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Petroleum Engineer’s Guide to Oil Field Chemicals and Fluids Second Edition Petroleum Engineer’s Guide to Oil Field Chemicals and Fluids Second Edition Johannes Fink AMSTERDAM • BOSTON • HEIDELBERG • LONDON NEW YORK • OXFORD • PARIS • SAN DIEGO SAN FRANCISCO • SINGAPORE • SYDNEY • TOKYO Gulf Professional Publishing is an imprint of Elsevier Gulf Professional Publishing is an imprint of Elsevier 225 Wyman Street, Waltham, MA 02451, USA The Boulevard, Langford Lane, Kidlington, Oxford, OX5 1GB, UK © 2015, 2012 Elsevier Inc All rights reserved No part of this publication may be reproduced or transmitted in any form or by any means, electronic or mechanical, including photocopying, recording, or any information storage and retrieval system, without permission in writing from the publisher Details on how to seek permission, further information about the Publisher’s permissions policies and our arrangements with organizations such as the Copyright Clearance Center and the Copyright Licensing Agency, can be found at our website: www.elsevier.com/permissions This book and the individual contributions contained in it are protected under copyright by the Publisher (other than as may be noted herein) Notices Knowledge and best practice in this field are constantly changing As new research and experience broaden our understanding, changes in research methods, professional practices, or medical treatment may become necessary Practitioners and researchers must always rely on their own experience and knowledge in evaluating and using any information, methods, compounds, or experiments described herein In using such information or methods they should be mindful of their own safety and the safety of others, including parties for whom they have a professional responsibility To the fullest extent of the law, neither the Publisher nor the authors, contributors, or editors, assume any liability for any injury and/or damage to persons or property as a matter of products liability, negligence or otherwise, or from any use or operation of any methods, products, instructions, or ideas contained in the material herein British Library Cataloguing in Publication Data A catalogue record for this book is available from the British Library Library of Congress Cataloging-in-Publication Data A catalog record for this book is available from the Library of Congress For information on all Gulf Professional publications visit our website at http://store.elsevier.com/ ISBN: 978-0-12-803734-8 Preface to Second Edition This manuscript is an extension and update from Petroleum Engineer’s Guide to Oil Field Chemicals and Fluids, which appeared in 2010 The most recent literature including articles as well as mostly US patents that appeared since 2010 are collected and introduced in the new text Last but not the least, I want to thank the publisher for kind support, in particular, Katie Hammon and Kiruthika Govindaraju J.K.F March 9, 2015 v Preface This manuscript is an extension and update from Oil Field Chemicals, which appeared in 2003 The text focuses mainly on the organic chemistry of oil field chemicals As indicated by the title, preferably engineers with less background in organic chemistry will use this text Therefore, various sketches of the chemicals and additional explanations and comments are included in the text to those an educated organic chemist is certainly familiar The material presented here is a compilation from the literature, including patents The text is arranged in the order as needed by a typical job It starts with drilling fluids and related applications, such as fluid loss, bit lubricants, etc Then it crosses over to the next major topics, cementing, fracturing, enhanced recovery, and it ends with pipelines and spill Some of the chemicals are used in more than one main field For example, surfactants are used in nearly all of the applications The last three chapters are devoted to these chemicals As environmental aspects are gaining increasing importance, this issue is also dealt carefully HOW TO USE THIS BOOK INDEX There are three indices: an index of acronyms, an index of chemicals, and a general index In a chapter, if an acronym is occurring the first time, it is expanded to long form and to short form, for example, acrylic acid (AA) and placed in the index If it occurs afterwards it is given in the short form only, i.e., AA If the term occurs only once in a specific chapter, it is given exclusively in the long form In the chemical index, bold face page numbers refer to the sketches of structural formulas or to equations which refer reactions BIBLIOGRAPHY The bibliography is given per chapter and is sorted in the order of occurrence After the bibliography, a list of tradenames that are found in the references and which chemicals are behind these names, as far as laid open is added ACKNOWLEDGMENTS The continuous interest and the promotion by Professor Wolfgang Kern, the head of the department is highly appreciated I am indebted to our university librarians, Dr Christian Hasenhüttl, Dr Johann Delanoy, Franz Jurek, Margit Keshmiri, Dolores Knabl, Friedrich vii viii Preface Scheer, Christian Slamenik, and Renate Tschabuschnig for their support in the acquisition of literature This book could not have been otherwise compiled Thanks are given to Professor I Lakatos, University of Miskolc who directed my interest to this topic J.K.F CHAPTER Drilling muds According to American Petroleum Institute (API), a drilling fluid is defined as a circulating fluid used in rotary drilling to perform any or all of the various functions required in drilling operations Drilling fluids are mixtures of natural and synthetic chemical compounds used to cool and lubricate the drill bit, clean the hole bottom, carry cuttings to the surface, control formation pressures, and improve the function of the drill string and tools in the hole They are divided into two general types: water-based drilling muds (WBMs) and oil-based drilling muds (OBMs) The type of fluid base used depends on drilling and formation needs, as well as the requirements for disposition of the fluid after it is no longer needed Drilling muds are a special class of drilling fluids used to drill most deep wells Mud refers to the thick consistency of the formulation Drilling fluids serve several fundamental functions [1, 2]: • • • • • control of downhole formation pressures, overcoming the fluid pressure of the formation, avoiding damage of the producing formation, removal of cuttings generated by the drill bit from the borehole, and cooling and lubricating of the drill bit In addition to these fundamental functions of drilling fluids, drilling fluids preferably possess several desirable characteristics which can greatly enhance the efficiency of the drilling operation To perform these functions, an efficient drilling fluid must exhibit numerous characteristics, such as desired rheological properties (plastic viscosity, yield value, low-end rheology, and gel strengths), fluid loss prevention, stability under various temperature and pressure operating conditions, stability against contaminating fluids, such as salt water, calcium sulfate, cement, and potassium contaminated fluids [1] Preferably, the drilling fluid exhibits penetration enhancement characteristics, by having physical properties, which wet the drill string and keep the cutting surfaces of the drill bit (whether of the roller cone or other configuration) clean The wetting attribute is at least in part a function of the surface tension of the fluid The drilling fluid also preferably has a high degree of lubricity, to minimize friction between the drill string and the wall of the borehole, an extremely valuable result being the minimizing of differential sticking In this situation, the hydrostatic Petroleum Engineer’s Guide to Oil Field Chemicals and Fluids http://dx.doi.org/10.1016/B978-0-12-803734-8.00001-1 © 2015 Elsevier Inc All rights reserved CHAPTER Drilling muds pressure of the drilling fluid column is sufficiently higher than the formation pressure so that the drill string is forced against the wall of the borehole and stuck Yet another desirable characteristic is the prevention from swelling of the solids of the formation, that is, primarily clays and shales, which further reduces incidents of drill string sticking, undergauge holes, etc Inhibition of clay swelling, in general, results from preventing the clays from adsorbing water 1.1 CLASSIFICATION OF MUDS The classification of drilling muds is based on their fluid phase alkalinity, dispersion, and the type of chemicals used The classification according to Lyons [3] is reproduced in Table 1.1 Drilling muds are usually classified as either WBMs or OBMs, depending upon the character of the continuous phase of the mud However, WBMs may contain oil and OBMs may contain water [4] OBMs generally use hydrocarbon oil as the main liquid component with other materials such as clays or colloidal asphalts added to provide the desired viscosity together with emulsifiers, polymers, and other additives including weighting agents Water may also be present, but in an amount not usually greater than 50 volume percent of the entire composition If more than about 5% of water is present, the mud is often referred to as an invert emulsion, that is, water-in-oil emulsion WBMs conventionally contain viscosifiers, fluid loss control agents, weighting agents, lubricants, emulsifiers, corrosion inhibitors, salts, and pH control agents The water makes up the continuous phase of the mud and is usually present in any amount of at least 50 volume percent of the entire composition Oil is also usually present in minor amounts but will typically not exceed the amount of the water so that the mud will retain its character as a water-continuous phase material Potassium muds are the most widely accepted water mud system for drilling water sensitive shales K+ ions attach to clay surfaces and lend stability to shale Table 1.1 Classification of Drilling Muds Class Description Fresh water mudsa pH from to 9.5, include spud muds, bentonite-containing muds, phosphate-containing muds, organic thinned muds (red muds, lignite muds, lignosulfonate muds), organic colloid muds Water-based drilling muds that repress hydration of clays (lime muds, gypsum muds, sea water muds, saturated salt water muds) Contain less than 3-6% of solids Most contain an organic polymer Oil in water and water in oil (reversed phase, with more than 5% water) Contain less than 5% water; mixture of diesel fuel and asphalt Inhibited mudsa Low-solids mudsb Emulsions OBMs a Dispersed systems systems b Nondispersed 1.1 Classification of muds exposed to drilling fluids by the bit The ions also help hold the cuttings together, minimizing dispersion into finer particles Potassium chloride, KCl, is the most widely used potassium source Others are potassium acetate, potassium carbonate, potassium lignite, potassium hydroxide, and potassium salt of partially hydrolyzed poly(acrylamide) (PHPA) For rheology control, different types of polymers are used, for example, xanthan gum and PHPA For fluid loss control, mixtures of starch and polyanionic cellulose (PAC) are often used Carboxymethyl starch, hydroxypropyl starch, carboxymethyl cellulose (CMC), and sodium poly(acrylate) are also used PHPA is widely used for shale encapsulation Salt water muds contain varying amounts of dissolved sodium chloride (NaCl) as a major component Undissolved salt may also be present in saturated salt muds to increase density or to act as a bridging agent over permeable zones Starch and starch derivatives for fluid loss control and xanthan gums for hole cleaning are among the few highly effective additives for salt water muds Sea water mud is a WBM designed for offshore drilling whose make-up water is taken from the ocean Sea water has a relatively low salinity, containing about 3-4% of NaCl, but has a high hardness because of Mg+2 and Ca+2 ions Hardness is removed from sea water by adding NaOH, which precipitates Mg+2 as Mg(OH)2 and by adding Na2 CO3 , which removes Ca+2 as CaCO3 Mud additives are the same as those used in fresh water muds [4]: • • • • • • bentonite clay, lignosulfonate, lignite, CMC, or PAC, and caustic soda Xanthan gum may also be used in place of bentonite Silicate-mud is a type of shale-inhibitive water mud that contains sodium or potassium silicate as the inhibitive component High pH is a necessary characteristic of silicate muds to control the amount and type of polysilicates that are formed The pH of the mud is controlled by addition of NaOH (or KOH) and the appropriate silicate solution Silicate anions and colloidal silica gel combine to stabilize the wellbore by sealing microfractures, forming a silica layer on shales and possibly acting as an osmotic membrane, which can produce in-gauge holes through troublesome shale sections that otherwise might require an oil mud Lime mud is a type of WBM that is saturated with lime, Ca(OH)2 , and has excess, undissolved lime solids maintained in reserve Fluid loss additives include starch, hydroxypropyl starch, CMC, or PAC [4] 1.1.1 DISPERSED NONINHIBITED SYSTEMS Drilling fluids used in the upper hole sections are referred to as dispersed noninhibited systems They are formulated from fresh water and may contain bentonite The CHAPTER Drilling muds Table 1.2 Classification of Bentonite Fluid Systems Solid-Solid Interactions Inhibition Level Dispersed Dispersed Noninhibited Inhibited Nondispersed Nondispersed Noninhibited Inhibited Drilling Fluid Type Fresh water clay NaCl