to remove inorganic and organic deposits from the tubulars andthe formation face.

acid fracturing: Acid is injected into low-permeability carbonate formationsat pressures greater than the formation fracturing pressure.

matrix acidizing: Acid is injected radially into the matrix structure of theformation below the fracturing pressure. The acid reacts with rock andplugging materials, removing damage and restoring permeability to thenear-wellbore reservoir rock.

remove scale and buildup of compounds on the inner walls of pipes used inoil and gas wells

clean perforations before fracturing treatments

provide reactive environment during perforation operations to enhanceperforation clean up

help free stuck pipe

provide miscellaneous other uses.




3.2 Historical BackgroundThe use of acids in oil wells began over 100 years ago (Figure 3-1).

Figure 3-1: Pumping Acid in the Old Days

The following significant dates and events mark the development of wellstimulation.

1895: Ohio Oil Company used hydrochloric acid to acidize wells. It was reportedthat oil wells increased production three times and gas wells four times.

March 1896: A patent for using hydrochloric acid (HCl) for acidizing limestonewas issued to Herman Frasch, a chief chemist with Standard Oil Company.

Unfortunately, the use of corrosion inhibitors was not considered and the acidseverely corroded the well casing. The technique declined in popularity and wasdormant for about 30 years.

1931: Dr. John Grebe of the Dow Chemical Company discovered that arsenicinhibited the action of HCl on metal. The Gypsy Oil Company performed anumber of well treatments in sandstone formations, in which inhibited HCl wasused in an attempt to remove gyp deposits (calcium sulfate). The treatmentresults were mostly unimpressive, and no patents were filed on the process.


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February 1932: The first use of an inhibited acid on a limestone formationwas by Dow Chemical Company, which siphoned 500 galUS of HCl containing2 galUS of an arsenic inhibitor through a garden hose into a well owned bythe Pure Oil Company. The acid was then displaced with an oil flush and thepreviously dead well began producing 16 bbl/d.

November 1932: Dow Well Service Group was renamed Dowell in November1932 to provide acidizing services.

1933: A patent for the use of hydrofluoric acid (HF) in sandstone formations wasissued to J. R. Wilson of the Standard Oil Company. Wilsons patent suggestedin-situ generation of HF in HCl by using sodium fluoride (NaF). It was not knownthat NaF, in the presence of HCl, produces the insoluble compound Na3SiF6.

1933: Halliburton Services performed the first treatment using HF blended withHCl in a 1,500-ft well. The results were disappointing due to possible pluggingeffect on the well permeability, and as a result, Halliburton discontinued the useof HF blends until the 1950s.

1935: Halliburton Oil Well Cementing Co. started providing a commercialacidizing service in Kansas.

1940: Schlumberger accomplished the first commercially successful use ofmixtures of HCl and HF in the Gulf Coast area by using mud acid. The HF wasgenerated in a solution of HCl by using ammonium bifluoride (NH4HF2).

Mud acid dissolved the drilling mud deposited as a filter cake during the drillingprocess.

1949: Halliburton performed the first hydraulic fracturing treatment. Thefirst treatments were probably performed with acid, although they were notrecognized as such at the time. Wells in tight carbonate formations usuallywill not accept acid until a critical pressure is reached. Once this pressure isreached, acid can easily be injected at high rates. It was later recognized thatthese wells had been hydraulically fractured.

3.3 Acid System SelectionThe two main acid systems used in the oil industry are designed to treat eithercarbonate (limestone, dolomite, and oolite) or sandstone (silica, quartz, feldspar,clay) reservoirs. For the two formation types, the following acids used are

Carbonates (e.g., limestone; refer to Figure 3-2): HCl is the most commonacid used in carbonate acidizing because of its low cost, availability, andsoluble reaction products. Organic acids, such as acetic and formic acids, are




used for high-temperature applications, because of their low corrosiveness,ease of inhibition, and retarded reaction characteristics. Blends of HCl witheither formic or acetic acids are also used because of cost efficiency and thereduced corrosivity provided by the organic acids.

Figure 3-2: Limestone

Sandstones: Sandstone formations (refer to Figure 3-3 for an example) aretypically treated with a mixture of hydrochloric acid (HCl) and HF, commonlycalled mud acid. The acid and other fluids used in sandstone formationsdepend on the mineralogy of the rock as well as on the damage type. Otheracids used in sandstone formations include lower concentrations of HCl andHF with fluoboric acid (HBF4) added. These mixtures are called clay acidsand are designed specifically for acidizing sensitive sandstone formationsand providing stabilization of clays and other fines.

Figure 3-3: Sandstone


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3.4 Description of Acids Used in the OilfieldTable 3-1 lists the properties of common acids used by Schlumberger in theoilfield.

Table 3-1: Properties of Common Acids Used by Schlumberger

ChemicalCode

Product Name Form SG at 60degF

FlashPoint(degF)

pH

H005 Hydrochloric acid (HCl) 5% Colorless liquid 1.025 > 200 0H075 Hydrochloric acid 7.5% Liquid 1.037 > 200 0H010 Hydrochloric acid 10% Liquid 1.050 > 200 0

H015 Hydrochloric acid 15% Colorless-lightyellow liquid

1.075 > 200 0

H020 Hydrochloric acid 20% Liquid 1.100 > 200 0


1.140 > 200 0


1.18 > 200 0

H152 HCl/HF acid 25/20 Colorless toyellow liquid

1.20 > 200 0

H200 Hydrofluoric (HF) acid 20% Colorless liquid 1.20 > 200 4.1at20%(wt)

H700 Hydrofluoric acid 70% Used by Schlumberger vendor to prepare 20% HFin our storage tanks

Y001 Intensifier Y1 ammoniumbifluoride

White crystals 1.50 > 200 2 at0.5%(wt)

H948 Dilute mud acid

Any solution with up to 7.5%HCl and 1.5% HF

Colorless liquid > 200 0

H949 Regular mud acid

Any solution with 7.6% to12% HCl and 1.6 to 3.0% HF

Colorless liquid 1.10 > 200 0

H950 Super mud acid

Any solution with 12.1% to16% HCl and 3.1% to 6% HF





ChemicalCode

Product Name Form SG at 60degF

FlashPoint(degF)

pH

Y006 Intensifier Y6 White granularpowder

1.40 > 200 5.1at

1%(wt)

H813 Full strength clay acid

7.8% HBF4 + 0.6% HF +0.3% HCl


H814 Full strength clay acid LT

7.8% HBF4 + 0.6% HF +5.5% HCl


H913 Half-strength clay acid

4.1% HBF4 + 0.3% HF +0.15% HCl

Colorless liquid 1.1 > 200 < 2

H914 Half-strength clay acid

4.0% HBF4 + 0.3% HF +2.9% HCl

Colorless liquid 1.1 > 200 0.1

L400 Glacial acetic acid (100%acetic acid)

Colorless liquid 1.05 109 1.0at70%(wt)

L401 Acetic acid solution Colorless liquid 1.00 to 1.05 90 1.0

L036 Formic acid Colorless liquid 1.20 64 degC(147degF)

2.2

Additives, such as inhibitor, iron stabilizers, surfactants, demulsifying agents,and mutual solvents can be added as required depending on the fluid designfor the particular job.

Concentrated HF is dangerous to handle. Schlumberger employees are NOTpermitted to handle HF concentrations greater than 20% by weight. Higherconcentrations must be transported and mixed by vendors.


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3.4.1 Hydrochloric AcidHydrochloric acid (HCl) is a solution of hydrogen chloride gas in water. Thestrength of the acid depends on how much hydrogen chloride gas is dissolvedin a given quantity of water. The maximum concentration of commercial gradeHCl is about 36% by weight. Concentrations of HCl up to 28% by weight aregenerally used in oilfield treatments. In Well Services (WS) and Well InterventionServices (WIS), the chemical code for hydrochloric acid includes H005, H015,and H028, with the last three digits representing the concentration of HCl inpercent (for example, H028 is 28% hydrochloric acid).

3.4.2 Hydrofluoric AcidHydrofluoric acid (HF) is the second most frequently used acid in the oilfield andis always used with another acid, usually HCl. The most common form of HFis mud acid (refer to Section 3.4.3). HF reacts with and dissolves all materialsthat are soluble in HCl. HF also reacts with, dissolves, or partially dissolvesbentonite, naturally occurring formation clays, and other siliceous materials.

3.4.3 Mud AcidMud acid is a mixture of inhibited HCl and HF. It is used primarily to restorepermeability to damaged sandstones. There are three main classifications:

dilute mud acid any solution containing up to and including 7.5% HCland 1.5% HF

regular mud acid any solution containing 7.6 to 12.0% HCl and 1.6 to3.0% HF

super mud acid any solution containing 12.1 to 16% HCl and 3.1 to 6%HF..

3.4.4 Clay AcidClay acid is a mixture of HCl, intensifier Y001 (ammonium bifluoride), andintensifier Y006, which contains boron. Clay acids slowly release HF from thehydrolysis of HBF. There are four clay acid formulations:

full strength clay acid, used for 130 to 300 degF [54 to 149 degC]

full strength clay acid LT, used for 100 to 130 degF [38 to 54 degC]




half-strength clay acid

half-strength clay acid LT.

3.4.5 Acetic AcidAcetic acid (CH3CO2H) can be prepared using either glacial acetic acid (usingstabilizing agent L400, 100% acetic acid) or a low freezing point acetic acidsolution (using stabilizing agent L401). The big advantage of acetic acid is thatconcentrations of up to 12% acetic acid can be adequately inhibited from causingsteel corrosion at temperatures up to 350 degF for extended periods of time. Inmost cases, acetic acid is used in conjunction with HCl.

3.4.6 Formic AcidFormic acid (HCO2H) is a mixture of 9% L036 and water. It is much stronger thanacetic acid, but it is also more difficult to inhibit. It can be used at temperaturesas high as 400 degF [204 degC].

3.4.7 Other Acid SystemsThere are many other acid systems that are mixtures of the acids discussed inthe previous sections with alcohols, oils, gelling agents, and surfactants.

Other acids, such as citric acid, are used in some industrial cleaning applications.

For details, refer to the Matrix Materials Manual (MMM), InTouch content ID#4013354.

3.5 Acid AdditivesAcid solutions are mixed with one or more additives to allow them to be usedeffectively in oilfield applications. Schlumberger stimulation acids always containwater, concentrated acid, and a corrosion inhibitor.

NoteClean, rust-free tanks must be used when preparing all acid mixtures.

Other additives commonly used include

a nonemulsifier


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a surfactant to reduce surface tension, suspend fines, or create foam

a mutual solvent

an iron ion stabilizer

an acid diverter.

NoteAll the additives used in a specific acid solution must be compatible with thecarrier fluid, with each other, and with the formation and reaction products.Compatibility tests must be performed in a laboratory.

3.5.1 Inhibitors and Inhibitor AidsAn acid corrosion inhibitor is added to acid to decrease the destructive reactionof acid with metals. The inhibitor eliminates more than 99% of the metal lossesthat would occur if the inhibitor were not present.

Inhibitor type and concentration depends on the acid system and thetemperature. Inhibitor aids are used to extend the performance range of acidinhibitors. Corrosion testing is performed to determine the concentrations ofinhibitor and inhibitor aid required to give the desired protection time.

Inhibitor examples include A261, A262, A270, and A272. The most commoninhibitor aid is A201.

Inhibitors and inhibitor aids are hazardous materials. Extreme care should betaken when handling these products (refer to the MSDSs).

For more details, refer to the Corrosion Inhibitor Reference Page (InTouchcontent ID# 3300767).

3.5.2 SurfactantsA surfactant is a chemical that alters liquid-liquid or gas-liquid interfacialproperties. Surfactants reduce the interfacial tension and change the contactangle at the interface between liquid and solid. Surfactants are used to




reduce surface or interfacial tension and capillary force

control or change rock wettability

prevent or break water blocks and emulsions

disperse and suspend fines.

Common surfactants include F78, F103, and F105.

3.5.3 Foaming AgentsFoams are used in stimulation treatments as a diverter and to improve cleanup.To ensure that the foam is stable (that is, that the gas is well dispersed in theliquid), a foaming agent is added. Foaming agents are surfactants.

Antifoams and alcohol tend to neutralize the actions of these foaming agents.Common foaming agents include F78, F100, F105, and F107.

3.5.4 Mutual SolventsMutual solvents are multifunctional, nonionic agents soluble in oil, water, acid,and brines. The mutual solvents act as wetting agents, nonemulsifiers andsurface/interfacial tension reducers. They dissolve oil on the rock surface and offfines generated during acidizing, leaving them water wet. Water-wet fines donot tend to stabilize emulsions.

Mutual solvents are used in large quantities of 5% to 80% solutions. They tendto penetrate deep into the formation, aid in the injection of the treating fluid intothe rock matrix, and help clean up the treatment quicker.

U66 and U100 are common mutual solvents.

3.5.5 Antisludge AgentsAcid sludges are precipitates comprising asphaltenes, resins, asphaltogenicacids, and/or other high-molecular hydrocarbons. These sludges are formedwhen acid contacts the crude oil.

Antisludge additives stabilize the colloidal asphaltic materials found in crudesand prevent the formation of sludge.

W60 and W54 are common antisludge agents.


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3.5.6 Nonemulsifying AgentsMost crudes contain emulsifying agents capable of generating very stableemulsions downhole, resulting in formation damage. When a treating fluid comesin contact with crude oil, varying degrees of emulsion takes place.

Nonemulsifiers are added to the treating fluid. They help prevent the formation ofemulsions and also break existing emulsions.

W53 and W54 are common nonemulsifying agents.

3.5.7 Iron-Control AgentsWhen iron is dissolved during matrix treatments, iron precipitation and formationdamage may occur. Iron precipitation can be prevented by adding complexingagents and reducing agents.

Common iron control agents include L1, L41, U42, and L58.

3.5.8 Specialty AdditivesSpecialty additives can be added to the acid or pre- and postflushes to helpimprove the effectiveness of a stimulation treatment. These include

clay stabilizers

alcohols

antifoam agents

formation cleaners

emulsifiers

scale inhibitors

bactericides.

For more information about these and all of the other additives, refer tothe Matrix Materials Manual (MMM), InTouch content ID# 4013354 or theAcidizing_Additives.htm TBT found in the Well Services SWBT IT Modules,Matrix Acidizing, InTouch content ID# 4135038.



4-i JET Manual 10 / Safety Considerations 4-i

4 Safety Considerations

4.1 Safety Standards _______________________________________________ 4-14.2 Responsibilities ________________________________________________ 4-24.3 Personal Protective Equipment _________________________________ 4-3

4.3.1 Eye and Face Protection _____________________________________ 4-44.3.2 Hand Protection _____________________________________________ 4-54.3.3 Skin and Body Protection _____________________________________ 4-54.3.4 Respiratory Protection ________________________________________ 4-64.3.5 Treating HF Acid Exposure ___________________________________ 4-74.4 Hazard Communication Documents ____________________________ 4-7

4.4.1 Material Safety Data Sheets __________________________________ 4-84.4.2 Chemical Labels _____________________________________________ 4-84.4.3 Dangerous Goods Warning ___________________________________ 4-94.5 Transportation ________________________________________________ 4-14

4.5.1 Hazardous Materials Transportation Placards _________________ 4-144.5.2 EU TREM Cards ____________________________________________ 4-14


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4-1 JET Manual 10 / Safety Considerations 4-1

4 Safety ConsiderationsJET 10, JET Manual 10, WS Training & Development,Acid Storage, Acid Handling, Acid Transportation, AcidEquipment, Mixing, Spills and Disposal, Acid

Acids and acid additives are hazardous materials, because they can causeinjury, a health hazard, or damage to property and equipment. To minimizethe risks while working with acids and acid additives, appropriate precautionsshould be taken. For example, water should never be added to the concentratedacid, because the solution could boil and splash into your face or on your body.Always add acid to water.

4.1 Safety StandardsPersonnel involved in handling and using any acid or acid additive must reviewand be certified in the following standards:

Schlumberger QHSE Standard S008 (Environment), InTouch content ID#3605373: details the requirements and procedures designed to protect theenvironment, prevent pollution, minimize environmental impact, and complywith environmental laws and regulatory requirements.

Schlumberger QHSE Standard S003 (Personal Protective Equipment),InTouch content ID# 3260259.

Well Services (WS) QHSE Std 04: Equipment, InTouch content ID# 3313678.

WS QHSE Std 05: Wellsite Operations, InTouch content ID# 3313681, andthe technology-based training (TBT) at InTouch content ID# 3318425.

WS QHSE Std 12: Permit to Work, InTouch content ID# 3313688, becausethe tanks used to store acids and acid chemicals are considered confinedspaces and personnel must meet all the confined space requirements beforeentering them.

WS QHSE Std 17: Storage and Handling of Oxidizers, InTouch content ID#3313693, and the TBT at InTouch content ID# 3334298.

WS QHSE Std 18: Chemical Product Management, InTouch content ID#3313694, details specific rules and procedures that must be followed at alllocations at which hazardous materials are handled and used in operations;also refer to the TBT at InTouch content ID# 3348663.




4.2 ResponsibilitiesManagement is responsible for

complying with these standards; supplying the necessary personal protectiveequipment (PPE)

providing the training for personnel

applying for exemptions when compliance is not possible.

Job supervisors are responsible for

ensuring that all Schlumberger employees and contractors at the work sitecomply with these standards

recognizing the risks associated with the operation and reducing these risksto the greatest extent possible

ensuring that all Schlumberger personnel on site are competent to driveand/or operate their assigned equipment

taking the appropriate action, up to and including terminating the job, ifunacceptable risks exist.

All employees are responsible for complying with these standards andrecognizing and reducing (to the extent possible), the risks associated with theoperation.


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4.3 Personal Protective EquipmentPersonal Protective Equipment (PPE) must be worn while working as mandatedin Schlumberger QHSE Standard S003 (Personal Protective Equipment),InTouch content ID# 3260259. When handling acids and acid additives,any additional PPE required is listed in the MSDS for each product (visithttp://slb-chemicals.slb.com/Msds.cfm). Refer to Table 4-1 for a list of theapproved PPE for each type of acid.

Table 4-1: Approved PPE for Handling Different Acid Types

Hand Protection Gloves (Impervious) Eye & FaceProtection

Respirator Skin & BodyProtectionAcid

Butyl Neoprene Nitrile PVC Viton

Hydrochloricacids (HCl)

X X X X

Hydrofluoricacids (HF)

X X X X

Acetic acid(L400, L401)

X

Formic acid(L036)

X

Mud acids(HCl + HF)

X X X

Clay acids(HBF4 + HF +HCl)

X X X

NIOSH-approvedrespirator with

organic vapor/acidgas protection(color-codedyellow).

Y001 intensifier X

Y006 intensifier

X

Tightly-fittingsafetygoggles.

Face shield.

NIOSH-approvedrespirator withdust and mistprotection (3M

8210).

Chemical-resistantsuit, boots.




4.3.1 Eye and Face ProtectionWear close-fitting chemical splash goggles (indirect-vented chemical goggles)at a minimum. Where splash hazard to face is present, also wear a full-lengthtransparent face shield (refer to Figure 4-1 and Figure 4-2). Protection shouldmeet ANSI standard Z87.1 - 1989 or European Standard 166.

NoteDo NOT wear contact lenses; they could contribute to severe eye damage.

Figure 4-1: Goggles Figure 4-2: Face Shield


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4.3.2 Hand ProtectionImpervious gloves (Butyl, Neoprene, Nitrile, PVC, or Viton) must be worn (referto Table 4-1).

4.3.3 Skin and Body ProtectionYou must wear a chemical-resistant apron and chemical-resistant boots, suchas neoprene or polyvinyl chloride (PVC) (refer to Figure 4-3). Ensure that allpotentially affected body parts are covered, using such precautions as tapingsleeves and pant legs to gloves and boots and buttoning clothing to the neck.

Figure 4-3: Protective Suit

NoteA safety shower and eyewash station should be located in the immediate workarea.




4.3.4 Respiratory ProtectionWhen exposure levels could exceed 5 ppm, a NIOSH-approved air-purifyingrespirator with an acid-gas cartridge (color-coded yellow) in combination with ahigh-efficiency particulate air filter (HEPA) is recommended (refer to Figure 4-4).

When exposure levels could exceed 50 ppm, a self-contained breathingapparatus with a full face piece is recommended (refer to Figure 4-5).

Figure 4-4: Respirator Figure 4-5: Breathing Mask


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4.3.5 Treating HF Acid ExposureHydrofluoric acid (HF) will cause excruciatingly painful, deep-seated skin burnsthat are slow to heal. The effects of dilute solutions (


4.4.1 Material Safety Data SheetsThe Material Safety Data Sheet (MSDS), InTouch content ID# 5277326, is thereference document for all material hazard, safety, and handling informationfor each acid or acid additive.

A complete list of MSDSs can be found at http://slb-chemicals.slb.om/Msds.cfm.

The following requirements include all Well Services (WS) and Well InterventionServices (WIS) chemicals, purchased products, and purchased maintenancematerials, which are hazardous items:

The identity of the material on the container label must be the same as thaton the MSDS. This identity enables the correct MSDS to be found usingthe material name or code.

For locally purchased products, a copy of the vendor MSDS must be kept onfile.

The local manager is responsible for making sure that a current MSDS is onfile for any material or product from other companies.

Current MSDSs must be available to any person in the workplace who workswith or has exposure to hazardous materials.

MSDSs must be in the work areas where they are easy to find.

MSDSs must be supplied for any materials purchased from WS or WIS andto customers upon request.

4.4.2 Chemical LabelsAll chemical materials that cause a physical, health, or environmental hazardmust comply with the WS and WIS policy for labels. This includes chemicalssupplied by WS and WIS, repackaged chemicals, laboratory chemicals, rawmaterials, and common chemicals such as solvents, coolants, and fuels.

Each material package or container must be clearly marked with the followinginformation:

chemical name or code of the chemical. This identity must show thealphanumeric WS or WIS code and the trade name, and must be the sameas the description of the material in the MSDS (e.g., H015 hydrochloric acid15%).


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hazard warnings

name and address of the manufacturer, the company packaging the product,distributor, and so on.

Other requirements include the following:

Replace missing or worn labels immediately.

Do NOT remove or damage labels on purchased products.

Old labels may be replaced with new labels that meet WS and WISrequirements.

4.4.3 Dangerous Goods WarningAll containers for materials must be marked with a warning that defines thepossible hazards of the product. The design of this label can change in differentlocations, but it is normally included with the product label.

HMIS (Hazardous Materials Identification System) Label (Figure 4-6): Allproducts from the US must have the HMIS label, which contains three boxes:

health hazard

flammability hazard

reactivity hazard.

Each of the boxes contains a number from 0 to 4 indicating the hazard level:0 = no risk; 4 = high risk.

EU Label (Figure 4-7): Products from Europe must have the EU label, whichshows a series of symbols to define physical, health, and environmentalhazards. These symbols do NOT indicate the potential hazards.

Canadian WHMIS Label (Figure 4-8): Products from Canada must have theCanadian WHMIS label, which has symbols that define physical, health,and environmental hazards.




Figure 4-6: US Chemical Label for 15% HCI


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Figure 4-7: EU Chemical Label for 33% HCI




Figure 4-8: Canadian Chemical Label for 15% HCI


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NFPA 704 is a standard maintained by the U.S. National Fire ProtectionAssociation. It defines the fire diamond used by emergency personnel to quicklyand easily identify the risks posed by hazardous materials. This helps determineif any specialty equipment should be used, procedures followed, or precautionstaken during the first moments of an emergency response. For example, Figure4-9 shows the fire diamond for hydrochloric acid; each color represents a hazardtype and each number rates the hazard. The higher the number, the greater thehazard. COR means it is corrosive.

Figure 4-9: Fire Diamond NFPA 704




4.5 TransportationTransporting acid presents several issues and concerns. This section describesthe different types of transportation cards used when transporting acids.

4.5.1 Hazardous Materials Transportation PlacardsTransportation regulations in the majority of countries require hazardousmaterials (HAZMAT) placards when shipping hazardous materials or dangerousgoods.

Acids are classified as Class 8: corrosive fluids, so they will likely have aHAZMAT placard, depending on the country. These placards should be placedin the placard holders on acid transport trailers and tanks (refer to Figure4-10). Ensure compliance with all applicable and country-specific placardingrequirements.

Figure 4-10: Transport Placards

4.5.2 EU TREM CardsIn Europe, the ADR (Laccord europen relatif au transport international desmarchandises dangereuses par route, or the European agreement for theinternational transport of dangerous goods by road) controls the road transport ofhazardous materials, such as acids. In addition to driver training and certification,TREM (transport emergency) cards must accompany the driver and truck.The TREM cards (refer to Figure 4-11) detail the hazardous material beingtransported and safety information and instructions.


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Figure 4-11: ADR TREM Card for 15% HCl



5-i JET Manual 10 / Acid Supply 5-i

5 Acid Supply

5.1 Acid Supply Packaging _________________________________________ 5-15.2 Material Specifications _________________________________________ 5-35.3 Procedure to Receive Acid at the District _______________________ 5-35.4 Inventory Control ______________________________________________ 5-4


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5-1 JET Manual 10 / Acid Supply 5-1

5 Acid SupplyJET 10, JET Manual 10, WS Training & Development,Acid Storage, Acid Handling, Acid Transportation, AcidEquipment, Mixing, Spills and Disposal, Acid

Schlumberger uses approximately 80 acid suppliers around the world, with 60%of the supply coming from five suppliers. The locations in which the largest useof acid occur are US land, Canada, and the Arabian Gulf.

5.1 Acid Supply PackagingAcid is purchased and supplied in four ways (in descending order of volumes):

bulk acid in road transporters: conventional acid transporters (Figure 5-1)provided by the acid supplier or Schlumberger. Various capacities are useddepending on availability. The transporters are usually rubber lined.

Figure 5-1: Commercial Acid Transporter

bulk acid in rail cars: Large volumes of bulk acid can be supplied inrubber-lined, 22,000 to 23,500 gallon acid railcars (Figure 5-2) if the districtis close to a rail system. In technologically-advanced countries, most acidcars are fitted with loading and unloading devices on a single nozzle, thusprotecting workers and the environment. In other locations, it is necessary tounload the acid with an acid transfer pump and hoses.

Figure 5-2: Acid Railcar in Kazakhstan




intermediate bulk containers (IBCs): IBCs are 1000-liter or 250-galUS totetanks (Figure 5-3) made of a steel-tube cage with an inner container madeout of high-density polyethylene. When containing fluids of SG = 1.30, theycan be stacked in threes. IBCs have a fill port equipped with a 2-in sealedscrew cap, and discharge through a 2-in butterfly valve at the bottom. Thedimensions are: 1.2 m x 1.0 m x 1.16 m with a tare weight of 59 kg.

NoteIn the US, IBC containers and drums must be removed from the transportvehicle and set on the ground prior to unloading contents unless there isproper exemption from the regulations.

Figure 5-3: Acid Tote Tank (IBC)

polyethylene drums (220 L): the drums are blow molded in one operationtogether with the top and bottom out of high molecular weight - high densitypolyethylene (HMW-HDPE), and have an integrated L-ring on the top (Figure5-4). The drums are optimally drainable and can be stacked three to fourhigh on pallets. Refer to WS QHSE Std 18: Chemical Product Management,InTouch content ID# 3313694, for stacking requirements.

Figure 5-4: 220-Liter Acid Drums


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5.2 Material SpecificationsEach product that Schlumberger buys must meet purchasing specifications. Allshipments must comply with these specifications.

NoteProduct specifications are confidential.

The specifications list the following:

product code and name, e.g., H036, HCl 36% uninhibited H36

nominal composition information (chemical composition)

quality control test criteria (type of test, acceptable limits, and test method)

acknowledgements.

Acid delivered by suppliers generally contains


3. Ensure that transport units equipped with air compressors from third-partycompanies must use their air supply equipment to unload products.

4. Make sure that acid is transferred to a storage tank containing the samematerial or to a clean, empty tank. If acid is received in drums or tote tanks,then they should be stored in a safe area.

5. Before transferring acid into Schlumberger storage tanks, check the specificgravity of the acid using a hydrometer and determine the acid concentration.

NoteEnsure that the verification of acid type and acid strength is consistent withWS QHSE Std 18: Chemical Product Management (InTouch content ID#3313694) and KSQR testing methods.

6. Confirm that the volume of acid ordered matches the volume received.

NoteIf the acid received does not match the strength and volume ordered, informyour supervisor immediately.

7. Complete a material reception form, stating the supplier, receipt date,quantity, and description. Be sure to note any differences.

8. Enter the acid description, concentration, volume received, and storagelocations in the inventory system.

9. Follow safe procedures to flush all lines with water before the equipmentis disconnected.

NoteWhen flushing acid out of lines, valves, and pumps with fresh water, makesure that you use a flush rate high enough to ensure all the acid is flushed out.

5.4 Inventory ControlThe stock levels of acid and acid additives must be controlled and monitored.This is very important for the profitability of the company. Effective inventorycontrol reduces waste and costs, ensuring resources are optimized.

In some parts of the world, it is also a legal requirement to keep acid in a securefacility and maintain legal records of acid stocks.


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6-i JET Manual 10 / Acid Storage 6-i

6 Acid Storage

6.1 Safety Equipment _____________________________________________ 6-116.1.1 Acid Bulk Plant Area ________________________________________ 6-126.1.2 Lining for Acid Storage Area _________________________________ 6-136.1.3 Loading Slab _______________________________________________ 6-136.1.4 Signage ____________________________________________________ 6-146.1.5 Safety Shower and Eye Wash Stations _______________________ 6-156.1.6 Spill Kit _____________________________________________________ 6-176.1.7 Fire Extinguisher ____________________________________________ 6-186.2 Acid Storage Tanks ___________________________________________ 6-18

6.2.1 Polyethylene Tanks _________________________________________ 6-196.2.2 Steel Tanks with Lining ______________________________________ 6-206.2.3 Tank Linings and Coatings ___________________________________ 6-226.2.4 Pipe Work and Valves _______________________________________ 6-236.3 Fume Scrubber ________________________________________________ 6-24

6.3.1 Absorber ___________________________________________________ 6-266.4 Water Storage _________________________________________________ 6-276.5 Acid Mix/Transfer Tank ________________________________________ 6-286.6 Liquid Additive System ________________________________________ 6-306.7 Dry Additive System __________________________________________ 6-316.8 Pipe Work, Valves, and Fittings ________________________________ 6-316.9 Acid Transfer __________________________________________________ 6-32

6.9.1 Pressure Transfer ___________________________________________ 6-326.9.2 Transfer Pumps _____________________________________________ 6-33

6.9.2.1 Delasco Pump __________________________________________ 6-336.9.2.2 Air-Over-Fluid Chugger Pump __________________________ 6-356.9.2.3 Other Pumps ____________________________________________ 6-376.9.3 Standalone Centrifugal Pumps _______________________________ 6-386.10 Liquid Additive Pumps ________________________________________ 6-396.11 Transfer Hoses and Connections ______________________________ 6-40

6.11.1 Connections ________________________________________________ 6-406.11.2 Hoses ______________________________________________________ 6-41


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6-1 JET Manual 10 / Acid Storage 6-1

6 Acid StorageJET 10, JET Manual 10, WS Training & Development,Acid Storage, Acid Handling, Acid Transportation, AcidEquipment, Mixing, Spills and Disposal, Acid

Acid storage (Figure 6-1) refers to equipment used primarily at the district or jobsite to hold acid until it is needed for a job.

Figure 6-1: Acid Storage Tanks at a Schlumberger Location

The equipment used at Schlumberger districts for acid storage varies widelydepending on location, local laws and regulations, and the level of acidizingservices provided.

The preferred storage facility for an acid plant includes

acid storage tanks

water storage tanks

transfer pumps

mix tanks and other mixing equipment

acid fume scrubber

liquid additive system and additive storage facilities

revetment with a protective coating

loading dock.

The facility may also include warehouse storage for acid tote tanks, drums, orboth. Some facilities may have a single high volume bulk storage capacity formore than one acid type with several acid storage tanks in it. There is a widevariety of tanks and facilities across different locations.


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Figure 6-2 through Figure 6-7 show the Hassi-Messaoud, Algeria, facility.

Figure 6-2: Fume Scrubber with ElectricWater Pump

Figure 6-3: Acid and Water Storage Tanks

Figure 6-4: Wilden Transfer Pumps andAcid Mix Tank

Figure 6-5: Acid Mixing Tank with ElectricPaddle

Figure 6-6: Liquid Additive Storage Tanksand Pumps

Figure 6-7: Acid Loading Area with LoadingArm/Hose




Figure 6-8 through Figure 6-11 show the Midland, Texas, USA, facility.

Figure 6-8: Acid Storage Tanks and LoadingArea

Figure 6-9: Control Panel for Acid Plant

Figure 6-10: Liquid Additive Storage Tanksand Fume Scrubbers

Figure 6-11: Liquid Additive Storage Totes,Fume Scrubbers and Loading Arm


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Figure 6-12 through show the Jebel Ali, UAE, facility. Figure 6-12 shows thesecondary containment and warning signs on rubber-lined tanks.

Figure 6-12: 20,000 galUS Acid StorageTanks with Suction and Filler-Up Lines

Figure 6-13: Rear of Acid Storage Tanks

Figure 6-14: Acid Valve and Suction onAcid Storage Tanks

Figure 6-15: Restricted Access to AcidPlant




Figure 6-16 through Figure 6-19 show the Tengiz, Kazakhstan, facility.

Figure 6-16: General View of Acid Storage Tanks, Water Supply Tank,and Fume Scrubber (with Lagged Point)

Figure 6-17: Acid Storage Tanks, Piping, and Walkway (Notice Secondary ContainmentWall)

Figure 6-18: Eye Wash Station (NoticeLagging for Cold Weather)

Figure 6-19: Acid Plant with Acid Railcarto be Offloaded


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Figure 6-20 through Figure 6-24 show the Montrose, Scotland facility.

Figure 6-20: Acid Bulk Plant Tank Figure 6-21: Manifolding Between AcidTanks

Figure 6-22: 2 x 30,000-galUS Rubber Lined Acid Tanks and Fume Scrubber withSecondary Containment and Warning Signs

Figure 6-23: Safety Shower and Equipmentat Loading Point

Figure 6-24: Acid Transfer Pumps




Figure 6-25 shows the plant at Aracaju, Mexico. Figure 6-26 through Figure6-29 show a few more plants.

Figure 6-25: Acid Bulk Plant Figure 6-26: Acid Storage Plant

Figure 6-27: Bakersfield, California, Acid Bulk Plant

Figure 6-28: Loading Acid, Villahemosa,Mexico (View 1)

Figure 6-29: Loading Acid, Villahemosa,Mexico (View 2)


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Figure 6-30 shows the Galaxie stimulation vessel in West Africa with 28,400galUS raw acid storage capacity.

Figure 6-30: Galaxie Stimulation Vessel

Figure 6-31 shows the BIGORANGE 25 stimulation vessel in the Persian Gulf.With acid tanks installed on its back deck, the raw acid storage capacity is120,000 galUS.

Figure 6-31: BIGORANGE 25 Stimulation Vessel




Figure 6-32 through Figure 6-37 show various DeepSTIM* vessels.

Figure 6-32: DeepSTIM Stimulation Vessel

Figure 6-33: DeepSTIM III Stimulation Vessel


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As shown in Figure 6-34, the DeepSTIM has an 8,400-galUS raw acid storagecapacity on the back deck.

Figure 6-34: DeepSTIM Acid Storage

Figure 6-35: BIGORANGE XVIII (North Sea) Figure 6-36: BIGORANGE XVIII LiquidAdditive Storage and Pumps




Figure 6-37: BIGORANGE XVIII

6.1 Safety EquipmentThe minimum safety requirements for acid plants are stated in WS QHSE Std04: Equipment, InTouch content ID# 3313678. The type and quantity of safetyequipment available must be determined by the requirements on the MSDSand the number of workers at the plant.


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6.1.1 Acid Bulk Plant Area

NoteAll chemicals, except for bulk dry chemicals, must be stored on concrete padsthat provide secondary containment (refer to Figure 6-38).

Figure 6-38: Revetment Area Before the Installation of Acid Tanks

The secondary containment must hold no less than 110% of the volume of thelargest container in the storage area. In addition, while not required by thestandard, an additional 12 inches of revetment wall height is recommended as itwill aid in spill containment.

Both

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