Petroleum Engineer's Guide to Oil Field Chemicals and Fluids

Petroleum Engineer’s Guide to Oil Field Chemicals and Fluids

Second Edition

Johannes Fink

Table of Contents

Cover image

Title page

Copyright

Preface to Second Edition

Preface

How to use this book

Acknowledgments

Chapter 1: Drilling muds

Abstract

1.1 Classification of muds

1.2 Mud compositions

1.3 Additives

1.4 Cleaning operations

1.5 Drilling fluid disposal

1.6 Characterization of drilling muds

Chapter 2: Fluid loss additives

Abstract

2.1 Mechanism of action of fluid loss agents

2.2 Inorganic additives

2.3 Organic additives

2.4 Poly(saccharide)s

2.5 Humic acid derivates

2.6 Synthetic polymers

Chapter 3: Clay stabilization

Abstract

3.1 Properties of clays

3.2 Mechanisms causing instability

3.3 Inhibitors of swelling

3.4 Inhibitors in detail

3.5 Test methods

Chapter 4: Lubricants

Abstract

4.1 Synthetic greases

4.2 Lubricant compositions

4.3 Special issues

Chapter 5: Bacteria control

Abstract

5.1 Mechanisms of growth

5.2 Treatments with biocides

5.3 Biocides

Chapter 6: Corrosion inhibitors

Abstract

6.1 Specific issues

6.2 Corrosion: application of chicory as corrosion inhibitor for acidic environments

6.3 Classification of corrosion inhibitors

6.4 Fields of application

6.5 Application techniques

6.6 Characterization

6.7 Side effects

6.8 Inhibitor chemicals

6.9 Miscellaneous inhibitors

Chapter 7: Scale inhibitors

Abstract

7.1 Scale prediction

7.2 Classification and mechanism

7.3 Mathematical models

7.4 Inhibitor chemicals

7.5 Characterization

Chapter 8: Gelling agents

Abstract

8.1 Placing gels

8.2 Basic mechanisms of gelling agents

8.3 Gelling in oil-based systems

8.4 Gelling in water-based systems

8.5 In situ formed polymers

Chapter 9: Filter cake removal

Abstract

9.1 Simulation of a filter cake formation

9.2 Bridging agents

9.3 Degradation by acids

9.4 Orthoesters

9.5 Enzymatic degradation

9.6 Nonaqueous breaker fluids

9.7 Peroxides

9.8 Degradation by oligosaccharides

9.9 Breaking by emulsions

9.10 Special issues

Chapter 10: Cement additives

Abstract

10.1 Cementing technologies

10.2 Basic composition of portland cement

10.3 Special cement types

10.4 Classification of cement additives

Chapter 11: Transport

Abstract

11.1 Tracers

11.2 Modelling of the viscosity

11.3 Pretreatment of the products

11.4 Corrosion control

11.5 Carbon dioxide removal

11.6 Paraffin inhibitors

11.7 Pour point depressants

11.8 Drag reducers

11.9 Hydrate control

11.10 Additives for slurry transport

11.11 Additives for odorization

11.12 Cleaning

Chapter 12: Drag reducers

Abstract

12.1 Operating costs

12.2 Mechanism of drag reducers

12.3 Drag reducer chemicals

Chapter 13: Gas hydrate control

Abstract

13.1 Naturally occurring gas hydrates

13.2 Problems with gas hydrates in petroleum technology

13.3 Nature of inclusion compounds

13.4 Conditions for formation

13.5 Formation and properties of gas hydrates

13.6 Test Procedures for Inhibitors

13.7 Hydrate reformation in methane hydrate bearing sediments

13.8 Inhibition of gas hydrate formation

13.9 Hydrate inhibitors for drilling fluids

Chapter 14: Antifreeze agents

Abstract

14.1 Theory of action

14.2 Antifreeze chemicals

14.3 Heat transfer liquids

14.4 Special uses

Chapter 15: Odorization

Abstract

15.1 General Aspects

15.2 Measurement and odor monitoring

15.3 Additives for odorization

15.4 Industrial synthesis of odorants

15.5 Uses and properties

Chapter 16: Enhanced oil recovery

Abstract

16.1 Waterflooding

16.2 Caustic waterflooding

16.3 Smart waterflooding

16.4 Acid flooding

16.5 Emulsion flooding

16.6 Chemical injection

16.7 Polymer waterflooding

16.8 Combination flooding

16.9 Foam flooding

16.10 Carbon dioxide flooding

16.11 Steamflooding

16.12 In situ combustion

16.13 Special techniques

16.14 Microbial enhanced oil recovery techniques

16.15 Reservoir properties

16.16 Treatment of produced water

16.17 Soil remediation

Chapter 17: Fracturing fluids

Abstract

17.1 Stresses and fractures

17.2 Comparison of stimulation techniques

17.3 Types of hydraulic fracturing fluids

17.4 Water-based systems

17.5 Oil-based systems

17.6 Foam-based fracturing fluids

17.7 Fracturing in coal-beds

17.8 Horizontal wells

17.9 Propping agents

17.10 Acid fracturing

17.11 Matrix acidizing

17.12 Matrix stimulation

17.13 Special problems

17.14 Characterization of fracturing fluids

Chapter 18: Water shutoff

Abstract

18.1 Classification of the methods

18.2 In situ polymerization

18.3 Acrylic gels

18.4 Special applications

18.5 Thermally stable gels

18.6 Blocked isocyanate gels

18.7 Disproportionate permeability reduction

18.8 Silicate-based agents

18.9 Resin types

18.10 Cement with additives

18.11 Organosilicones

18.12 Non-Crosslinked copolymers

18.13 Inorganic colloids

18.14 Water swelling additives

18.15 Wastes

18.16 Surfactants

18.17 Tailoring the hydrodynamic volume

Chapter 19: Oil spill treating agents

Abstract

19.1 History

Chapter 20: Waste disposal

Abstract

20.1 Produced water

20.2 Drilling fluids

20.3 Cuttings

20.4 Injection techniques

Chapter 21: Dispersions, emulsions, and foams

Abstract

21.1 Dispersions

21.2 Emulsions

21.3 Foams

Chapter 22: Defoamers

Abstract

22.1 Theory of defoaming

22.2 Classification of defoamers

22.3 Uses in petroleum technology

Chapter 23: Demulsifiers

Abstract

23.1 Emulsions in produced crude oil

23.2 Waterflooding

23.3 Oil spill treatment

23.4 Desired properties

23.5 Mechanisms of demulsification

23.6 Performance testing

23.7 Classification of demulsifiers

23.8 Demulsifiers in detail

Abbreviation Index

Chemical Index

Index

Copyright

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

Preface

J.K.F.

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 Hasenhttl, Dr. Johann Delanoy, Franz Jurek, Margit Keshmiri, Dolores Knabl, Friedrich 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.

Chapter 1

Drilling muds

Abstract

This chapter deals with compositions for drilling muds and special chemicals used for drilling muds. 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. Drilling muds are divided into two general types: water-based drilling muds and oil-based drilling muds. Each type needs special additives which are discussed in this chapter. 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.

Keywords

Noninhibited systems

Water-based muds

Sea water muds

Low-solids fresh water muds

Gas-based muds

Cleaning operations

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 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.

Table 1.1

Classification of Drilling Muds

a Dispersed systems.

b Nondispersed systems.

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 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 gumand 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 Na2CO3, 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 classification of bentonite-based muds is shown in Table 1.2. The flow properties are controlled by a flocculant or thinner, and the fluid loss is controlled with bentonite and CMC.

Table 1.2

Classification of Bentonite Fluid Systems

1.1.2 Phosphate-treated muds

Phosphates are effective only in small concentrations. The mud temperature must be less than 55 °C. The salt contamination must be less than 500 ppm sodium chloride. The concentration of calcium ions should be kept as low as possible. The pH should be between 8 and 9.5. Some phosphates may decrease the pH, so adding more NaOH is required.

1.1.3 Lignite muds

Lignite muds are high-temperature resistant up to 230 °C. Lignite can control viscosity, gel strength,and fluid loss. The total hardness must be lower than 20 ppm.

1.1.4 Quebracho muds

Quebracho is a natural product extracted from the heartwood of the Schinopsis trees that grow in Argentina and Paraguay. Quebracho is a well characterized polyphenolic and is readily extracted from the wood by hot water. Quebracho is widely used as a tanning agent. It is also used as a mineral dressing, as a dispersant in drilling muds, and in wood glues. Quebracho is commercially available as a crude hot water extract, either in lump, ground, or spray-dried form, or as a bisulfite treated spray-dried product that is completely soluble in cold water. Quebracho is also available in a bleached form, which can be used in applications where the dark color of unbleached quebracho is undesirable [5].

Quebracho-treated fresh water mudswere used in shallow depths. It is also referred to as red mud because of the deep red color. Quebracho acts as a thinner. Poly(phosphate)s are also added when quebracho is used. Quebracho is active at low concentrations and consists of tannates.

1.1.5 Lignosulfonate muds

Lignosulfonate fresh water muds contain ferrochrome lignosulfonate for viscosity and gel strength control. These muds are resistant to most types of drilling contamination because of the thinning efficiency of the lignosulfonate in the presence of large amounts of salt and extreme hardness.

1.1.6 Lime muds

Lime muds contain caustic soda, an organic thinner, hydrated lime, and a colloid for filtrate loss. From this a pH of 11.8 can result, with 3-20 ppm calcium ions in the filtrate. Lime muds exhibit low viscosity, low gel strength, and good suspension of weighting agents. They can carry a larger concentration of clay solids at lower viscosities than other types of mud. At high temperatures, lime muds present a danger of gelation.

1.1.7 Sea water muds

The average composition of sea water is shown in Table 1.3. Sea water muds have sodium chloride concentrations above 10,000 ppm. Most of the hardness in sea water is caused by magnesium. Sea water muds are composed of bentonite, thinner (lignosulfonate or lignosulfonate with lignite), and an organic filtration control agent.

Table 1.3

Composition of Sea Water

1.1.8 Nondispersed noninhibited systems

In nondispersed systems no special agents are added to deflocculate the solids in the fluid. The main advantages of these systems are the higher viscosities and the higher yield point-to-plastics viscosity ratio. These alterated flow properties provide a better cleaning of the borehole, allow a lower annular circulating rate, and minimize the washout of the borehole.

1.1.9 Low-solids fresh water muds

Clear fresh water is the best drilling fluid in terms of penetration rate. Therefore, it is desirable to achieve a maximal drilling rate using a minimal amount of solid additives. Originally, low-solids mud formulations were used in hard formations, but they now also tend to find use in other formations. Several types of flocculants are used to promote the settling of drilled solids by flocculation.

1.1.10 Variable density fluids

Variable density fluids are those that having a density that varies as a function of pressure into the subterranean formation. Such a fluid comprises a base fluid and a portion of elastic particles.

The presence of the elastic particles in a variable density fluid allows the density of the variable density fluid to vary as a function of pressure. For instance, as the elastic particles encounter higher downhole pressures, they compress, thereby lowering their volume. The reduction in the volume of the elastic particles in turn increases the density of the variable density fluid.

When the elastic particles are fully compressed, the density increases considerably. The increase in volume of the elastic particles in turn reduces the overall density of the variable density drilling fluid. The resulting change in density may be sufficient to permit the return of the variable density fluid through the riser to the surface without any additional pumps or subsurface additives [6].

The elastic particles can be a copolymer of styrene and divinylbenzene, a copolymer of styrene and acrylonitrile, or a terpolymer of styrene, vinylidene chloride, and acrylonitrile [6].

1.1.11 Gas-based muds

Although natural gas (methane) exhaust or other combustion gases can be used, air is most common in such drilling fluids. Air is used to produce the so called foam muds in which air bubbles are surrounded by a film of water containing a foam-stabilizing substance or film-strengthening materials, such as organic polymers or bentonite.

This type of mud is not recirculated and is particularly used for reduced-pressure drilling to improve the hole stability in caving formations. However, this type of mud has some limitations with respect to drilling water producing or wet formations, as well as a limited salt tolerance.

1.1.12 Drill-in fluids

After drilling a well to the total depth, it is a normal practice to replace the drilling mud with a completion fluid. This fluid is a clean, solids-free, or acid soluble, non-damaging formulation, intended to minimize reductions in permeability of the producing zone. Prior to producing from the formation, it is usually necessary to cleanup what is left by the original mud and the completion fluid, by breaking and degrading the filter cake with an oxidizer, enzyme, or an acid solution.

Nowadays, many wells exploit the pay-zone formations horizontally and for long distances. It is no longer practical in these wells to drill the pay-zone with conventional solids-laden muds as the extended cleanup process afterwards is much more difficult. Consequently, the modern generation of drill-in fluids were developed.

Heavy brine completion fluids

Drill-in fluids are drilling fluids used in drilling through a hydrocarbon producing zone, also addressed as a pay-zone [7]. Completion fluids are fluids used in completing or working over a well. Completion operations normally include perforating the casing and setting the tubing and pumps prior to, and to facilitate, initiation of production in hydrocarbon recovery operations.

As the pay-zone is penetrated horizontally, these fluids must provide the multifunctional requirements of drilling fluids in addition to the non-damaging attributes of completion fluids. In practice, the normal drilling mud is replaced with a drill-in fluid just before the pay-zone is penetrated, and used until the end of the operations.

Choosing the right completion fluid is important because inappropriate fluids can have a significant impact on a project, not only during completion operations and well production startup, but also throughout the well’s productive life. Experience has shown that some completion practices that work well in one location, but may not work well in a different location.

The importance of using clear completion and workover fluids to minimize formation damage is well recognized and the use of clear heavy brines as completion fluids is now widespread [7].

Most heavy brines used by the oil and gas industry are calcium halide brines, particularly calcium chloride or calcium bromide brines, or formate brines. However, halide brines can cause structural failure in corrosion resistant alloys, and chloride and bromide brines in particular are known to cause pitting corrosion and stress corrosion cracking of corrosion resistant alloys if oxygen or carbon dioxide is present. In contrast, formate brines do not cause such corrosion and cracking but are more costly to purchase and have some solubility problems at high density.

A phosphate based heavy brine drill-in or completion fluid has been described [7]. The fluid is prepared with a phosphate brine, preferably consisting essentially of water with phosphates dissolved therein, preferably in a quantity ranging from about 1.2-2.4 kg l−1.

Such a phosphate solution may be economically obtained from waste product from a sewage treatment plant, for example. This phosphate solution in turn is blended with water, preferably fresh water although sea water might alternatively be used, in a quantity such that the phosphate solution comprises more or less of the blend or even approximately half of the blend.

Also, corrosion inhibitors and clay inhibitors may be added to the blend, although the fluid is less corrosive without inhibitors than calcium halide brines. Non-amine based corrosion inhibitors designed to prevent oxygen corrosion in monovalent brines are most effective [7].

1.2 Mud compositions

Commercial products are listed in the literature. These include bactericides, corrosion inhibitors, defoamers, emulsifiers, fluid loss and viscosity control agents, and shale control additives [8–12].

1.2.1 Inhibitive water-based muds

Minimizing the environmental impact of the drilling process is a highly important part of drilling operations to comply with environmental regulations that have become stricter throughout the world. In fact, this is a mandatory requirement for the North Sea sector. The drilling fluids industry has made significant progress in developing new drilling fluids and ancillary additives that fulfill the increasing technical demands for drilling oil wells. These additives have very little or no adverse effects on the environment or on drilling economics.

New drilling fluid technologies have been developed to allow the continuation of oil-based performance with regard to formation damage, lubricity and wellbore stability aspects and thus penetration rates. These aspects were greatly improved by incorporating polyols or silicates as shale inhibitors in the fluid systems.

Polyols based fluids contain a glycol or glycerol as a shale inhibitor. These polyols are commonly used in conjunction with conventional anionic and cationic fluids to provide additional inhibition of swelling and dispersing of shales. They also provide some lubrication properties.

Sodium silicates or potassium silicates are known to provide levels of shale inhibition comparable to that of OBMs. This type of fluids is characterized by a high pH (>12) for optimum stability of the mud system. The inhibition properties of such fluids are achieved by the precipitation or gelation of silicates on contact with divalent ions and lower pH in the formulation, providing an effective water barrier that prevents hydration and dispersion of the shales.

1.2.2 Water-based muds

These muds have water as the continuous phase. Water may contain several dissolved substances. These include alkalies, salts and surfactants, organic polymers in colloidal state, droplets of emulsified oil, and various insoluble substances, such as barite, clay, and cuttings in suspension.

The mud composition selected for use often depends on the dissolved substances in the most economically available make-up water or on the soluble or dispersive materials in the formations to be drilled. Several mud types or systems are recognized and described in the literature such as:

• spud muds,

• dispersed/deflocculated muds,

• lime muds,

• gypsum muds,

• salt water muds,

• nondispersed polymer muds,

• inhibitive potassium muds,

• cationic muds, and

• mixed metal hydroxide muds.

Despite their environmental acceptance, conventional WBMs exhibit major deficiencies relative to OBMs/pseudo oil-based drilling muds (POBMs) with regard to their relatively poor shale inhibition, lubricity, and thermal stability characteristics. To overcome those deficiencies, specific additives may, however, be added into the WBM compositions to deliver properties close to OBMs/POBMs, performance while minimizing the environmental impact.

Consequently, to meet the new environmental regulations while extending the technical performance of water-based drilling fluids, a new generation of water-based fluids, also called inhibitive drilling fluids was developed to compete against OBMs. Also, to minimize the formation damage, new types of non-damaging drilling fluids, called drill-in fluid, have been developed to drill the pay-zone formations.

Components for WBMs are shown in Table 1.4. Various methods for the modification of lignosulfonates have been described, for example, by condensation with formaldehyde [19] or modification with iron salts [20]. It has been found that chromium-modified lignosulfonates, as well as mixed metal lignosulfonates of chromium and iron, are highly effective as dispersants and therefore are useful in controlling the viscosity of drilling fluids and in reducing the yield point and gel strength of the drilling fluids. Because chromium is potentially toxic, its release into the natural environment and the thereof is continuously being reviewed by various government agencies around the world.

Table 1.4

Water-Based Drilling Muds

Therefore, less toxic substitutes are desirable. Less toxic lignosulfonates are prepared by combining tin or cerium sulfate and an aqueous solution of calcium lignosulfonate, thereby producing a solution of tin or cerium sulfonate and a calcium sulfate precipitate [21].

Compositions with improved thermal stability

To avoid the problems associated with viscosity reduction in polymer-based aqueous fluids, formates, such as potassium formate and sodium formate are commonly added to the fluids to enhance their thermal stability. However, this technology of using the formates is very expensive. The thermal stability of polymer-based aqueous fluids can be improved without the need of using formates [22].

The stability of a wellbore treatment fluid may be maintained at temperatures up to 135-160 °C (275-325 °F). Various poly(saccharide)s may be included in the fluid. The apparent viscosities of drilling fluids containing xanthan gum and poly(acrylamide) (PAM) before and after rolling at 120 °C are shown in Table 1.5.

Table 1.5

Apparent Viscosity Before and After Rolling [22]

Shale encapsulator

A shale encapsulator is added to a WBM in order to reduce the swelling of the subterranean formation in the presence of water. A shale encapsulator should be at least partially soluble in the aqueous continuous phase in order to be effective.

A conventional encapsulator is a quaternary PAM, which is preferably a quaternized poly(vinyl alcohol). Suitable examples of anions that are useful include halogen, sulfate, nitrate, formate, etc. [23].

By varying the molecular weight and the degree of amination, a wide variety of products can be tailored. It is possible to create shale encapsulators for the use in low salinity, including fresh water [23]. The repeating units of quaternized etherified poly(vinyl alcohol) and quaternized PAM are shown in Figure 1.1.

Figure 1.1 Quaternized etherified poly(vinyl alcohol) and quaternized poly(acrylamide) [ 23 ].

Membrane formation

In order to increase the wellbore stability, it is possible to provide formulations for water-based drilling fluids, which can form a semi-permeable osmotic membrane over a specific shale formation [24]. This membrane allows a comparatively free movement of water through the shale, but it significantly restricts the movement of ions across the membrane and thus into the shale.

The method of membrane formation involves the application of two reactants to form in situ a relatively insoluble Schiff base, which deposits at the shale as a polymer film. This Schiff base coats the clay surfaces to build a polymer membrane.

The first reactant is a soluble monomer, oligomer, or polymer with ketone or aldehyde or aldol functionalities or precursors to those. Examples are carbon hydrates, such as dextrin, linear of branched starch. The second reactant is a primary amine. These compounds are reacting by a condensation reaction to form an insoluble crosslinked polymerized product. The formation of a Schiff base is shown in Figure 1.2.

Figure 1.2 Formation of a Schiff base [ 24 ].

Figure 1.2 illustrates the reaction of a dextrine with a diamine, but other primary amines and poly(amine)s will of course react in the same way. Long chain amines, diamines, or poly(amine)s with a relatively low amine ratio may require supplemental pH adjustment using materials such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, or calcium hydroxide [24]. The Schiff base formed in this way must be essentially insoluble in the carrier brine in order to deposit a sealing membrane on the shale during drilling of a well.

By carefully selecting the primary polymer and the crosslinking amine, the relative concentrations of these components, together with the adjustment of pH, crosslinking and polymerization and precipitation of components occurs which effectively forms an osmotically effective membrane on or within the face of the exposed rock.

The polymerization and precipitation of the osmotic membrane on the face of the exposed rock significantly retards water or ions from moving into or out of the rock formation, typically shale or clay. The ability to form an osmotic barrier results in an increased stability in the clays or minerals, which combine to make the rock through which the borehole is being drilled [24].

1.2.3 Oil-based drilling muds

They have oil as the continuous phase. The oil most often selected is diesel oil, mineral oil, and low toxicity mineral oil. Because some water will always be present, the OBM must contain water-emulsifying agents. If water is purposely added (for economical reasons), the OBM is called an invert emulsion mud. Various thickening and suspending agents as well as barite are added. The emulsified water may contain alkalies and salts.

Due to their continuous phase, OBMs are known to provide unequaled performance attributes with respect to the rate of penetration, shale inhibition, wellbore stability, high lubricity, high thermal stability, and high salt tolerance. However, they are subjected to strict environmental regulation regarding their discharge and recycling.

OBMs are being replaced now by synthetic muds. Diesel oil is harmful to the environment, particularly to the marine environment in offshore applications. The use of palm oil derivatives could be considered as an alternative oil-based fluid that is harmless to the environment [25]. Hydrated castor oil can be used as a viscosity promoter instead of organophilic quaternized clays [26].

An OBM can be viscosified with maleated ethylene-propylene elastomers [27]. The elastomers are ethylene-propylene copolymers or ethylene-propylene-diene terpolymers. The maleated elastomers are far more effective oil mud viscosifiers than the organophilic clays used. On the other hand, specific organophilic clays can provide a drilling fluid composition less sensitive to high temperatures [28].

Poly-α-olefins (PAOs) are biodegradable and nontoxic to marine organisms. They also meet viscosity and pour point specifications for the formulation into OBMs [29]. The hydrogenated dimer of 1-decene [30] can be used instead of conventional organic fluids, as can n-1-octene [31].

Poly(ether)cyclicpolyols

Poly(ether)cyclicpolyols possess enhanced molecular properties and characteristics and permit the preparation of enhanced drilling fluids that inhibit the formation of gas hydrates; prevent shale dispersion; and reduce the swelling of the formation to enhance wellbore stability, reduce fluid loss, and reduce the filter cake thickness.

Drilling muds incorporating the poly(ether)cyclicpolyols are substitutes for OBMs in many applications [32–36]. Poly(ether)cyclicpolyols are prepared by thermally condensing a polyol, for example, glycerol to oligomers and cyclic ethers.

Emulsifier for deep drilling

Two major problems are encountered when using OBMs for drilling very deep wells [37]. The first is a problem with the stability of the emulsions with temperature. The emulsifying agents that are stabilizing the emulsions must maintain water droplets in an emulsion up to temperatures of 200 °C.

If the emulsion separates by coalescence of the water droplets, the fluid loses its rheological properties. The second is an environmental problem. The emulsification agents must not only be effective, but also as nontoxic as possible.

Fatty acid amides consisting of N-alkylated poly(ether) chains are used as emulsifiers. For those the term polyalkoxylated superamides has been coined [38]. As a cosurfactant, tall oil fatty acids or their salts can be used.

Biodegradable composition

In compositions of oil-based biodegradable drilling fluids biodegradability can be imparted. There, the main oil phase component is a mixture of methyl esters from biodegradable fatty acids. A typical formulation of a biodegradable drilling fluid is shown in Table 1.6.

Table 1.6

Biodegradable Drilling Fluid [39]

Electric conductive nonaqueous mud

A wellbore fluid has been developed that has a nonaqueous continuous liquid phase that exhibits an electrical conductivity increased by a factor of 10⁴ to 10⁷ compared with conventional invert emulsion. 0.2-10% by volume of carbon black particles and emulsifying surfactants are used as additives. Information from electrical logging tools, including measurements while drilling can be obtained [40].

Water removal

Water can be removed from OBMs by the action of magnesium sulfate [41].

1.2.4 Synthetic muds

Synthetic muds are expensive. Two factors influence the direct cost: the costs per barrel and mud losses. Synthetic muds are the technical equivalent of OBMs when drilling intermediate hole sections. They are technically superior to all water-based systems when drilling reactive shales in directional wells. However, with efficient solids-control equipment, optimized drilling, and good housekeeping practices, the cost of the synthetic mud can be brought to a level comparable with OBM [42].

POBMs or synthetic OBMs are made on the same principle as OBMs. They have been developed to maintain the performance characteristics of OBMs while reducing their environmental impact. The objective behind the design of these drilling fluids is to exchange the diesel oil or mineral oil base with an organic fluid which exhibits a lower environmental impact. The organic fluids used are esters, polyolefins, acetal, ether, and linear alkyl benzenes. As with OBMs, POBMs may contain various ingredients, such as thickening and suspending agents, emulsifying agents as well as weighting agents.

POBMs were developed to technically maintain the performance characteristics of OBMs while reducing their environmental impact. They are, however, not as stable as OBMs depending upon the continuous phase. From environmental perspective, the current legislation is becoming as strict for POBMs as for OBMs. The mud selection process is based on the mud’s technical performance, environmental impact, and financial impact.

Skeletally isomerized linear olefins exhibited a better high-temperature stability in comparison with a drilling fluid prepared from a conventional PAO. The fluid loss properties are good, even in the absence of a fluid loss additive [43–46]. Although normal α-olefins are not generally useful in synthetic hydrocarbon-based drilling fluids, mixtures of mostly linear olefins are minimally toxic and highly effective as the continuous phase of drilling fluids [44, 47].

Acetals as mineral oilsubstitutes exhibit good biodegradability and are less toxic than mineral oils [48, 49]. Acrylic acid (AA) salts are formed by the neutralization reaction of AA in aqueous solution [50].

Alginates are hydrocolloids, which are extracted from brown marine microalgae. Water-soluble alginates are prepared as highly concentrated, pumpable suspensions in mixtures of propylene glycol and water by using hydroxypropylated guar gum in combination with carboxymethylated cellulose, which is used as a suspending agent [51].

1.2.5 Inverted emulsion drilling muds

Inverted emulsion muds are used in 10-20% of all drilling jobs. Historically, first crude oils, then diesel oils and mineral oils, have been used in formulating invert drilling fluids. Considerable environmentally damaging effects may occur when the mud gets into the sea. Drilling sludge and the heavy mud sink to the seabed and partly flow with the tides and sea currents to the coasts. All of these hydrocarbons contain no oxygen and are not readily degraded [52].

Because of problems of toxicity and persistence, which are associated with these oils, in particular for offshore use, alternative drilling oils have been developed. Examples of such oils are fatty acid esters and branched chain synthetic hydrocarbons such as PAOs. Fatty acid ester-based oils have excellent environmental properties, but drilling fluids made with these esters tend to have lower densities and are prone to hydrolytic instability.

PAO-based drilling fluids can be formulated to high densities and have good hydrolytic stability and low toxicity. They are, however, somewhat less biodegradable than esters. Further, they are expensive. The fully weighted, high-density fluids tend to be overly viscous [31].

Esters

Esters of C6 to C11 monocarboxylic acids [53–57], acid-methyl esters [58], and polycarboxylic acid esters [59], as well as oleophilic monomeric and oligomeric diesters [60], have been proposed as basic materials for inverted emulsion muds. Natural oils are triglyceride ester oils [61] and are similar to synthetic esters. Diesters also have been proposed [60, 62–65].

Acetals

Acetals and oleophilic alcohols or oleophilic esters are suitable for the preparation of inverted emulsion drilling muds and emulsion drilling muds. They may replace the base oils, diesel oil, purified diesel oil, white oil, olefins, and alkyl benzenes [52, 66]. Examples are isobutyraldehyde, di-2″-ethylhexyl acetal, dihexyl formal. Also mixtures with coconut alcohol, soya oil, and α-methyldecanol are suitable. Some aldehydes are shown in Figure 1.3.

Figure 1.3 Aldehydes.

Inverted emulsion muds are more advantageous in stable, water sensitive formations and in inclined boreholes. They are stable up to very high temperatures and provide excellent corrosion protection. Disadvantages are the higher price, the greater risk if gas reservoirs are bored through, the more difficult handling for the team at the tower, and greater environmental problems.

The high setting point of linear alcohols and the poor biologic degradability of branched alcohols limit their use as an environment-friendly mineral oil substitute. Higher alcohols, which are still just somewhat water-soluble, are eliminated for use in offshore muds because of their high toxicity to fish. Esters and acetals can be degraded anaerobically on the seabed.

This possibility minimizes the environmentally damaging effect on the seabed. When such products are used, rapid recovery of the ecology of the seabed takes place after the end of drilling. Acetals, which have a relatively low viscosity and in particular a relatively low setting point, can be prepared by combining various aldehydes and alcohols [52, 67].

Anti-settling properties

Ethylene-AA copolymer neutralized with amines such as triethanolamine or N-methyl diethanolamine enhances anti-settling properties [68, 69].

Glycosides

The advantage of using glycosides in the internal phase is that much of the concern for the ionic character of the internal phase is no longer required. If water is limited in the system, the hydration of the shales is greatly reduced.

The reduced water activity of the internal phase of the mud and the improved efficiency of the shale is an osmotic barrier if the glycoside interacts directly with the shale. This helps to lower the water content of the shale, thus increasing rock strength, lowering effective mean stress, and stabilizing the wellbore [70].

Methyl glucosides also could find applications in water-based drilling fluids and have the potential to replace OBMs [71]. The use of such a drilling fluid could reduce the disposal of oil-contaminated drilling cuttings, minimize health and safety concerns, and minimize environmental effects.

Miscellaneous

Other base materials proposed are listed in Table 1.7. Quaternary oleophilic esters of alkylolamines and carboxylic acids improve the wettability of clay [83, 84]. Nitrates and nitrites can replace calcium chloride in inverted emulsion drilling muds [85].

Table 1.7

Other Materials for Inverted Emulsion Drilling Fluids

Reversible phase inversion

Invert emulsion fluids have been developed in which the emulsion can be readily and reversibly converted from a water-in-oil type emulsion to an oil-in-water type emulsion. The essential ingredient is an amine based surfactant as additive. The amine surfactant may be diethoxylated tallow amine, diethoxylated soya amine, or N-tallow-1,3-diaminopropane [86].

The invert emulsion is admixed with an acid that is functionally able to protonate the amine surfactant. When sufficient quantities of the acid are utilized, the invert emulsion is converted so that the oleaginous fluid becomes the discontinuous phase and the non-oleaginous fluid becomes the continuous phase.

The conversion of the phases is reversible so that upon addition of a base capable of deprotonating the protonated amine surfactant, a stable invert emulsion in which the oleaginous liquid becomes the continuous phase and the non-oleaginous fluid become the discontinuous phase can be formed [86].

In other words, when the drilling fluid is converted into an oil-in-water type emulsion, solids, now substantially water-wet, may now be separated from the fluid by gravity or mechanical means for further processing or disposal. The fluid may then be mixed with a base, the base being functionally able to deprotonate the protonated amine surfactant.

The base should be in sufficient quantities so as to convert the oil-in-water type emulsion formed upon the addition of acid, back to a water-in-oil emulsion. The resulting water-in-oil emulsion may then be used as it is or reformulated into a drilling fluid suitable for the drilling conditions in another well [86].

1.2.6 Foam drilling

While drilling low-pressure reservoirs with nonconventional methods, it is common to use low-density dispersed systems, such as foam, to achieve underbalanced conditions. To choose an adequate foam formulation, not only the reservoir characteristics but also the foam properties need to be taken into account.

Parameters such as stability of foam and interactions between rock-fluid and drilling fluid-formation fluid are among the properties to evaluate while designing the drilling fluid [87].

A foaming composition having a specific pH and containing an ionic surfactant and a polyampholytic polymer whose charge depends on the pH is circulated in a well. By varying the pH, it is possible to destabilize the foam in such a way as to more easily break the foam back at the surface and possibly to recycle the foaming solution [88].

1.2.7 Chemically enhanced drilling

Chemically enhanced drilling offers substantial advantages over conventional methods in carbonate reservoirs. Coiled tubing provides the perfect conduit for chemical fluids that can accelerate the drilling process and provide stimulation while drilling [89]. The nature of the chemical fluids is mainly acid that dissolves or disintegrates the carbonate rock.

Temperature and salinity effects

Coiled tubing applications include drilling operations, hydraulic fracturing, well completions, removing sand or fill from wellbore, and other applications that involve pumping fluids at high temperatures and high salinity. Because of curvature effects in coiled tubing, huge pressure losses occur, limiting the maximum flow rate achieved. By adding specific chemicals known as friction reducers or drag reducers to the fluids, these pressure losses can be minimized to a great extent.

Only a few number of studies have been reported that relate to temperature and salinity effects on drag reduction in fluids flowing through coiled tubing [90].

An experimental study of two commonly used drag reducers (ASP-700 and ASP-820) flowing through coiled tubing with different salinities and temperatures has been presented [90]. Both small-scale and large-scale flow loops have been used. The small-scale flow loop includes a 0.5 in. outside-diameter smooth coiled tubing, while the large-scale flow loop includes 2 3/8 in. rough coiled tubings. Elevated temperature tests and salinity tests were conducted using optimum concentrations of drag reducers in fresh water, 2% KCl, and synthetic seawater.

Correlations were developed that can predict the drag reduction at different salinities and temperatures. The developed correlations show a reasonable agreement with the experimental data [90].

1.2.8 Supercritical carbon dioxide drilling

The efficiency of drilling operations can be increased using a drilling fluid material that exists as supercritical fluid or a dense gas at temperature and pressure conditions occurring in the drill site, such as carbon dioxide.

A supercritical fluid exhibits physical-chemical properties intermediate between those of liquids and gases. Mass transfer is rapid with supercritical fluids. Their dynamic viscosities are nearer to those in normal gaseous states.

In the vicinity of the critical point the diffusion coefficient is more than 10 times that of a liquid. Carbon dioxide can be compressed readily to form a liquid. Under typical borehole conditions, carbon dioxide is a supercritical fluid.

The viscosity of carbon dioxide at the critical point is only 0.02 c P, increasing with pressure to about 0.1 c P at 70 MPa (about 10,000 psi). Because the diffusivity of carbon dioxide is so high, and the rock associated with petroleum-containing formations is generally porous, the carbon dioxide is quite effective in penetrating the formation.

This penetration is beneficial. Carbon dioxide is commonly used to stimulate the production of oil wells, because it tends to dissolve in the oil, reducing the oil viscosity while providing a pressure gradient that drives the oil from the formation.

Carbon dioxide can be used to reduce mechanical drilling forces, to remove cuttings, or to jet erode a substrate. Supercritical carbon dioxide is preferably used with coiled-tube drilling equipment. The very low viscosity of supercritical carbon dioxide provides efficient cooling of the drill head and efficient cuttings removal.

Furthermore, the diffusivity of supercritical carbon dioxide within the pores of petroleum formations is significantly higher than that of water, making jet erosion using supercritical carbon dioxide much more effective than jet erosion using water. Supercritical carbon dioxide jets can be used to assist mechanical drilling, for erosion drilling, or for scale removal. Spent carbon dioxide can be vented to the atmosphere, collected for reuse, or directed into the formation to aid in the recovery of petroleum [91].

1.3 Additives

1.3.1 Thickeners

A variety of compounds useful as thickeners is shown in Table 1.8. Subsequently, the individual compounds are explained in detail.

Table 1.8

Thickeners

a Stable up to temperatures of about 180°C.

b Solubilized in acidic solution.

Polymers

Thickener polymers include poly(urethane)s (PUs), poly(ester)s, PAMs, natural polymers, and modified natural polymers [110].

pH responsive thickeners

The viscosity of ionic polymers is dependent on the pH. In particular, pH responsive thickeners can be prepared by copolymerization of acrylic or methacrylic acid ethyl acrylate or other vinyl monomers and tristyrylpoly(ethyleneoxy)x methyl acrylate. Such a copolymer provides a stable aqueous colloidal dispersion at an acid pH lower than 5.0 but becomes an effective thickener for aqueous systems upon adjustment to a pH of 5.5 to 10.5 or higher [111, 112].

Mixed metal hydroxides

By addition of mixed metal hydroxides, typical bentonite muds are transformed to an extremely shear thinning fluid [113]. At rest these fluids exhibit a very high viscosity but are thinned to an almost water like consistency when shear stress is applied.

In theory, the shear thinning rheology of mixed metal hydroxides and bentonite fluids is explained by the formation of a three dimensional, fragile network of mixed metal hydroxides and bentonite.

The positively charged mixed metal hydroxide particles attach themselves to the surface of negatively charged bentonite platelets. Typically, magnesium aluminum hydroxide salts are used as mixed metal hydroxides.

Mixed metal hydroxides demonstrate the following advantages in drilling [114]:

• high cuttings removal,

• suspension of solids during shutdown,

• lower pump resistance,

• stabilization of the borehole,

• high drilling rates, and

• protection of the producing formation.

Mixed metal hydroxide drilling muds have been successfully used in horizontal wells, in tunneling under rivers, roads, and bays, for drilling in fluids, for drilling large-diameter holes, with coiled tubing, and to ream out cemented pipe.

Mixed metal hydroxides can be prepared from the corresponding chlorides treated with ammonium [115]. Experiments done with various drilling fluids showed that the mixed metal hydroxides system, coupled with propylene glycol [116], caused the least skin damage of the drilling fluids tested.

Thermally activated mixed metal hydroxides, made from naturally occurring minerals, especially hydrotalcites, may contain small or trace amounts of metal impurities besides the magnesium and aluminum components, which are particularly useful for activation [117].

Mixed hydroxides of bivalent and trivalent metals with a three dimensional spaced-lattice structure of the garnet type (Ca3Al2[OH]12) have been described [118, 119].

1.3.2 Lubricants

Bit lubricants are dealt with in chapter 4 in detail. During drilling, the drill string may develop an unacceptable rotational torque or, in the worst case, become stuck. When this happens, the drill string cannot be raised, lowered, or rotated. Common factors leading to this situation include:

• cuttings or slough buildup in the borehole,

• an undergauge borehole,

• irregular borehole development embedding a section of the drill pipe into the drilling mud wall cake, and

• unexpected differential formation pressure.

Differential pressure sticking occurs when the drill pipe becomes imbedded in the mud wall cake opposite a permeable zone.

The difference between the hydrostatic pressure in the drill pipe and the formation pressure holds the pipe in place, resulting in a sticking pipe. Differential sticking may be prevented, and a stuck drill bit may be freed, using an OBM or an oil-based or water-based surfactant composition.

Such a composition reduces friction, permeates drilling mud wall cake, destroys binding wall cake, and reduces differential pressure. Unfortunately, many of such compositions are toxic to marine life.

Hagfish slime

Hagfish are marine craniates of the class Agnatha or Myxini are also known as Hyperotreti. Some researchers regard Myxini as not belonging to the subphylum Vertebrata, because they are the only living animals that have a skull but not a vertebral column [120].

Despite their name, there is some debate about whether they are strictly fish, since they belong to a much more primitive lineage than any other group that is placed in the category of fish (Chondrichthyes and Osteichthyes). The earliest fossil record dates back approximately 550 million years, or earlier to the Lower Cambrian period. Their unusual feeding habits and slime-producing capabilities have led members of the scientific community and popular media to dub the hagfish as the most disgusting of all sea creatures. Although hagfish are sometimes called slime eels, they are not eels at all.

Hagfish are long and vermiform, and can excrete copious quantities of a slime or mucus of unusual composition. When captured and held, for example, by the tail, they secrete the slime, which expands into a gelatinous and sticky goo when combined with water. If they remain captured, they can tie themselves in an overhand knot which works its way from the head to the tail of the animal, scraping off the slime as it goes and freeing them from their captor, as well as the slime.

Recently it has been reported that the slime entrains water in its microfilaments, creating a slow-to-dissipate viscoelastic substance, rather than a simple gel, and it has been proposed that the primary protective effect of the slime is related to impairment of the function of a predator fish’s gills [121]. It has been observed that most of the known predators of hagfish are varieties of birds or mammals. It has been proposed that the lack of marine predators can be explained by a gill-clogging hypothesis, wherein one purpose of the slime is to impair the gill function of marine animals that attempt to prey on the hagfish. If true, it could be regarded as a highly successful evolutionary strategy against predatory fish.

Free-swimming hagfish also excrete slime when agitated and will later clear the mucus off by way of the same traveling-knot behavior.

The reported gill-clogging effect suggests that the traveling-knot behavior is useful or even necessary to restore the hagfish’s own gill function after sliming. An adult hagfish can secrete enough slime to turn a 20 l bucket of water into slime in a matter of minutes. Research is ongoing regarding the properties of the components of hagfish slime filament protein.

Drilling formations below the bottom of a body of water have been described [122].

Hagfish may be caused to generate bodily slime in a container at the surface. One or more hagfish may be deployed in the container and agitated to cause secretion of the slime. The slime may be lowered in a separate container along with the drilling system when it is deployed on the water bottom. The slime may be mixed with sea water for use as a drilling fluid during the drilling operations. Effective mixtures may range from about one part hagfish slime to 10 parts of water to about one part hagfish slime to about 20 parts of water. Drilling operations may be performed as known in the art of sea floor drilling using the above described hagfish slime-water mixture [123].

1.3.3 Bacteria

Bacterial contamination of drilling fluids contributes to a number of problems. Many of the muds contain sugar-based polymers in their formulation that provide an effective food source to bacterial populations. This can lead to direct degradation of the mud. In addition, the bacterial metabolismcan generate deleterious products.

Most notable among these is hydrogen sulfide, which can lead to decomposition of mud polymers, formation of problematic solids such as iron sulfide, and corrosive action on drilling tubes and drilling hardware [124]. Moreover, hydrogen sulfide is a toxic gas.

Many polymers are used in drilling fluids as fluid loss control agents or viscosifiers. Because of the degradation of the polymers by bacteria in drilling fluids, an increase in fluid loss can occur. All naturally occurring polymers are capable of being degraded by bacterial action. However, some polymers are more susceptible to bacterial degradation than others. One solution, besides using bactericides, is replacing the starch with low viscosity PAC, polyanionic lignin, or other enzyme-resistant polymers [125].

Certain additives are protected from biodegradation while drilling deep wells by quaternary ammonium salts [126]. This results in a considerably reduced consumption of the additives needed.

Bacteria control is important not only in drilling fluids, but also for other oil and gas operations. The topic is treated more extensively in Chapter 5. Some bactericides especially recommended for drilling fluids