Petroleum Engineer'sGuide to Oil Field

Chemicals and Fluids

Johannes Karl Fink

ELSEVIER

AMSTERDAM • BOSTON • HEIDELBERG • LONDON

NEW YORK • OXFORD • PARIS • SAN DIEGO

SAN FRANCISCO • SINGAPORE • SYDNEY • TOKYO

Glilf Professional Publishing is an Imprint of Elsevier

G

P

P

HI

Contents

Preface xxi

1. Drilling Muds

Classification of Muds 2

Dispersed Noninhibited Systems 4

Phosphate-treated Muds 4

Lignite Muds 4

Quebracho Muds 5

Lignosulfonate Muds 5

Lime Muds 5

Sea Water Muds 5

Nondispersed Noninhibited Systems 5

Low-solids Fresh Water Muds 6

Variable Density Fluids 6

Gas-based Muds 7

Drill-in Fluids 7

Mud Compositions 7

Inhibitive Water-based Muds 7

Water-based Muds 8

Oil-based Drilling Muds 12

Synthetic Muds 13

Inverted Emulsion Drilling Muds 15

Foam Drilling 18

Chemically Enhanced Drilling 18

Supercritical Carbon Dioxide Drilling 19

Additives 19

Thickeners 19

Lubricants 21

Bacteria 22

Corrosion Inhibitors 23

Viscosity Control 24

Clay Stabilization 24

Formation Damage 24

Shale Stabilizer 24

Fluid Loss Additives 26

Scavengers 28

Surfactants 29

v

Hydrate Inhibitors

Weighting Materials

Organoclay CompositionsMiscellaneous

Multicomponent Additives

Cleaning Operations

Cuttings Removal

Junk Removal

Filter Cake Removal

Drilling Fluid DisposalToxicityConversion Into Cements

Environmental RegulationsCharacterization of Drilling Muds

ViscosityAPI Filtration

Alkalinity and pHTotal Hardness

Roller Oven

References

Tradenames

Fluid Loss Additives

Mechanism of Action of Fluid Loss AgentsAction of Macroscopic Particles

Action of Cement Fluid Loss Additives

Testing of Fluid Loss Additives

Formation DamageReversible Gels

Bacteria

Inorganic Additives

Benton ite

Sodium Metasilicate

Ultra-fine Filtrate-Reducing AgentsBridging Agents for Fluid Loss Control

Organic Additives

Tall Oil Pitch

Mercaptans for Iron Control

PolysaccharidesCellulose-based Fluid Loss Additives

Starch

Borate Crosslinkers

Guar

SuccinoglycanPolyether-modified PolysaccharidesScleroglucanGellan

Contents GD

Humic Acid Derivates 78

Oil-based Well Working Fluids 79

Lignosulfonates 79

Synthetic Polymers 82

Polyorthoesters 82

Polyhydroxyacetic Acid 83

Polydrill 84

Latex 85

Polyvinyl Alcohi 87

Polyethyleneimi 88

Acrylics 88

Silicones 93

Phthalimide as a Diverting Material 94

Special Applications 95

References 106

Tradenames 114

3. Clay Stabilization

Properties of Clays 125

Swelling of Clays 127

Montmorillonite 130

Guidelines 130

Mechanisms Causing Instability 131

Kinetics of the Swelling of Clays 131

Hydrational Stress 131

Borehole Stability Model 132

Shale Inhibition with Water-based Muds 132

Inhibiting Reactive Argillaceous Formations 132

Thermal Treatment to Increase the Permeability 132

Formation Damage by Fluids 133

Formation Damage in Gas Production Shut-in 133

Swelling Inhibitors 133

Salts 133

Quaternary Ammonium Salts 134

Potassium Formate 135

Saccharide Derivatives 136

Sulfonated Asphalt 136

Grafted Copolymers 137

Polyoxyalkylene Amines 137

Anionic Polymers 139

Amine Salts of Maleic Imide 139

Comparative Study 139

Test Methods 142

Shale Erosion Test 142

HasslerCell - 142

References(

143

Tradenames 147

Contents

4. Lubricants

Synthetic Creases 149

Base Fluids 150

Extreme Pressure Agents 151

Anti-seize Agents 152

Anti-wear Additives 153

Metal Deactivators 154

Solubility Aids 154

Antioxidants 154

Base stocks 154

Lubricant Compositions 154

Molybdenum disulfide 154

Polarized Graphite 155

Ellipsoidal Glass Granules 156

Calcium-Sulfonate-based Greases 156

Paraffins 157

Olefins 157

Phospholipids 157

Alcohols 158

Ethers 161

Esters 162

Polymers 165

Starch 166

Amides 171

Special Issues 172

Side Reactions 172

Silicate-Based Muds 172

Studies on Pipe Sticking 174

Differential Sticking Reducer 174

References 174

Tradenames 133

5. Bacterial Control

Mechanisms of Growth 185

Growth of Bacteria Supported by Oil Field Chemicals 185

Mathematical Models 186

Detection of Bacteria 1 qj

Sulfate-reducing Bacteria 190

Bacterial Corrosion 191

Mechanisms of Microbial Corrosion 191

Corrosion Monitoring 193

Assessment of the Activity of Biocides

Synergistic Action of Biocides

Treatments with Biocides

Previously Fractured Formations

Intermittent Addition of Biocide

Nonbiocidal Control

Contents QD

Biocides197

Various Biocides 198References

209Tradenames

216

6. Corrosion Inhibitors

Classification of Corrosion Inhibitors 218Fields of Application 218Acidization

219Oil Storage Tanks

219Pipelines 220Production Wells

220Scale Removal Treatments Using Acids 220Application Techniques 220Batch Versus Continuous Application 220Emulsions

221Application in Solid Form 221Characterization

221Dye Transfer Method 221Liquid Chromatography 222Thin Layer Chromatography 222Ultraviolet Spectroscopy 222Corrosion Tests

222Side Effects

223Stabilizer for Emulsions

223

Antisynergism with Alcohols 223Synergism with Surfactants 223Interactions with Kinetic Gas Hydrate Inhibitors 224Effect of Flow on Inhibitor Film Life 224Inhibitor Chemicals 225Amides and Imidazolines 225Salts of Nitrogenous Bases 228Nitrogen Quaternaries 228

Polyoxylated Amines, Amides, and Imidazolines 229

Mercaptan Modified Products 229Nitrogen Heterocyclics 233

Carbonyl Compounds 236Silicate-based inhibitors 237Thioacetals 237Miscellaneous Inhibitors 239

Antimony Halides 239Aldol-amine Adducts 239

Encapsulated Types 241Anti-biofoulant Corrosion inhibitors 241Formic Acid Free Formulation 242Intensifiers 242References

- 244Tradenames 252

Contents

7. Scale Inhibitors

Classification and Mechanism 253

Thermodynamic Inhibitors 255

Kinetic Inhibitors 256

Adherence Inhibitors 256

Mathematical Models 256

Optimal Dose 256

Precipitation Squeeze Method 256

Inhibitor Chemicals 257

Water-soluble Inhibitors 258

Oil-soluble Scale Inhibitors 263

Inhibitors for Special Tasks 264

Characterization 267

Spectroscopic Methods 267

Turbidimetry 267

Static Bottle Test 267

References 268

Tradenames 274

8. Gelling Agents

Placing Gels 275

Basic Mechanisms of Gelling Agents 276

Polymer-Crosslinker-Retarder Systems 276

Gelling in Oil-based Systems 277

Aluminum Phosphate Ester Salts 278

Less Volatile Phosphoric Acid Esters 278

Aluminum Trichloride 279

Biopolymers 280

Organic Polysilicate Ester 281

Latex 281

Gelling in Water-based Systems 282

Xanthan Gum 282

Carboxymethyl Cellulose 282

Polyacrylamide-based Formulations 283

Polyacrylic Acid 287

Alkali-Silicate Aminoplast Compositions 288

In Situ Formed Polymers 288

Epoxide Resins 288

Urea-formaldehyde Resins 288

Vinyl Monomers 289

References 290

Tradenames 293

9. Filter Cake Removal

Bridging Agents 296

Degradable Bridging Agents 296

Dissolvable Bridging Agents 298

Contents

Degradation by Acids 298Citric Acid 298Acetic Acid

299Acid Generating Coatings 299Acidic Foam 300Orthoesters

301

Enzymatic Degradation 302Peroxides

303

Hydrogen Peroxide 303Metal Peroxides 303

Magnesium Peroxide in Filter Cake 303Degradation by Oligosaccharides 304Breaking by Emulsions 304Surfactant Nanotechnology 305Special Issues

305Manganese tetroxide 305

Multiply Active Compositions 306Self-destructing Filter Cake 307

Oscillatory Flow 307References 307

10. Cement Additives

Cementing Technologies 312

Primary Cementing 312Secondary Cementing 312Squeeze Cementing 312

Plug Cementing 312Basic Composition of Portland Cement 313

Manufacturing 313Active Components in Cements 314

Chemistry of Setting 314Standardization of Cements 315Mixing with Additives 315Important Properties of Cement Slurries and Set Cement 316Special Cement Types 317Resin Cement

317Oil-based Cement 318

High-temperature Cement 319Low-temperature Cement 320High-alumina Cement 320

Magnesian Cement 321Fiber Cement 321Acid Gas Resistant Cement 322Permeable Cement 322Salt-water Stable Latex Cement 322Settable Drilling Fluids 322Classification ofCement Additives 323Light-weight Cement 324

GD Contents

Foam Cement328

Density-increasing or Weighting Agents 329Control of Thickening and Setting Time 330Viscosity Control

334Dispersants 335Expansion Additives

335Set Strength Enhancement 337Adhesion Improvement 338Fluid Loss Control

338

Clay Control Additives341

Anti-gas-migration Agents 342Corrosion Inhibitors 342Other Chemical Attack

343Use of Waste from Other Industrial Branches 343References

345Tradenames

358

11. Transport

Pretreatment of the Products351

Pretreatment for Corrosion Prevention351

Natural Gas362

Sulfur Contamination of Refined Products354

Demulsifiers354

Heavy Crudes355

Corrosion Control355

Crude Oil Treatment355

Chemical Inhibition366

Coatings 367Paraffin Inhibitors

368Pour Point Depressants 36gDrag Reducers

369

Drag Reduction in Gas Transmission Lines371

Synergism with Paraffin Deposition 371Hydrate Control

371Additives for Slurry Transport 371Additives for Odorization

373Cleaning 373Gelled Pigs 374References

374

12. Drag Reducers

Operating Costs37g

Mechanism of Drag Reduction^SQ

Damping of Transmission of Eddies3qq

Viscoelastic Fluid Thread3Q1

Polymer Degradation in Turbulent Flow381

Contents

Drag Reduction in Two-phase Flow 382Drag Reduction in Gas Flow

382Microfibrils

382Drag-reducing Surfactant Solutions 383Soapy Industrial Cleaner

383Lyophobic Performance of the Lining Material 383Interpolymer Complexes 383Drag-reducing Chemicals 384Ultra-high Molecular Weight Polyethylene 384Copolymers of a-Olefins

384Latex Drag Reducers

384Polyether Compounds for Oil-based Well Drilling Fluids 386Tylose

386Microencapsulated Polymers 386Aluminum Carboxylate 386References

387

13. Gas Hydrate Control

Naturally Occurring Gas Hydrates 392Problems with Gas Hydrates in Petroleum Technology 393Nature of Inclusion Compounds 394Gas Hydrates

395Conditions for Formation

397Water Content

397Decomposition 397Stability Diagram 397Clausius-Clapeyron Equation 397Hammerschmidt Equation 399Formation and Properties of Gas Hydrates 399Two-Step Mechanism of Formation 399Nucleation Particle Sizes

400

Clustering Before Nucleation400

. Experimental Methods400

Modeling the Formation of Gas Hydrates 401Test Procedures for Inhibitors 401Screening Method

402High Pressure Sapphire Cell

402Circulating Loop 402Inhibition of Gas Hydrate Formation 403Drying

403Thermodynamic Inhibition with Additives 403Kinetic Inhibition

403Nucleation Inhibitors

404Crystal Growth Inhibitors 404Agglomeration Inhibitors

416Gas Hydrate Inhibitors with Corrosion Inhibition 416Recyclable Antifreeze Agents 417

Contents

Hydrate Inhibitors for Drilling Fluids 419References 420Tradenames 426

14. Antifreeze Agents

Theory of Action 427Antifreeze Chemicals 428Heat Transfer Liquids 429Brines 430Alcohols

430Glycols 430

Toxicity and Environmental Aspects 433

Special Uses434

Hydraulic Cement Additives 434Pipeline Transportation of Aqueous Emulsions of Oil 434Low Temperature Drilling Fluids 435References

435

15. Odorization

General Aspects 438Limits of Explosion 438Desirable Properties of Odorants 438Measurement and Odor Monitoring 439Olfactoric Response 439

Physiological Methods441

Chemical and Physical Methods 444Additives for Odorization 446Sulfur Compounds 446Other Compounds 448Industrial Synthesis of Odorants 450Uses and Properties 451Odorant Injection Techniques 451Leak Detection 452Fuel Cells

452Odor-fading 453Environmental Problems 453References

454Tradenames

458

16. Enhanced Oil RecoveryWaterflooding 460Surfactants

460Interphase Structure 467Interfacial Rheological Properties 468Microemulsion Phase Diagrams 469Interfacial Tension

469Imbibition Experiments 469

Contents

Caustic Waterflooding 470

Injection Strategies 470

Foam-enhanced Caustic Waterflooding 470

Alkaline Surfactant Polymer Flooding 470

Interphase Properties 471

Clay Dissolution 471

Acid Flooding 471

Hydrochloric Acid 471

Sulfuric Acid 472

Emulsion Flooding 472

Micellar Polymer Flooding 473

Chemical Injection 474

Ammonium Carbonate 474

Hydrogen Peroxide 474

Alcohol-Waterflood i ng475

Chemical Injection of Waste Gases 475

Polymer Waterflooding 476

Low-tension Polymer Flood Technique 476

Influence of Viscosity on Ionic Strength 477

Modified Acrylics 477

Biopolymers 477

Combination Flooding 477

Low-tension Polymer Flood 477

Effect of Alkaline Agents on the Retention 478

Alkaline Steamflooding 478

Sediment-forming Materials 478

Water-alternating Gas Technology 479

Hydrocarbon-assisted Steam Injection 479

Foam Flooding 479

Basic Principles of Foam Flooding 479

Ambient Pressure Foam Tests 480

Polymer-enhanced Foams 483

Carbon Dioxide Flooding 483

Steamflooding 484

Carbon Dioxide 484

Air Injection 484

Chemical Reactions 485

In Situ Combustion 485

Special Techniques485

Viscous Oil Recovery485

Low-permeability Flooding 486

Microbial-Enhanced Oil Recovery Techniques 487

Basic Principles and Methods 487

Economics 488

Strict Anaerobic Bacteria 492

Ultramicrobacteria 493

Scale Inhibitors as a Microbial Nutrient 494

Interfacial Properties494

Tracers 495

G5D

Thermal Stability, of Alkyl Benzene Sulfonate

Asphaltene DepositionStabilizer DispersantReservoir PropertiesReservoir Models

Profile Control

Formation DamageWettabilityFlooding of Oil in Chalk

Treatment of Produced Water

Soil Remediation

References

17. Fracturing Fluids

Stresses and Fractures

Comparison of Stimulation TechniquesAction of a Fracturing Fluid

Stages in a Fracturing Job

Types of Hydraulic Fracturing Fluids

Comparison of Different TechniquesExpert Systems for Assessment

Water-Based SystemsThickeners and Gelling AgentsConcentrates

Friction Reducers

Fluid Loss Additives

pH Control Additives

Clay Stabilizers

Biocides

Surfactants

Crosslinkers

Gel Breaking in Water-based SystemsScale Inhibitors

Oil-Based SystemsOrganic Gel Aluminum Phosphate Ester

Increasing the Viscosity of Diesel

Gel Breakers

Foam-Based Fracturing Fluids

Defoamers

Fracturing in Coal-Beds

Propping AgentsSand

Ceramic Particles

Bauxite

Light-weight ProppantsPorous Pack with Fibers

Contents

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497

498

498

498

500

501

501

501

502

502

519

520

520

521

521

524

526

526

526

534

535

535

537

538

539

539

541

546

552

553

553

554

554

555

556

558

559

559

559

560

560

560

Contents

Coated Proppants 560

Anti-settling Additives 561

Proppant Flowback 562

Acid Fracturing 564

Encapsulated Acids 565

The In Situ Formation of Acids 565

Fluid Loss 565

Gel Breaker for Acid Fracturing 565

Special Problems 566

Corrosion Inhibitors 566

The Problem of Iron Control in Fracturing 566

Enhanced Temperature Stability 567

Chemical Blowing 567

Frost-resistant Formulation 568

Formation Damage in Gas Wells 569

Characterization of Fracturing Fluids 569

Rheological Characterization 569

Zirconium-based Crosslinking Agent 570

Oxidative Gel Breaker 570

Size Exclusion Chromatography 570

Assessment of Proppants 570

References 571

Tradenames 583

18. Water Shutoff

Classification of Methods 585

In Situ Polymerization 586

Acrylic Gels 587

Crosslinkers 587

Special Applications 590

Shear-Initiated Inversion of Emulsions 591

Thermally Stable Gels 591

Disproportionate Permeability Reduction 591

Field Experience 592

Silicate-based Agents 592

Combined Polymer-Silicate Technology 593

Gel-Foam Technique 593

Resin Types 595

Epoxide Resins 595

Urea-Formaldehyde Resins 595

Furan-Silicone Resins 597

Cement with Additives 597

Polymethyl Methacrylate Modified with Monoethanolamine 597

Crude Light Pyridine Bases 597

Granulated Fly Ash 598

Phosphonic Acid Derivates 598

(xviii) Contents

Phosphonium Complexone 599

Aerated Plugging Solution 599

Compressed Foam Mixture 600

Furfuramide 600

Cellulosics and Polyacrylics 600

Smectite Clays 601

Plasticizers 601

Water Glass 602

Organosilicones 602

Formaldehyde Resin 603

Liquid Metal Alloy 603

Bentonite,

604

Blast Furnace Slag 604

Fiber Reinforcement 605

Gels from Aluminum Hydroxychloride 605

Organosilicones 606

Non-Crosslinked Copolymers 607

Anchoring 607

Inorganic Colloids 607

Water Swelling Additives 608

Water-swelling Cellulose 608

Hydrolyzed Polyacrylonitrile 608

Guar 609

Clays 609

Wastes 609

Waste Oil Sludge 609

Aluminum Trichloride 610

Antifoaming with Sulfite-waste Liquor 611

Surfactants 611

Polymeric Surfactants 611

Viscoelastic Surfactant Solutions 612

Tailoring the Hydrodynamic Volume 613

Temperature-Sensitive Latex Particles 614

References 615

Tradenames 623

19. Oil Spill Treating Agents

History 625

List of Major Oil Spills 625

General Requirements 627

Mechanisms 627

Application 628

Environmental Aspects 630

Implementation Application Programs 632

Tests 633

Subsurface, Soil, and Ground Water 638

In Situ Chemical Oxidation 639

Ground Water 639

Contents

Chemicals in Detail 639

References 641

20. Waste Disposal

Drilling Fluids 647

Bioremediation 647

Assessment of Biodegradability 648

Supercritical Fluid Extraction 649

Cuttings 649

Environmental Impact 649

Modeling the Discharge 650

Microwave Treatment 651

Discharge in Cement 654Fillers in Bitumen 655

Chromium Removal 655

Injection Techniques 655

Acid Gas Injection 656

Storage of Carbon Dioxide 656

Slurry Fracture Injection Technique 656

Use as Sealants 658

References 660

Tradenames 662

21. Dispersions, Emulsions, and Foams

Dispersions 664

Dispersants 664

Emulsions 670

Oil-in-water Emulsions - Invert Emulsions 671

Water-in-water Emulsions 673

Oil-in-water-in-oil Emulsions 673

Microemulsions 674

Solids-stabilized emulsion 674

Biotreated Emulsion 676

Shale Inhibition 677

Transportation 678

Acid-rich Oils 678

Characterization of Emulsions 678

Low Fluorescence Emulsifiers 682

Foams 683

Aphrons 684

References 688

Tradenames 693

22. Defoamers

Theory of Defoaming 695

Stability of Foams 695

Action of Defoamers 696

Contents

Classification of Defoamers 698

Active Ingredients 698

Ancillary Agents 699

Uses in Petroleum Technology 699

Aqueous Fluid Systems 699

Well Treatment and Cementation 700

Plugging Agents 701

Gas-Oil Separation 701

Natural Gas 702

Distillation and Petroleum Production 702

Antimicrobial Antifoam Compositions 703

References 703

23. Demulsifiers

Emulsions in Produced Crude Oil 705

Waterflooding 706

Oil Spill Treatment 706

Desired Properties 706

Mechanisms of Demulsification 706

Stabilization of Water-oil Emulsions 706

Interfacial Tension Relaxation 706

Performance Testing 707

Spreading Pressure 707

Characterization by Dielectric Constant 707

Shaker Test Methods 707

Viscosity Measurements 707

Screening 708

Classification of Demulsifiers 708

Common Precursor Chemicals 708

Demulsifiers in Detail 710

Polyoxyalkylenes 710

Vinyl Polymers 713

Polyamines 716

Polyamides 718

Phenolics 718

Alkoxylated Fatty Oils 719

Biodemulsifiers 719

References 720

Appendix 1: List of Tradenames 727

Appendix 2: List of Acronyms 735

Index

Chemical Index 739

Subject Index 767