harry n. giles clifford o. mills crude oils...mills has been involved with astm methods development...

Harry N. Giles is retired from the Department of Energy where he was manager of crude oil quality programs for the Strategic Petroleum Reserve. This included development and management of analytical programs for monitoring quality of stocks, and research related to the biological and geochemical aspects of petroleum stockpiling. Harry was employed by the Department of Energy for over 30 years, prior to which he held several positions with other U.S. Government agencies and at the University of Manchester (UK). Following retirement from the Department of Energy, Harry became Executive Director of the Crude Oil Quality Association, a position he held until resigning in 2013. Following his resignation, he was named Executive Director Emeritus. Harry has authored or co-authored a number of articles on crude oil analysis, characterization, and storage, and on fuel stability and cleanliness. He has been a member of ASTM Committee D02 on Petroleum Products, Liquid Fuels, and Lubricants since the 1980s, and is past chairman of Subcommittee D02.14 on Stability , Cleanliness and Compatibility of Liquid Fuels. Harry remains active in several D02 Subcommittees, and is a technical advisor to ASTM for their Crude Oil Proficiency Testing Program (PTP). In 2005, he and Clifford Mills developed the ASTM training course on “Crude Oil: Sampling, Testing, and Evaluation.” In 2008, he received the ASTM International George V. Dyroff Award of Honorary Committee D02 Membership. Other memberships include the API Committee on Measurement Quality, and IASH, the International Association for Stability, Handling, and Use of Liquid Fuels. He is chairman emeritus of IASH, and was elected to honorary membership in 2009.

Clifford O. Mills is retired from CONOCO where he served in numerous capacities. At retirement, after 35 years, he was a laboratory consultant with an emphasis on crude oil analysis. Mr. Mills has been involved with ASTM methods development since the early 1980s. Until recently, he was chairman of ASTM D02.05 on Properties of Fuels, Petroleum Coke and Carbon Material, and also chaired D02.H0 on Liquefied Petroleum Gas for several years. He continues to be active in D02.03, D02.04, D02.05, D02.06 and D02.H0. Mr. Mills has been actively involved in development of numerous ASTM methods of analysis. Together with Mr. Giles, he serves as technical advisor to ASTM for their Crude Oil ILCP. For several years, Mr. Mills served as co-instructor for the crude oil training course and, together with Mr. Giles, presented this at numerous locations worldwide. He is a member of the Crude Oil Quality Association, and author of an authoritative paper on crude contaminants and analysis requirements presented at one of their meetings. This paper is now widely referenced and used as an instructional aid. In 2008, he received the ASTM International George V. Dyroff Award of Honorary Committee D02 Membership.

ASTM INTERNATIONAL Manual

Crude Oils: Their Sampling, Analysis, and Evaluation2ND Edition

Harry N. Giles Clifford O. Mills

ASTM INTERNATIONAL Helping our world work better

ISBN: 978-0-8031-7104-6 Stock #: MNL68-2ND

www.astm.org

Giles | M

illsC

rude Oils: Their S

ampling, A

nalysis, and Evaluation | 2N

D Edition

Harry N. Giles and Clifford O. Mills

Crude Oils: Their Sampling, Analysis, and Evaluation—2nd EditionASTM Stock Number: MNL68-2ND

ASTM International100 Barr Harbor DrivePO Box C700West Conshohocken, PA 19428-2959

Printed in U.S.A.

BK-AST-MNL68-180177-FM.indd 1 8/21/18 11:32 AM

Copyright © 2018 ASTM International, West Conshohocken, PA. All rights reserved. This material may not be reproduced or copied, in whole or in part, in any printed, mechanical, electronic, film, or other distribution and storage media, without the written consent of the publisher.

Photocopy RightsAuthorization to photocopy items for internal, personal, or educational classroom use, or the internal, personal, or educational classroom use of specific clients, is granted by ASTM International provided that the appropriate fee is paid to the Copyright Clearance Center, 222 Rosewood Drive, Danvers, MA 01923, Tel: (978) 646-2600; http://www.copyright.com/

Publisher:ASTM International100 Barr Harbor DrivePO Box C700West Conshohocken, PA 19428-2959Phone: (610) 832-9585 Fax: (610) 832-9555

ISBN 978-0-8031-7104-6

ASTM Stock Number: MNL68-2NDDOI: 10.1520/MNL68-2ND-EB

ASTM International is not responsible, as a body, for the statements and opinions advanced in the publication. ASTM International does not endorse any products represented in this publication.

Printed in Mayfield, PAAugust, 2018

Library of Congress Cataloging-in-Publication Data

Names: Giles, Harry N., author. | Mills, Clifford O., author.Title: Crude oils : their sampling, analysis, and evaluation / Harry N. Giles and Clifford O. Mills.Description: 2nd edition. | West Conshohocken, PA : ASTM International, 2018. | Includes bibliographical references and index.Identifiers: LCCN 2018026759 | ISBN 9780803171046 (alk. paper)Subjects: LCSH: Petroleum—Analysis.Classification: LCC TP691 .G545 2018 | DDC 665.5—dc23LC record available at https://lccn.loc.gov/2018026759


iii

Foreword

The second edition of Crude Oils: Their Sampling, Analysis, and Evaluation, spon-sored by ASTM Committee D02 on Petroleum Products, Liquid Fuels and Lubricants, has been expanded from the original edition that appeared in 2010. The new edition includes 16 new ASTM methods and reviews of 79 revised methods. It is intended principally for those involved with the sampling, analysis, and use of crude oils after they are produced and stabilized.

Methods and procedures are rapidly changing, requiring revision to existing methods from D56–D7482, and the standardization of new methods D7578–D8150. Modern data handling and advances in computerization allow highly detailed com-positional analyses to be readily performed. More elemental analyses, especially for mercury, have been standardized, and more techniques for metal analyses are being introduced.

Industry and governmental requirements for accurate and more detailed data are now required for crude oil transportation as they have been for decades with products. Shale-derived crude oil has driven improved sampling and analyses of vapor pressure. Detailed analyses in a shorter time frame have resulted in substan-tial method changes and development of “synthetic assays” that fill a gap between inspection and comprehensive assays. Rapid instrumental techniques incorporating automatic sampling and online analyses are seeing greater applications. However, many fundamental physical and chemical analyses recognized as established tech-niques are still used, as evidenced in salt analyses in which D3230 conductivity remains preferred over D6470 potentiometric titration. The established methods are discussed in this manual as well as those recently developed.

The importance of sampling, quality control, and field methods are discussed. Adherence to a rigorous sampling protocol to ensure that samples represent the bulk material is essential. Likewise, quality assurance is considered from the limits of precision and accuracy defined in the test methods used. Inaccurate data can have severe financial and operational consequences. Field methods can provide data for quick decisions. Future analytical needs are discussed.

This manual will continue to be an influential guide to the sampling, analysis, and evaluation of crude oil. The strategic importance of crude oil will last for years to come, and this manual helps measure its economic value.


http://www.astm.org/Standards/D02







v

Contents

Preface vii

Acknowledgments ix

Glossary of Terms xi

1 Introduction 1Brief History of Crude Oil Use and Exploitation 2Strategic Importance of Crude Oil 4Developments in Analysis of Crude Oil 4Crude Oil Classification 5

2 Sampling 7Manual Sampling 8Automatic Sampling 8Sampling Volatile Crude Oil 8Sample Containers 8Mixing and Handling of Samples 8Sample Chain of Custody 10Sample Archive 10Summary 10

3 Inspection Analyses 13API Gravity and Density 13Sulfur Content 15Water and Sediment 16Salt Content 20Fluidity—Pour Point and Viscosity 21Vapor Pressure 22Total Acid Number 23Carbon Residue 24Characterization Factor 24Trace Elements 25Nitrogen Content 30Organic Halides 31Asphaltenes 33Boiling Point Distribution 35Other Tests 37Referee Test Methods 40Summary 40

4 Comprehensive Analyses and Fraction Evaluations 41True Boiling Point Distillation 41Gas 44Naphtha Fractions 44Kerosene 44Distillate Fuel Oil 44


vi Crude Oils: Their Sampling, Analysis, and Evaluation—2nd Edition

Vacuum Gas Oil Fractions 47Residuum 47Summary 47Conclusion 48

5 Quality Assurance 49

6 Crude Oil Compatibility and Stability 53Asphaltenes 53Waxes 54

7 Quality Case Studies 57Organic Chloride Contamination 57Sediment and Water Determination 57Green Distillate 57Wax Precipitation and Incompatibility 58Dumbbell Crude 58Lookalike Crude 58Metals Contamination 58Vapor Pressure Determination 59Common Carrier Pipeline Issue 59Inadequate Contract Quality Requirements 59Summary 59

8 Crude Oil as Fuel 61

9 Future Needs in Crude Oil Characterization 63

Postscript 67

Appendix X1. Procedures for Collecting Samples for H2S Determination 69Narrow-Mouth HDPE Bottles—1-L Capacity 69Floating Piston Cylinders (Sulfinert®-Treated) 69

Appendix X2. Referenced ASTM and Other Standards 71

Appendix X3. Excerpts from Standards Used for Sampling, Handling, and Analysis 73Sampling and Handling Practices 73Test Methods 77

References 105

Index 113


vii

Since publication of the first edition of this manual in 2010, sev-eral new ASTM test methods for crude oils have been approved and a number of existing methods revised. Moreover, interest in topics such as vapor pressure has grown with the increase in transportation of crude by rail and a number of fiery accidents related thereto. Hydraulic fracturing of shale deposits is intro-ducing numerous chemicals in the produced crude oil that potentially adversely affect processing. Each of these topics is addressed in this revised and expanded edition. Furthermore,

some of the historical background in development of a number of the test methods has been added to provide the reader insight into their significance, use, and application. A new chapter on quality case studies has been added to illustrate the importance of obtaining comprehensive analyses of crude oil streams and the need for including detailed requirements in sales and purchase agreements. The references have been expanded considerably to provide the reader further sources of detailed information on the topics covered.

Preface


ix

This manual is based on the ASTM International Technical and Professional Training Course of the same name that has been taught by the authors at a number of locations worldwide numer-ous times since 2005. This manual would not have been possible without the support and encouragement of many of our colleagues and participants in the course. We are grateful to many individu-als and companies for providing us some of the material included herein. We appreciate their willingness to share this information, as it makes our task easier illustrating some of the topics. The fol-lowing individuals and companies provided some of the material included in the course and used in this manual: Baker Hughes and Larry Kremer; Peg Broughton; the Canadian Crude Quality Technical Association and Andre Lemieux; Chevron Energy Technology Company and Anne Shafizadeh; Gordon Chiu; E. Chomery; the Crude Oil Quality Association; DynMcDermott Petroleum Operating Co.; Dräger Safety AG & Co.; Patti Edens

and Shell Pipeline; R. Goodrich and KBC; Haverly Systems and Ken Spencer; Institute of Chemical Technology (Prague); Intertek; KBW Process Engineers; Koehler Instruments; LK Industries; Sam Lordo and Nalco Champion; G. A. Mansoori; Northrop Grumman Mission Systems; PetroTech Intel and Patrice Perkins; P. Rahimi; R. Segato and Syncrude; Stanhope-Seta and I. Mylrea and M. Sherratt; Pat Swafford; Bahman Tohidi; Dan Villalanti; Anne Brackett Walker; Gary Weimer; and Welker Engineering and David Fish. We apologize if we neglected to mention anyone that has assisted us; this is not intentional. Al Verstuyft kindly reviewed the manuscript and provided many valuable comments that helped us improve the contents. We also thank the staff at ASTM International that helped in making the course a reality and to the members of the publications department for their guid-ance, support and, most of all, their patience during the prepara-tion of this manual.

Acknowledgments


xi

Additive—Substance added to a crude oil stream in relatively minor amounts to facilitate its production and transportation and minimize adverse effects on equipment. These include pour point depressants, drag-reducing agents, demulsifiers, and cor-rosion inhibitors.

API gravity—A special function of relative density (specific grav-ity) 60/60°F represented by °API = 141.5/(sp gr 60/60°F) – 131.5. ASTM D287

Analysis (assay)—A combination of physical and chemical data that uniquely describes a crude oil.

Bitumen—A category of crude oil that is highly viscous and semi-solid at ambient temperatures, will not flow without dilution, and generally has an API of less than 10°.

Challenging (or challenged) crude—See Opportunity crude.Compatibility—The capability of two or more crude oils to be com-

mingled without asphaltenes or waxes precipitating or flocculat-ing out of the mixture (c.f. Incompatibility).

Condensate—Liquid mixture usually recovered from natural gas, consisting primarily of hydrocarbons from approximately C6 to C12–15 and having an API gravity greater than about 45°. The mixture may also contain hydrogen sulfide, thiols, carbon diox-ide, nitrogen, and other nonhydrocarbon compounds. Some consider condensate to be a light, sweet crude oil. Other terms include gas condensate, natural gas liquids, lease condensate, and natural gasoline.

Contaminant—Any material added to a crude oil stream that is not naturally occurring or exceeds the concentration normally present.

Crude oil—Naturally occurring hydrocarbon mixture, generally in a liquid state, that may also contain compounds of sulfur, nitrogen, oxygen, metals, and other elements. ASTM D4175

Dead crude oil—Crude oil with sufficiently low vapor pressure that, when exposed to normal atmospheric pressure at room temperature, does not result in boiling of the sample. ASTM D6377

Degradation—A lessening in the quality of a crude oil stream com-monly resulting from mixing of another stream of poorer qual-ity. Degradation of a crude oil can also result from biological activity.

Differentiation—Natural development of a density differential from top to bottom in a storage container (c.f. Stratification).

Impurity—Nonhydrocarbons naturally occurring in crude oil. These typically include sediment, water, salts, organic acids, het-eroatomic compounds of sulfur, nitrogen, and oxygen, and met-als—particularly nickel and vanadium.

Incompatibility—Agglomeration or flocculation of asphaltenes or waxes, or both, from a mixture of two or more crude oils (c.f. Compatibility).

Live crude oil—Crude oil with sufficiently high vapor pressure that it would boil if exposed to normal atmospheric pressure at room temperature. ASTM D6377

Opportunity crude—A crude oil priced below market value. An opportunity crude may be produced from a new field with little or no processing history, a distressed cargo, or a crude oil with a known history that reduces refinery profitability, the last of which can result from the crude having a high total acid num-ber, sulfur content, or metals, problematic contaminants, or is difficult to upgrade or has unattractive yields.

Referee test method—An analytical method designated in testing protocols to be used in case of disputes.

Relative density (specific gravity)—The ratio of the mass of a given volume of liquid at a specific temperature to the mass of an equal volume of pure water at the same or different temperature. Both reference temperatures must be explicitly stated. ASTM D1298

Representative sample—A portion extracted from a total volume that contains the constituents in the same proportion as are present in the total volume. ASTM D4057

Sampling—All steps required to obtain an aliquot representative of the contents of any tank, pipeline, or other system and to place the sample into a suitable laboratory sample container. ASTM D6470

Slop Oil—A combination of off-specification fuel, water, refinery wastes, and transmix. Slop oil is usually processed in the gener-ating refinery but is occasionally exported or shipped domesti-cally for use as an inexpensive feedstock for processing in atmospheric units or as a low-BTU fuel.

Stability—The ability of a crude oil when produced, transported, or stored to endure without physical or chemical change, such as flocculation or precipitation of asphaltenes or waxes, or both.

Stratification—The intentional layering of different crudes oils in a storage container taking advantage of differences in their den-sity (c.f. Differentiation).

Glossary of Terms

BK-AST-MNL68-180177-FM.indd 11 8/21/18 6:30 PM








xii Crude Oils: Their Sampling, Analysis, and Evaluation—2nd Edition

Synthetic crude oil—Stream derived by upgrading oil sand bitu-men and extra heavy crude oil. Upgrading processes include hydroprocessing and coking to yield a more fungible, lighter, less viscous stream.

Tight oil (also known as shale oil and light, tight oil)—Crude oil produced by hydraulic fracturing of geologic formations such as shale. In the United States, this is typified by production from

the Bakken Formation in North Dakota and the Eagle Ford Formation and Permian Basin in Texas.

Transmix—Transportation mixture is the material present at the interface between different quality crude oils batched in a common carrier pipeline system. Generally, at a terminal, the mixture will be relegated to the lower-quality crude oil.


Harry N. Giles is retired from the Department of Energy where he was manager of crude oil quality programs for the Strategic Petroleum Reserve. This included development and management of analytical programs for monitoring quality of stocks, and research related to the biological and geochemical aspects of petroleum stockpiling. Harry was employed by the Department of Energy for over 30 years, prior to which he held several positions with other U.S. Government agencies and at the University of Manchester (UK). Following retirement from the Department of Energy, Harry became Executive Director of the Crude Oil Quality Association, a position he held until resigning in 2013. Following his resignation, he was named Executive Director Emeritus. Harry has authored or co-authored a number of articles on crude oil analysis, characterization, and storage, and on fuel stability and cleanliness. He has been a member of ASTM Committee D02 on Petroleum Products, Liquid Fuels, and Lubricants since the 1980s, and is past chairman of Subcommittee D02.14 on Stability , Cleanliness and Compatibility of Liquid Fuels. Harry remains active in several D02 Subcommittees, and is a technical advisor to ASTM for their Crude Oil Proficiency Testing Program (PTP). In 2005, he and Clifford Mills developed the ASTM training course on “Crude Oil: Sampling, Testing, and Evaluation.” In 2008, he received the ASTM International George V. Dyroff Award of Honorary Committee D02 Membership. Other memberships include the API Committee on Measurement Quality, and IASH, the International Association for Stability, Handling, and Use of Liquid Fuels. He is chairman emeritus of IASH, and was elected to honorary membership in 2009.

Clifford O. Mills is retired from CONOCO where he served in numerous capacities. At retirement, after 35 years, he was a laboratory consultant with an emphasis on crude oil analysis. Mr. Mills has been involved with ASTM methods development since the early 1980s. Until recently, he was chairman of ASTM D02.05 on Properties of Fuels, Petroleum Coke and Carbon Material, and also chaired D02.H0 on Liquefied Petroleum Gas for several years. He continues to be active in D02.03, D02.04, D02.05, D02.06 and D02.H0. Mr. Mills has been actively involved in development of numerous ASTM methods of analysis. Together with Mr. Giles, he serves as technical advisor to ASTM for their Crude Oil ILCP. For several years, Mr. Mills served as co-instructor for the crude oil training course and, together with Mr. Giles, presented this at numerous locations worldwide. He is a member of the Crude Oil Quality Association, and author of an authoritative paper on crude contaminants and analysis requirements presented at one of their meetings. This paper is now widely referenced and used as an instructional aid. In 2008, he received the ASTM International George V. Dyroff Award of Honorary Committee D02 Membership.

ASTM INTERNATIONAL Manual

Crude Oils: Their Sampling, Analysis, and Evaluation2ND Edition

Harry N. Giles Clifford O. Mills

ASTM INTERNATIONAL Helping our world work better

ISBN: 978-0-8031-7104-6 Stock #: MNL68-2ND

www.astm.org

Giles | M

illsC

rude Oils: Their S

ampling, A

nalysis, and Evaluation | 2N

D Edition

harry n. giles clifford o. mills crude oils...mills has been involved with astm methods development...

Documents