Elemental Analysis of

Fossil Fuels and Related MaterialsR.A. Kishore Nadkarni

Nadkarni

Elemental Analysis of Fossil Fuels and Related M

aterials

Dr. R.A. KISHORE NADKARNI received his Ph.D. in analytical chemistry at the University of Bombay. Since then he has worked as a research associate at the University of Kentucky,

manager of the Materials Science Center Analytical Facility at Cornell University, and analytical leader in the ExxonMobil Company. In his last position he was responsible for technical quality management of the Paramins Division’s global plant laboratories.

He has authored more than 120 technical publications in the area of analytical chemistry and quality management. He is a member of the American Chemical Society and ASTM International. He is very active in ASTM and ISO in the petroleum products and lubricant field, holding the position of immediate past chairman of ISO/TC28, chairman of ASTM’s

D02.03 on Elemental Analysis, vice-chairman of D02.92 on Proficiency Test Programs, D02.94 on Quality Assurance and Statistics. Dr. Nadkarni has received the Award of Appreciation (1991) and Awards for Excellence (1998, 1999, and 2013) from ASTM’s D02 Committee for his contribution to the oil industry, the Award of Merit (2005) and the George Dyroff Award of Honorary D02 membership (2006), and the Sydney Andrews D02 Scroll of Achievement Award (2005).

He is the author or editor of STP 1109, Modern Instrumental Methods of Elemental Analysis of Petroleum Products and Lubricants (1991); STP 1468, Elemental Analysis of Fuels and Lubricants (2005); Manual 44, Guide to ASTM Test Methods for the Analysis of Petroleum Products and Lubricants (2007); Manual 61, Guide to ASTM Test Methods for the Analysis of Coal and Coke (2008); Monograph 9, Spectroscopic Analysis of Petroleum Products and Lubricants (2011); and the forthcoming Monograph 11, Sulfur: Chemistry and Analysis of Fossil Fuel Products.

About the Autor

www.astm.orgISBN: 978-0-8031-7044-5Stock #: MONO10

Elemental Analysis of Fossil Fuelsand Related Materials

R. A. Kishore Nadkarni

ASTM Stock Number: MONO10

Library of Congress Cataloging-in-Publication Data

Nadkarni, R. A.Elemental analysis of fossil fuels and related materials / R.A. KishoreNadkarni.

pages cm — (Monograph ; 10)“ASTM Stock Number: MONO 10.”ISBN 978-0-8031-7044-5

1. Petroleum products—Analysis. 2. Fuel—Analysis. I. Title.TP691.N329 2014662.6—dc23 2013037794

Copyright ª 2014 ASTM International, West Conshohocken, PA. All rightsreserved. This material may not be reproduced or copied, in whole or in part,in any printed, mechanical, electronic, film, or other distribution and storagemedia, without the written consent of the publisher.

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ASTM International is not responsible, as a body, for the statements and opin-ions advanced in the publication. ASTM International does not endorse anyproducts represented in this publication.

Printed inEgan, MN

March, 2014

ForewordTHIS PUBLICATION, Elemental Analysis of Fossil Fuels and RelatedMaterials, was sponsored by Committee D02 on Petroleum Productsand Lubricants. This is Monograph 10 in ASTM International’s mono-graph series.

iii

AcknowledgmentsIt has been said that “it takes a village to raise a child.” In my case itprobably took several villages, many cities, two countries on two conti-nents, and three universities to do the task. Only a few of the people Ibenefited from can be mentioned here because this is a technical trea-tise, not a memoir.

I want to gratefully thank the eminent teachers under whom Ilearned the art of analytical science. These include late ProfessorBarun Chandra Haldar of the (Royal) Institute of Science at BombayUniversity; Professor William D. Ehmann of the University of Ken-tucky; and late Professor George H. Morrison of Cornell University. Istand on the shoulders of these giants to peek at my little domain ofminutia (Isaac Newton).

While at the above universities, my research work was supportedover the years by the Council of Scientific and Industrial Research(India); the U.S. Fulbright Educational Foundation; the U.S. Depart-ment of Agriculture; the National Aeronautics and Space Administra-tion; the National Science Foundation; and the U.S. Department ofEnergy. I am thankful to these federal government organizations fortheir financial support in the research and development of science.

I also have to thank my former employers who provided facilitiesand allowed me to pursue my research interests in analytical chemis-try: Exxon Research and Engineering Company; Exxon Chemical Com-pany–Paramins Manufacturing Technology Division; ExxonMobilResearch and Engineering Company; and Infineum USA, LLC.

Additionally, I am indebted to the following colleagues in the abovecompanies: Dr. Ricardo Bloch, Kevin Bly, Dr. Bob Botto, Dr. JimBover, Dr, Larry Engel, Dr. Mike Granchi, Dr. Richard Ledesma, JackMackey, Alan Malanowicz, Dr. David Martella, Dr. Frank McElroy, Dr.Elisa Santos, Dr. Catherine Schenck, Dr. Ralph Spohn, the late RollieWilliams, and Everett Wixom. I also thank the following colleaguesfrom the oil industry involved in ASTM work: Dr. Don Becker ofAmoco, John Crnko of ASI, Dr. Mike Pohl of Horiba Instruments, Dr.David Hwang of Chevron, and Bill Tanguay of Metrotech Systems. Allof them helped me in this work and know far more about the subjectthan I do.

Special thanks are due to various ASTM staff members, principalamong them David Bradley and Earl Sullivan, current and former staffmanagers of the D02 Committee on Petroleum Products and Lubricants;Kathy Dernoga, publications manager; and Anne McKlindon, formerdirector, PTP Services. Special credit must be given to Rebecca Edwards

v

of Cenveo Publisher Services for her painstaking efforts in copyeditingand proofreading the manuscript. The book would not be in the goodshape it is in without her unfailing help in correcting syntax, spelling,references, and content throughout the publishing process.

I am, of course, eternally grateful to my beloved wife, Nancy Joanne,for her unfailing support while I was busy writing, teaching, travelingaround the world, and in general having one hell of a good time whileshe took care of the home and our children. And regarding these chil-dren of ours who made it all worthwhile, what can I say? “Thanks foreverything, Bobos! You are the greatest. I love you all beyond words.”

vi

ContentsForeword . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . iii

Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . v

Chapter 1—Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1

Chapter 2—Importance of Elemental Analysis of Fossil Fuels . . . . . . . . . . . . . . 37

Chapter 3—Analytical Techniques for Elemental Analysis of Fossil Fuels . . . . . 61

Chapter 4—Basic Protocols of Elemental Analysis. . . . . . . . . . . . . . . . . . . . . . 163

Chapter 5—Elemental Analysis of Coal, Coke, and Fly Ash. . . . . . . . . . . . . . . 248

Chapter 6—Elemental Analysis of Oil Shales . . . . . . . . . . . . . . . . . . . . . . . . . 395

Chapter 7—Elemental Analysis of Crude Oils . . . . . . . . . . . . . . . . . . . . . . . . . 457

Chapter 8—Elemental Analysis of Gasoline and Diesel . . . . . . . . . . . . . . . . . . 509

Chapter 9—Elemental Analysis of Lubricants and Additives . . . . . . . . . . . . . . 582

Chapter 10—Elemental Analysis of Lubricating Greases . . . . . . . . . . . . . . . . . 673

Chapter 11—Elemental Analysis of Other Petroleum Products . . . . . . . . . . . . 683

Chapter 12—Elemental Analysis of Process Catalysts . . . . . . . . . . . . . . . . . . . 700

Chapter 13—Elemental Analysis of Gaseous Fuels . . . . . . . . . . . . . . . . . . . . . 709

Chapter 14—Elemental Analysis of Biofuels . . . . . . . . . . . . . . . . . . . . . . . . . . 733

Chapter 15—Proficiency Testing Programs for Elemental Analysis ofFuels and Lubricants. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 776

Appendix 1—ASTM Standards for Elemental Analysis of Coal and Coke . . . . 799

Appendix 2—ASTM Standards for Elemental Analysis of PetroleumProducts and Lubricants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 802

Appendix 3—ASTM Standards for Elemental Analysis of Gaseous Fuels . . . . 809

Appendix 4—ASTM Research Reports for the Elemental Analysis ofCoal and Coke . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 811

Appendix 5—ASTM Research Reports for Catalyst Analysis . . . . . . . . . . . . . . 812

Appendix 6—ASTM Research Reports for the Elemental Analysis ofPetroleum Products and Lubricants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 813

Appendix 7—Practical Hints for Test Method Operation . . . . . . . . . . . . . . . . 816

Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 849

vii

Elemental Analysis of

Fossil Fuels and Related MaterialsR.A. Kishore Nadkarni

Nadkarni

Elemental Analysis of Fossil Fuels and Related M

aterials

Dr. R.A. KISHORE NADKARNI received his Ph.D. in analytical chemistry at the University of Bombay. Since then he has worked as a research associate at the University of Kentucky,

manager of the Materials Science Center Analytical Facility at Cornell University, and analytical leader in the ExxonMobil Company. In his last position he was responsible for technical quality management of the Paramins Division’s global plant laboratories.

He has authored more than 120 technical publications in the area of analytical chemistry and quality management. He is a member of the American Chemical Society and ASTM International. He is very active in ASTM and ISO in the petroleum products and lubricant field, holding the position of immediate past chairman of ISO/TC28, chairman of ASTM’s

D02.03 on Elemental Analysis, vice-chairman of D02.92 on Proficiency Test Programs, D02.94 on Quality Assurance and Statistics. Dr. Nadkarni has received the Award of Appreciation (1991) and Awards for Excellence (1998, 1999, and 2013) from ASTM’s D02 Committee for his contribution to the oil industry, the Award of Merit (2005) and the George Dyroff Award of Honorary D02 membership (2006), and the Sydney Andrews D02 Scroll of Achievement Award (2005).

He is the author or editor of STP 1109, Modern Instrumental Methods of Elemental Analysis of Petroleum Products and Lubricants (1991); STP 1468, Elemental Analysis of Fuels and Lubricants (2005); Manual 44, Guide to ASTM Test Methods for the Analysis of Petroleum Products and Lubricants (2007); Manual 61, Guide to ASTM Test Methods for the Analysis of Coal and Coke (2008); Monograph 9, Spectroscopic Analysis of Petroleum Products and Lubricants (2011); and the forthcoming Monograph 11, Sulfur: Chemistry and Analysis of Fossil Fuel Products.

About the Autor

www.astm.orgISBN: 978-0-8031-7044-5Stock #: MONO10