PETROLEUMGEOCHEMISTRY

Dr. D. SatyanarayanaVisiting Professor, Delta Studies Institute &

Former Professor of Marine ChemistryAndhra University, Visakhapatnam

2011DAYA PUBLISHING HOUSE

Delhi - 110 035

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© 2011, D. SATYANARAYANAISBN 81-7035-675-XISBN 978-81-7035-675-2

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Acknowledgements

I am grateful to the following publishers, Authors/Editors ofbooks for according permission to use their published illustrations.

P M/S Academic Press, R.C. Selley. Elements of PetroleumGeology (1998); J. Brooks (Ed). Organic Maturation Studiesand Fossil Fuel Exploration (1981).

P M/S Applied Science Publishers, G.D. Hobson (Ed).Developments in Petroleum Geology, Vol. I (1977) and Vol.II (1980).

P M/S Burgess Publishing Company, Douglas Waples.Organic Geochemistry for exploration Geologists (1981).

P M/S Chapman & Hall, Steven A Tedesco. SurfaceGeochemistry in Petroleum Exploration (1995).

P M/S Directorate General of Hydrocarbons (DGH). India–Petroleum Exploration and production Activities–2005-2006.

P M/S Elsevier Publishers, E.C Donaldson (Ed). Enhancedoil Recovery I : Fundamentals and analysis (1985).

P M/S Indian Petroleum Publishers, S.K. Biswas et al., (Eds).Proceedings of 2nd Seminar on Petroliferous Basins ofIndia. Vol. I and Vol. II (1993); Lakshman Singh. Oil andGas Fields in India (2000).

P M/S International Human Resource DevelopmentCorporation (IHRD), Douglas, W. Waples. Geochemistryin Petroleum Exploration (1985).

P M/S Kluwer Academic Publishers, M.D. Max (Ed). NaturalGas Hydrates (2000).

P M/S Springer–Verlag, B.P Tissot and D.H. Welte.Petroleum Formation and Occurrence (1984).

P M/S. Unwin Hyman Publishers, F.K. North. PetroleumGeology, 2nd edition (1990).

P M/S Freeman and Company, J.M. Hunt. PetroleumGeochemistry and Geology, 2nd edition (1996); A.I.Levorsen. Geology of Petroleum, 2nd edition (1967).

D. Satyanarayana

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Foreword

Petroleum Geochemistry is a branch of Organic Geochemistrythat deals with the study of distribution, composition andconstitution of petroleum, its constituents and its precursors insedimentosphere at gross and molecular levels to define principlesof occurrence and origin of petroleum in sedimentary basins, theubiquitous natural habitats of economically attractiveaccumulations.

The vicissitudes of basin evolutionary history of eachsedimentary basin are complex and no two points along dip or striketheoretically have identical depositional conditions. No techniqueof petroleum exploration is, therefore, equally sensitive and accuratein space and time. Petroleum exploration and exploitation is thusboth knowledge and technology intensive and is essentially amultidisciplinary task where an inadequacy of one discipline ortechnique is covered by strengths of one or other discipline ortechnique or set of disciplines or techniques. While geology andgeophysics are excellent in unraveling the types of rocks, theirphysical attributes, structural attitudes and their distribution andsuperposition in space and time in a basin, they are unable to dealdirectly with aspects of origin, migration and accumulation ofpetroleum.

One of the imperatives of the industry is to have knowledge onaspects of origin and occurrence of petroleum specific to each basinor part thereof. This is essential to ensure reduction of risk inpetroleum exploration. Petroleum Geochemistry helps explorationand development effort in each phase, right from reconnaissanceand stage of general assessment to the final stage of extraction of thelast producible content of hydrocarbons in a locale of accumulation,by providing geochemical concepts and data sets on various aspectsof origin, migration and accumulation of petroleum specific to eachbasin under exploration and development. Tremendousdevelopments have taken place in acquisition of petroleumgeochemical data since the nineteen sixties through availability ofrobust equipments and methods of chemical analysis. It is nowpossible to have practically real time geochemical data to beintegrated timely for making an exploration or development decision.

Synergy amongst Petroleum Geology, Petroleum Geochemistryand Geophysics has become an accepted practice for laying downrisk based priorities in a portfolio of exploration and developmentopportunities. The synergy also leads to working out manageableinvestments to initialize an E&P activity with cash flows that can bedeployed for further exploration and development efforts whileassuring market competitive returns during the entire cycle of anygiven exploration and development activity.

Dr. D. Satyanarayana of the Delta Studies Institute of AndhraUniversity has done yeoman’s service to Indian academia to bringout a maiden Indian text book on Petroleum Geochemistry. Thisbook will be found useful to graduate and postgraduate studentstaking courses in petroleum geology, petroleum exploration andpetroleum engineering. The book touches upon authentically allaspects of petroleum geochemistry that are relevant to explorationand development effort.

In India, Oil and Natural Gas Corporation commencedundertaking petroleum geochemical studies in 1957 and establishedformal laboratories in 1960. ONGC Limited has since 1963 best inclass research facilities in Petroleum Geochemistry at Keshav DevMalviya Institute of Petroleum Exploration (KDMIPE) along with astrong Basin Studies Group at Dehradun. ONGC Limited also has,since 1985, standard data acquisition laboratories in all operationalareas. Oil India has modern Petroleum Geochemistry laboratories

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since 1990. National Geophysical Research Institute has a NationalCentre of Excellence in Surface Geochemical Prospecting backed byOil Industries Development Board and Director GeneralHydrocarbons since 2001-02 which caters to the requirements ofgeochemical data acquisition of various private sector oil companiesand DGH to help evaluate prospectively of various acreages andexploration blocks. All private sector and joint venture majorupstream oil companies profusely integrate geochemical data inexploration decision making. This book of Dr. Satyanarayana istherefore has great practical value for the upstream petroleumindustry in general and especially for India where large acreagesstill remain explored, where deep and ultra deep water explorationhas just begun and where the ageing oil fields are being operated formaximizing recovery factors.

To students with enquiring and creative minds and aptitudefor innovation, the book surely would inspire to undertake basicand applied research. Dr. Satyanarayana joins the illustriouseminent academicians of the world, who brought out books born oflecture notes meant to disseminate in depth knowledge of PetroleumGeochemistry for geoscientists actively engaged in upstreamactivities.

The book is going to be a prized possession of academia ingeosciences and of all the scientists and engineers of the upstreampetroleum industry who are desirous to contribute their mite towardssustaining and augmenting global energy security through longtime availability of petroleum.

Kuldeep Chandra

Dehradun Former Executive Director R&D ONGC Limited,and

Chairman, Afro-Asian Association of Petroleum Geochemists

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Preface

During the last three decades there has been a rapid progress inpetroleum geochemistry. The aim of this book is to cover the advancesin a comprehensive way providing a background for understandingthe basic concepts and principles. It is designed to develop principlesof petroleum geochemistry and emphasise its applications tohydrocarbon exploration. Several geochemical and analyticaltechniques are described along with their relative merits andlimitations so that an appropriate technique can be selected in aparticular exploration programme. Application of principles ofpetroleum geochemistry to common exploration programmes arelucidly brought out by introducing worked out examples and casestudies.

The book is written primarily for postgraduate students of earthsciences and graduate students of engineering taking courses inpetroleum science or engineering. It is also useful for those workingin oil industry dealing with exploration and related fields. Eachgeochemical concept is explained in detail prior to its application.Adequate references are cited in the text. Exhaustive list of books,memoirs, papers published in journals and proceeding of WorldCongress, International Seminars and Symposia are included in thebibliography for further reading. The contents are arranged in thefollowing sequence so as to interpret geochemical data of varied

reliability and to unravel complex geochemical processes involvedin petroleum exploration and production.

P Role of petroleum geochemistry in prospect identification,prioritisation and risk reduction in hydrocarbonexploration and production. Composition, properties andgenetic classification of crude oil and natural gas.

P Occurrence of petroleum in sedimentary basins–Basintype, classification and hydrocarbon richness. Resourceestimation and production potential of typical Indianpetroliferous basins of proven commercial production.

P The origin of Petroleum-Inorganic (abiogenic) and organic(biogenic) theories and their relative merits andlimitations. Polymerisation theory of petroleum formationand its implications.

P Geochemical processes involved in generation, migrationand accumulation of hydrocarbons in sedimentary basins.Factors effecting them and optimum conditions forcommercial production of petroleum.

P Application of geochemical methods for the study oforganic maturation, evaluation of stratigraphic units anddistribution of organo facies for delineation ofhydrocarbon kitchens. Principles of source rockevaluation. Typical examples and case studies.

P Geochemical surface prospecting of hydrocarbons toidentify anomalous areas that prioritise targets for futureexploration. Relative merits and limitations of surfacegeochemical methods.

P Application of hydrogeochemical surveys in exploration.Genetic indicators for delineation of oil wells. Role of oilfield waters in enhanced oil recovery operations, andin situ oil degradation in reservoirs. Implications of scaleformation and corrosion in petroleum exploration andproduction operations.

P Role of biomarkers for characterization and evaluation ofsource organo facies and depositional environments.Application of high resolution geochemical techniquessuch as GC-MS, CF-IRMS, MRM-GC-MS for molecular levelstudies involving thermal cracking of light oil and

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condensates; oil-oil, oil-source rock correlations tounderstand migration pathways; petroleum system andpaleodepositional environments at micro level.

P Geochemical modeling of hydrocarbon generation basedon kinetics of kerogen degradation. Integration of the modelwith geological history of the basin to delineate prospectiveareas. Validity of the model and its application forevaluation of petroleum potential and determination oftiming of its formation for comparison with the age oftraps.

P Application of geochemical techniques to unconventionalpetroleum resources such as shale gas and oil shale;bituminous sands; basin centered (tight) gas sands; coalbed methane (CBM); gas hydrates. Study of theircharacteristics, depositional environments, resourcepotential, exploration and production strategies, andenvironmental concerns. Global and Indianunconventional petroleum resources.

I acknowledge with thanks the authorities of Andhra Universityfor offering an honorary professorship in Delta Studies Institute(DSI) which prompted me to write this book. It evolved from a seriesof lectures delivered on petroleum geochemistry to the students ofM.Tech. Petroleum Exploration and discussions with severaldistinguished visiting faculty members. I take this opportunity tothank Prof. D. Rajasekhara Reddy, Director (DSI) for offering facilities,and to Sri T. Karunakarudu and V. Jayasundar Reddy (TeachingAssistants) for their assistance in the institute. My thanks are alsodue to several visiting faculty of DSI and former scientists of ONGC–Sri P.V. Ramana Rao, GGM; Sri S.S. Yalamarty, GGM & BasinManager; Sri P.V. Ramana, G.G.M & Director, IRS; Sri G.S. Chari,D.G.M; Sri B.V. Rao, D.G.M; Dr. P.V.L.P. Babu, D.G.M for theirencouragement.

I am particularly grateful to Dr. Kuldeep Chandra, FormerExecutive Director, ONGC and President of Afro-Asian Associationof Petroleum Geochemists, for offering several constructivesuggestions and improving the quality of the text. I am very muchthankful and obliged for his kind gesture of writing the Foreword.

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My special thanks are due to Prof. V.R.R.M. Babu, FormerProfessor of Geology and Geoengineering; Prof. U. Muralikrishna,Former Professor of Chemistry of Andhra University; Sri K. AnantaKrishna, Former DGM, ONGC for critically going through the textand offering valuable suggestions. I am thankful to Prof.G.S.Roonwal, Former Professor of Geology, Delhi University; Dr.V.V. Sarma, Scientist G, Regional Centre of NIO, Visakhapatnam;Dr. I. Nageswara Rao, Research Scientist, School of Chemistry; Dr.P. Prabhakar, Chief Chemist, ONGC for their assistance.

My special appreciation goes to Sri V. Hari Prasad and Sri M.Santhosh Kumar, Technical Assistants of DSI, for diligently bringingout the text including Tables and Figures.

D. Satyanarayana

Visiting Professor, Delta Studies Institute &Former Professor of Marine Chemistry

Andhra University, Visakhapatnam

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Contents

Acknowledgements v

Foreword vii

Preface xi

1. Introduction 1

2. Composition and Properties of Petroleum 5

2.1. Saturated Hydrocarbons 72.2. Unsaturated Hydrocarbons 142.3. Compounds with Hetero (NSO) Atoms 182.4. Natural Gases 202.5. Physical Properties of Crude Oils 232.6. Thermal Alteration of Oil in the Reservoir 282.7. Classification of Crude Oils 28

3. Occurrence of Petroleum in Sedimentary Basins 34

3.1. Definition of a Sedimentary Basin 343.2. Classification of Indian Petroliferous

Sedimentary Basins 403.3. Cambay Basin 48

3.4. Mumbai Offshore Basin 553.5. Krishna–Godavari (K–G) Basin 643.6. Cauvery Basin 703.7. Assam-Arakan Basin 743.8. Rajasthan Basin 85

4. Origin of Petroleum 90

4.1. Inorganic (abiogenic) Theory 904.2. Organic (biogenic) Theory 954.3. Conclusion 97

5. Hydrocarbon Generation, Migration andAccumulation in Sedimentary Basins 98

5.1. The Carbon Cycle 985.2. Genesis of Petroleum 1025.3. Migration and Accumulation of Hydrocarbons 1135.4. Mechanism of Primary Migration 1155.5. Secondary Migration 1225.6. Accumulation and its Efficiency 125

6. Geochemical Methods in Petroleum Exploration 128

6.1. Isolation of Kerogen and Bitumen 1286.2. Petrographic Methods 1296.3. Geochemical Methods 1356.4. Stable Isotope Analysis 1386.5. Rock-Eval Pyrolysis Method 1416.6. Time–Temperature Index (TTI) 1486.7. Level of Organic Metamorphism (LOM) 1666.8. Correlation Between Geochemical and

Petrographic Techniques 172

7 Source Rock Evaluation and Correlations 176

7.1. Principles of Source Rock Evaluation 1767.2. Interpretation of Source Rock Data 181

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7.3. Quantitative Volumetric Estimation of SourceRock Hydrocarbons in a Basin 189

7.4. Oil-oil and Oil-Source Rock Correlations 1937.5. Alteration Processes of Crude Oil Composition 1977.6. Oil-oil Correlations 2007.7. Oil-Source Rock Correlations 2027.8. Correlation Parameters for Gases 2077.9. Case Studies 208

8. Surface Geochemical Prospecting of Hydrocarbons 220

8.1. Seepages 2208.2. Surface Geochemical Prospecting 2238.3. Categories of Surface Geochemical Methods 224

9. Hydro Geochemistry of Oil Field Waters 234

9.1. Types and Definitions of Oil Field Waters 2359.2. Classification of Oilfield Waters 2369.3. Physical Properties of Oil Field Waters 2389.4. Chemical Composition of Oil Field Waters 2399.5. Origin and Evolution 2429.6. Genetic Relation to Evaporites 2439.7. Patterns and Significance of Salinity Distribution 2449.8. Role of Oil Field Waters in Enhanced Oil

Recovery (EOR) Operations 2469.9. Oil Degradation in the Reservoir 249

10. Organic Geochemistry and Analytical Techniques 257

10.1. Biomarkers 25710.2. Specific Biomarkers 25910.3. Use of Biomarkers 27110.4. Analytical Techniques in Petroleum Exploration 27310.5. Column Chromatography 27610.6. Gas Chromatography (GC) 27710.7. Mass Spectrometry 281

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10.8. Spectroscopic Methods 28410.9. Thermogravimetry (TG) and Differential

Thermal Analysis (DTA) 291

11. Geochemical Basin Modeling: Applicationto Petroleum Exploration 294

11.1. Integrated Models of Hydrocarbon System 29411.2. Qualitative Models of Hydrocarbon System 29511.3. Quantitative Geochemical Models 29611.4. Mathematical Model of Kerogen Degradation

and Hydrocarbon Generation 29711.5. Application of the Model to Petroleum Exploration 308

12. Unconventional Petroleum Resources 314

12.1. Typical Unconventional Petroleum Systems 31412.2. Basinal (Deep) Gas (Tight Gas) Sands 31512.3. Shale Gas 31612.4. Oil Shale 31712.5. Bituminous (Tar) Sands 31812.6. Coal Bed Methane (CBM) 32012.7. Gas Hydrates 34212.8. Stability of Gas Hydrates 34812.9. Detection of Gas Hydrates 352

12.10. Distribution of Gas Hydrates 357

Appendices 363

References 371

Bibliography 405

Author Index 417

Subject Index 425

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