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Essential Readings in • I e as

Electrode Technology for Aluminum Production

Essential Readings in • I

Electrode Technology for Aluminum Production

Editors

Alan Tomsett

John Johnson

ISBN 978-3-319-48577-5

DOI 10.1007/978-3-319-48200-2

Chemistry and Materials Science: Professional

ISBN 978-3-319-48200-2 (eBook)

Copyright © 2016 by The Minerals. Metals & Materials Society

Published by Springer International Publishers, Switzerland, 2016

Reprint of the original edition published by John Wiley & Sons, Inc., 2013,978-1118-63663-3

This work is subject to copyright. All rights are reserved by the Publisher, whether the whole or part of the material is concerned. specifically the rights of translation. reprinting. reuse of illustrations, recitation, broadcasting, reproduction on microfilms or in any other physical way. and transmission or information storage and retrieval, electronic adaptation, computer software, or by similar or dissimilar methodology now known or hereafter developed. The use of general descriptive names, registered names, trademarks, service marks, etc. in this publication does not imply, even in the absence of a specific statement, that such names are exempt from the relevant protective laws and regulations and therefore free for general use. The publisher, the authors and the editors are safe to assume that the advice and information in this book are believed to be true and accurate at the date of publication. Neither the publisher nor the authors or the editors give a warranty, express or implied, with respect to the material contained herein or for any errors or omissions that may have been made.

Printed on acid-free paper

This Springer imprint is published by Springer Nature

The registered company is Springer International Publishing AG

The registered company address is: Gewerbestrasse 11.6330 Cham, Switzerland

Use of Under-Calcined Coke for the Production of Low Reactivity Anodes

J. Lhuissier, L. Bezamanifary, M Gendre, and M Chollier

P. Rhedey

R. Garbarino and R. Tonti Influence of Petroleum Coke Sulphur Content on the Sodium Sensitivity of Carbon Anodes ................................................

S. Hume, W: Fischer, R. Perruchoud, J. Melson, and R. Baker

L. Lossius, K. Neyrey, and L. Edwards

A. Adams, R. Cahill, Y. Belzile, K. Cantin, and M Gendron

R. Perruchoud, M Meier, and W: Fischer

J. Baron, S. McKinney, and R. Wombles

G. Romovacek

A. A/scher, R. Wild.forster, and J. Sharp

W. Fischer and R. Perruchoud

Baked Anode Production

Simulation of a Horizontal Flue Ring Furnace .................................................................................................

R. Bui, E. Demedde, A. Charette, and T. Bourgeois

Operation of Anode Baking

I. Holden, 0. Saeter, F. Aune, and T. Naterstad

F. Keller, P. Sulger, and W: Fischer

F. Keller, P. Sulger, M. Meier, D. Severo, and V. Gusberti

Evaluation of the Uniformity of Baking in Horizontal and Vertical Flue Ring Furnaces

D. Holdner, S. Nadkami, and D. DuTremblay

T. Foosnaes, N. Kulset, H. Linga, G. Naeumann, and A. Werge-Olsen

L. Lossius, I. Holden, and H. Linga

Parameters and the Resulting Anode

W: Fischer, F. Keller, R. Perruchoud, and S. Oderbolz

M. Vogt, K. Ries, and M. Smith

G. Bain, J. Pruneau, and J. Williams

E. Cutshall and V. Bullough

E. Cutshall

C. Dreyer

in tbe Design of Reduction Cell Anodes

D. Brooks and V. Bullough

M Ohlswager, G. Goeres, and R. Peterson

Drilling of Stub Holes in Prebaked Anodes

B. Aga, I. Holden, H. Linga, and K. Solbu

in Stub Hole Optimisation of Cast Iron Rodded Anodes ......................................................................................

D. Richard, P. Goulet, 0. Trempe, M. Dupuis, and M Fafard Real Time Temperature Distribution during Sealing Process and Room Temperature Air Gap Measurements of a HallHeroult Cell Anode

0. Trempe, D. Larouche, D. Ziegler, M Guillot, and M Fafard

of Carbonaceous Rodding Mix Formulation on Steel-Carbon Contact Resistance

P. Rhedey and L. Castonguay

S. Jones and R. Hildebrandt

on Anode Reactivity to Oxidant Gases

J. ReyBoero

Some Practical Consequences of Analyses of tbe Carboxy and Airburn Reactions of Anode Carbons

N Bird, B. McEnaney, and B. Sadler A Porosimetric Study of Sub-Surface Carboxy Oxidation in Anodes

B. Sadler and S. Algie

J. Rolle and Y. Hoang Anode Performance: Dusting A Review of Factors Affecting Carbon Anode Consumption in tbe Electrolytic Production of

P. Rhedey

S. Wilkening

Anode Dusting in Hall-Heroult Cells

T. Foosnaes, T. Naterstad, M Bruheim, and K Grjotheim

The Influence of Low Current Densities on Anode Performance ............................................................................................

S. Hume, M Utley, B. Welch, and R. Perruchoud

Generation and Accumulation for Changing Anode Quality and Cell Parameters

R. Perruchoud, K Hulse, W: Fischer, and W: Schmidt-Hatting

Anode Dusting from a Po!room Perspective at Nordural and Correlation with Anode Properties ..........................................

A. Fitchett, D. Morgan, and B. Welch

and Electrolytic Consumption of Anode Carbon with Various Additives

T. Muftiioglu and H. (2Jye

Impregnation of Carbon Anodes .....................................................................................................................................

R. Perruchoud, M Meier, and W: Fischer Anode Performance: Thermal Shock

of Coke and Formulation Variables on Cracking of Bench Scale Prebaked Anode Specimens ..................................

Shock in Anodes for the Electrolytic Production of Aluminium

E. Kummer and W: Schmidt-Hatting

Parameters Affecting Thermal Shock Cracking of Anodes in the Valco Smelter ..................................................

N. Ambenne and K. Ries

Shock of Anodes -A Solved Problem?

M Meier, W: Fischer, R. Perruchoud, and L. Gauckler

T. Liu, L. Edwards, C. Hughes, B. Mason, and R. McMellon An Approach for a Complete Evaluation of Resistance to Thermal Shock (Part 1): Applying to the Case of Anodes and Cathodes

C. Dreyer and B. Samanos

Laboratory Testing of Carbon Cathode Materials at Operational Temperatures .....................................................................

M Serlie and H. flJye

Changes in Carbon by Heat Treatment ...................................................................................................................

S. Brandtzaeg, H. Linga, and H. flJye

D. Dumas and C. Michel

D. Lombard, T. Beheregaray, B. Feve, and J. Jolas

I. Letizia, C. Bizzarri, and M. Lezzerini Stress Analysis of Cathode Bottom

B. Larsen and M. Serlie

L. Caruso, K Rye, and M. Serlie

M Ser/ie, B. Faaness, and J. Belmonte

B. Faaness, H. Gran, M Serlie, and H. flJye

F. Brunk

Siljan, 0. Junge, T. Svendsen, and K Thovsen

Schening, T. Grande, and 0. Siljan

A. Tabereaux and A. Fickel

E. Skybakmoen, L. Stoen, J. Kvel/o, and 0. Dare//

K. Tschiipe, J. Rut/in, T. Grande

Carbon Cathode Corrosion by Aluminium Carbide Formation in Cryolitic Melts

X Liao and H. @ye

Erosion of Cathode Blocks in 180 kA Prebake Cells .............................................................................................................. 999 A. Tabereaux, J. Brown, I. Eldridge, and T. A/com

Graphite Cathode Wear Study at Alouette IOOS P. Reny and S. Wilkening

Electrolytic Degradation within Cathode Materials ............................................................................................................... lOll P. Rafiei, F. Hillmann, M Hyland, B. James, and B. Welch

lniluence of Internal Cathode Structure on Behavior during Electrolysis Part II: Porosity and Wear Mechanisms in Graphitized Cathode Materials .............................................................................................................................................. 1017 P. Patel, M Hyland, and F. Hillmann

lniluence of Internal Cathode Structure on Behavior during Electrolysis Part ill: Wear Behavior in Graphitic Materials ... I023 P. Patel, M Hyland, and F. Hillmann

Spent Pot Lining

Formation and Distribution of Cysnide in the Lining of Aluminum Reduction Cells ...........................................................

R. Peterson, L. Blayden, and E. Martin

Potlining Flux in Making Steel... 1037 D. Augood, R. Schlager, and P. Belding

Thermal Treatruent of Spent Potliner in a Rotary Kiln ..........................................................................................................

D. Brooks, E. Cutshall, D. Banker, and D. Strahan

Treatruent and Reuse of Spent Pot Lining, an Industrial Application in a Cement Kiln I 049 P. Personnet

Co-Processing at Cement Plant of Spent Potlining from the Aluminum Industry ................................................................. I

V Gomes, P. Drumond, J. Neto, and A. Lira

Development Status ofProcessing Technology for Spent Potlining in China .......................................................................

W. Li and X Chen

Section Introduction

Part 3: Inert Anodes and Wettable Cathodes

Solubilities of Oxides for Inert Anodes in Cryolite-Based Melts I

D. DeYoung

Corrosion and Passivation of Cermet Inert Anodes in Cryolite-Type Electrolytes ............................................................... I

G. Tarcy

Testing of Cerium Oxide Coated Cermet Anodes in a Laboratory Cell I

J. Gregg, M. Frederick, H. King, and A. Vaccaro

A Non-Consumable Metal Anode for Production of Aluminum with Low Temperature Fluoride Melts

T. Beck

The Behaviour ofNickel Ferrite Cermet Materials as Inert Anodes

E. Olsen and J. Thonstad

Tio Dioxide-Based Ceramics as Inert Anodes for Aluminium Smelting: A Laboratory Study

A. Vecchio-Sadus, D. Constable, R. Dorin, E. Frazer, l Fernandez, G. Neal, S. Lathabai, and M Trigg

Inert Anodes: An Update

R. Pawlek

Wettable Cathodes

The Application of the Refractory Carbides aod Borides to Aluminum Reduction Cells .....................................................

C. Ransley

Use ofTiB 2 Cathode Material: Application aod Benefits io Convectional VSS Cells ..........................................................

L. Boxal/, A. Cooke, and H. Hayden

Use ofTiB 2 Cathode Material: Demonstrated Energy

A.

and W: Buchta

Review of RHM Cathode Development

C. McMinn

Properties of a Colloidal Alumina-Bonded TiB 2 Coating on Cathode Carbon Materials

H. V. de Nora, J. Duruz, and G. Johnston

Sodium aod Bath Penetration into TiB 2-Carbon Cathodes during Laboratory Aluminium Electrolysis

J. Xue and H.

Wettable Cathodes: An

R. Pawlek

PREFACE

The Light Metals proceedings are widely recognized as the definitive reference for electrode technology for aluminum production. The papers published in 1963 (based on the 1962 symposium) and then annually from 1971 to the present contain the combined knowledge of both industry and international research institutes.

The 1962 New York symposium, organized by Robert Lewis (Kaiser) and Phillip Stroup (Alcoa), was remarkable in many ways. First, ahnost every primary aluminum producer in the Western world participated. Second, the openness and willingness to share and disclose internally developed research or practices of both basic and operational relevancy, which could conceivably be regarded as "proprietary" or "corporately advantageous," was surprising and illuminating. This new-found freedom and reciprocity for sharing information possibly reflected the pride each company had in its internal technological strength. It may also have been prompted by a company's hidden agenda in promoting an aspect of the Hall-Heroult process that was perceived to be superior to competitors and therefore, potentially marketable. The meeting comprised sessions on the Bayer process, fundamentals, modeling, modern developments in cell design, methods of analysis relating to the Hall-Heroult process, anode and cathode technology, new processes and materials. The contacts made by the subcommittees organizing the agenda paved the way for what was to emerge in the future. The quality of the papers and the rapport and camaraderie of the attendees at that symposium were so evident and stimulating that it became the precursor for the subsequent Light Metals Symposia at the Annual Meeting of The Minerals, Metals & Materials Society.

This collection of the papers published between 1963 and 2011 provides a single reference for electrode technologists. It can be used by those new to the industry and require a rapid introduction to the technology or by more experienced practitioners and researchers who need information of what has been done on an issue in the past.

An international team of experts with more than 300 years of combined experience in the industry was formed to review the papers in the Light Metals books. The team members have all been regular contributors to Light Metals as authors, session chairs and/or the electrode symposium chair. The selected papers are those that the team assessed as:

• important and have had a large influence on work,

• having had a large impact on the industry,

• describing breakthroughs in the science of electrode technology, and

• important review papers that bring together the thinking of key topics at the time, and have stood the test of time.

The papers that were considered for the volume were based on the current definition of electrode technology at the TMS Annual Meeting. This required some transfer of papers between reduction technology and electrode technology from earlier years. The papers have been separated into three distinct sections:

1. Haii-Heroult Cell Carbon Anodes, including all papers on anode raw materials, anode production, and anode performance

2. Haii-Heroult Cell Cathodes, including papers on reduction cell materials and reduction cell failure mechanisms, but not modeling or start-up

3. Inert Anodes and Wettable Cathodes, including all papers on materials and performance

The papers have been sequenced to place like topics together and to have a technology rather than historical progression. It is expected that this will be a more usable format for the reader.

At the end of each section, there is an additional list of recommended reading on the topic. These are Light Metals papers that the editorial team believes are useful resources but could not be included in final volume due to the book production requirements.

The task of reviewing the papers was very large. Within electrode technology there have been 1,190 papers published between 1963 and 2011. We are extremely grateful to all the authors of these papers for recording their work in Light Metals. The time and efforts of the session and symposium chairs over the years for the review of papers and encouragement for the authors must

also be acknowledged.

This volume was only made possible with the outstanding contributions of the remainder of the editorial team:

• Carbon Anodes: Roy Cahill, Frank Cannova, Petter Lossius, Barry Sadler, and John Secasan

• Cathodes: Dick Jeltsch, JeffKeniry, Steve Wood, and Roy Cahill

• Inert Anodes and Wettable Cathodes: Gary Tarcy and Greg Hardie

All have donated a significant amount of time and effort to the project. Our heartfelt thanks go to this team for its assistance in making this project a success. We must also recognize and thank the production team at TMS and Wiley led by Matt Baker for their support and efforts in formatting and digitizing the papers.

It has been a rewarding experience re-reading and selecting the papers included in this book. We have prepared a volume that will be used as a reference book for many years to come. It is, however, not the end of the development of electrode technology. Through reading these papers, we hope we inspire new authors from industry and universities to contribute to future Light Metals volumes.

Alan Tomsett

John Johnson

Lead Editors

LEAD EDITORS

Alan Tomsett

Alan Tomsett has more than 25 years of experience in carbon anode and cathode technology. He received his B.Sc. and Ph.D. in Chemical Engineering from the University of New South Wales in Sydney, Australia. Alan joined the Comalco Research Centre in Melbourne, Australia in 1987 and has held numerous positions at Comalco/Rio Tmto/Pacific Aluminium including Carbon R&D Manager, Program Director for the global Rio Tinto Alcan Carbon Team, and Carbon Technical Manager for the Rio Tmto Alcan Pacific Region. In these roles, he has provided technical support on process and raw materials to the Australasian Carbon Plants, led the material development program for the Comalco D:rained Cathode Project, and evaluated carbon plant technologies for brownfield and greenfield expansions. Alan is now Technical Director for the Pacific Technology Centre, Pacific Aluminium. In this broader role, he provides technical support and advice across all areas of the Pacific Aluminium smelters. Alan has been a member of The Minerals, Metals & Materials Society since 1996 and has been the 2011 Electrode Symposium Chair, an Electrode Technology Session Chair, and Secretary of the TMS Alumiuum Committee in 2011 and 2012. He is the coauthor of several TMS papers, has been a guest lecturer for the University of New South Wales/ University ofAuckland Graduate Program in Smelting Technology, and a regular contributor to the Australasian Smelting Conference.

John A. Johnson

John A. Johnson holds a B.A. in chemistry and M.S. in Chemical Engineering. He has 42 years of experience in the aluminum, specializing in prebake and VSS anode technology; design, prebake cell design and development, and currently heads his own consulting business. He joined Martin Marietta Aluminum (MMA) in 1971 where he held positions of laboratory manger, carbon superintendent, project engineer, and technical manager. He was responsible for implementation of Sumotomo and Mitsubishi S0derberg dry anode technology at MMA, and became the technical manager for Commonwealth Aluminum (Comalco). In 1987, he left the industry for four years to become the engineering and production manager for Injection Metal Molding Production where he was responsible for developing processes and programs for the powder injection molding technology used to form near net shape sintered metal parts. He joined Kaiser Aluminum International in 1990 as technical manager for Kaiser's project at the JSC Krasnoyarsk Aluminium Plant. Later, as Technical Manager, Kaiser Aluminum International, he was responsible for technology transfer and sales. In 2001 he joined UC RUSAL's Engineering and Technical Centre Ltd., Krasnoyarsk, Russia, where he held the positions of Head of Carbon Department, Manager of Carbon Projects, and Manager of the RA 300 and RA 400 Cell Development program through December 2008. He was the editor of Light Metals 2010, has been a TMS author, and is a former member of the TMS Light Metals Division Aluminum Committee where he held the positions of Chair and Co-Chair of the TMS Light Metals Electrode Technology for Aluminum Production Symposium.

EDITORIAL TEAM

Roy Cahill

Roy Cahill started in the aluminum business in 1996 with Reynolds Metals Company. Since that time he has had positions within Alcoa and Rio Tinto Alcan, and is now working for Pacific Aluminium. Roy has worked in areas ranging from alumina production, coke calcination, carbon anode production, and spent cathode treatment processes. He is currently the Principal Carbon Consultant at the Pacific Aluminium, Pacific Technology Centre in Brisbane, Australia. Roy holds a Ph.D. in Chemistry from Texas A&M University.

Frank Cannova

Frank Cannova is presently the Technology Manager for BP's Coke and Bitumen Technology group based in Huntington Beach, California. Frank has worked in support ofBP's (and previously ARCO's) refining operations for more than 30 years and has been leading BP's Coke Product Technology Support efforts since 2000. He has had a varied career in the industry, holding positions in technology, operations, engineering, maintenance, and business development. Frank has been a regular contributor to the TMS Electrode sessions, contributing multiple technical papers and serving frequently as a session chair. He is an Engineering Authority in BP, received a bachelor's degree in Chemical Engineering from the New Jersey Institute ofTechnology, obtained an MBA from the California State University at Fullerton, and is a licensed professional engineer.

cres Hardie

Gn!g Ha:r:die is the Chief Teehnologist for Rio Tinto Alcan (RTA) T«.bnology based in Vbleppe, Frace. Greg joined Rio Tinto as a Me1allurgist at 1he Cockle Creek R emrch filcility in the Hulm:r Valley, Australia, in 1984. He has hold Illl!lle:rous technic:alrolos in 1he iron and aluminum divisions of Rio Tinto based in Gmnany, Westlml Alllllrlllia, Tasmaria,andCaaada GsegwasProjeaM.anagtrfor1heComalcoCoatcd Cell Proje<:t for more thaD 10 yeers. In his cummt role, Greg suppol111 1ho development and of IUIW tedmology in RTA. Gn!g has a B.E. with First Claas Honoum in Cbemical. Bngineering :tiom 1he UniverBity ofNew South Wale..

Richard Jelllch is a graduate of Case Westan Reserve Univmity, Cleveland, Ohio, with a Master of Science in Chemist!y. He spent 22 yoa:rs with Kaiser Alnminum in prooess e"DgiD.eerillg aad enviromnell1al ma:D.· agemcnt, with the last 12 years at Kaiser's Primary Produ.c1lJ Teclmical Cents' as Cathode Technology Specialist. Silw:e loavin,g Kaiser, Richard has spa1t 10 years consolting with an international in 1ho area of ealhode tedmology, specializing in cell life improvement and reduction cell autopsies. Ridlanl has pres •ted scva:a1 paper& at the TMS Amraal Meeting and has t-Il a lec1Urer on cathode technology for the TMS Alumimlln Electrol)'llia c:oW'!Ie aW:e 1999.

Jetl.Kenb'y

Jell'Kl:nil'y has beal. associated with aJmni•mm smeJtiag opmtiODB, project development, and tedmology fur 3S years. Co:!porate role& have included Technical Ma:napr with New Zoaland Aluminium Smelttml, and Gczer8J. Mmag« ofSmeltiag R&D with Comalc:o AJwnjnhrm He is cut· l'a!tly Din:ctor of Alamination Consulting, based in Mclbolll'l1.e, Austta· lia, and fur 1ho past 15 years has provided consultin,g services to some 2S' intmlational smelters on every continent. Jeff has degrees in Applied Scit.Dce tmd Business .AdmiDisttation fiom.AUBU'alian lllliveraities..

Lorentz Petter Lossius

Lorentz Petter Lossius has an M.Sc. in instrumental analysis from the Norwegian University of Science and Technology (NTNU) and completed his Dr.ing. at NTNU in 1991 with the thesis "Removing Impurities from Secondary Alumina." He then spent a year as a post-doc at the Universite de Fribourg, Suisse, studying the electrochemistry of batteries and three years with Harald A. 0ye as a research assistant/group leader at SINTEF/NTNU. He joined Norsk Hydro in 1996 and is a principal engineer in the Anode Production section of the Hydro Aluminium Primary Metal Technology research unit; his main area is pilot scale anode development and laboratory operational support. He is Chair of the ISO Technical Committee 226 "Materials for the production of primary aluminium" and is Secretary of ASTM Sub-committee D02.05 "Properties of fuels, petroleum coke and carbon material." He is on the board of the Norwegian X-ray Conference. He has more than 30 published papers including the 2008 TMS Light Metals Division Electrode Technology section award-winning "Coke and Anode Desulfurization Studies" (co-authored with Les Edwards and Keith Neyrey), and the 2010 TMS Light Metals Division award-winning "Charcoal in Anodes for Aluminium Production" (co-authored with Bodil Monsen and Arne Petter Ratvik). Both studies are based on original work mostly performed at the Hydro pilot scale facility in Ardal, Norway.

Barry Sadler has been involved in the aluminum industry for more than 30 years in a range of positions but always with a focus on anode carbon technology. He has a Ph.D. in Metallurgy, and commenced his career in 1982 at the Comalco Research Centre in Melbourne, Australia, before moving to Comalco's New Zealand Aluminium Smelter (NZAS) as Carbon Plant Manager in 1989. After more than 7 years at NZAS, Barry was appointed as a Corporate Technical General Manager at Comalco Aluminium's headquarters in Brisbane, Australia. Barry left Rio Tinto/Comalco in 2002 to set up Net Carbon Consulting Pty Ltd. As a consultant,

he provides advice, training, and support to clients on improving carbon plant performance and process technology, always maintaining a strong focus on the practical application of statistical thinking and methods to process management. Barry has authored or co-authored more than 27 technical papers, and is a regular lecturer on anode technology at postgraduate courses run by the University of Auckland. He has been an active member of the The Minerals, Metals & Materials Society for over 25 years as a presenter, session chair, subject organizer, 2013 Chair of the Aluminum Committee, and editor of Light Metals 2013.

John Secasan

John Secasan holds a B.S. in engineering from the University of Materials Science and Engineering, Cluj Napoca, Romania. During his time with Alcoa, he has held several technical positions with responsibilities in aerospace and primary metals. He has specialized in areas including carbon raw materials for anodes, carbon anode manufacturing, and carbon anode performance in the Hall-Heroult electrolysis cells. In these areas, he initiates and leads technical projects related to carbon raw materials and anode quality improvements and additionally provides technical expertise on carbon raw materials and anodes to Alcoa's Primary Metals division worldwide. John is currently a research and development engineer in the Technology Development Group within Alcoa's Technology, Innovation and Center of Excellence, located at the Alcoa Technical Center in Pittsburgh, Pennsylvania, USA.

GaryTarcy

Gary Tarcy is the Manager of Smelting R&D at Alcoa Technical Center, New Kensington, Pennsylvania, USA. Gary has worked for Alcoa for 34 years. He holds 26 patents and has published 31 papers. In 1986 he was the winner of the Alcoa Chapter of Sigma Xi best technical paper award and in 2000 the winner of Alcoa's Arthur Vining Davis Award for Technical Excellence. In 2005 he was the winner of the TMS Light Metals Award for best paper. In 2011 he won the TMS Light Metals Award for the best paper for the second time and also won the Professor Barry Welch Best Paper at the 1Oth Australasian Smelting Technology Conference. In 2006 he was the winner of the alumni of the year from the Department of Chemistry. Only six such awards have ever been given. Gary is also an invited lecturer for the TMS Industrial Electrolysis course and has been an invited lecturer at several of the Australasian Aluminum Smelting and Technology Conferences. Gary holds both B.S. and M.S. degrees in chemistry from Bowling Green State University where he specialized in the study of electrochemistry and photo-electrochemistry.

Steve Wood

Steve Wood is a graduate of Murray State University with degrees in chemistry and mathematics. He was a Staff Process Engineer at NSA in Hawesville, Kentucky, USA. Included in his responsibilities was the testing and evaluating of cathode materials and cathode design improvements with the long term goal of increasing cathode life and improving overall cell performance.

1. HALL-HEROULT CELL CARBON ANODES

Papers on carbon anodes bave been published in every Light Metals volume. Many of the early papers published are still relevant today and a review of the titles show reappearance of similar issues over the 40 years of publication. The papers selected do bave a historical perspective but also reflect today's industry and issues. There is a stronger focus on prebaked anode production and performance over Soderberg paste, and there are a number of papers relevant to current issues with coke quality and supply. In other areas such as thermal shock of anodes, the number of papers reduced after the mid 1990s, suggesting the 1994 paper by Meier et al. titled "Thermal Shock of Anodes- A Solved Problem?" was accurate in predicting that a solution to the problem could be identified.

The anode papers are separated into subsections related to raw materials, anode production, and anode performance. The objective is to allow readers to delve deeply into a specific topic and find like papers together. Where possible, review or general papers related to the topic are included first in each section, followed by papers tbat are more detailed or are related to a specific topic. The papers should be read in conjunction with the recommended reading list at the end of the section.

CALCINED COKE FROM CRUDE OIL TO CUSTOMER SILO

ARCOCQC

300 Oceangate Long Beach, California 90802

ABSTRACT

The quality of calcined petroleum coke used in primary aluminum production is affected by each of the refining and calcining processes including choice of crude, many of the initial refinery processing steps, coking, calcining as well as the handling systems between the refinery, calciner and fmal customer. This paper will discuss how each of these processes affects the final quality of the resulting calcined coke to give insight as to how refining economics will be affecting calcined coke quality in the future.

INTRODUCTION

Calcined coke quality is a complex, multi-variable topic. There have been many attempts to predict calcined coke quality in terms of metal content, sulfur content, porosity, structure etc. Many different equations have been used to predict how a coke will perform in an anode with respect to air burn, C02 reactivity, CTE etc. The need to use many different equations to predict the same anode performance property (1) suggests there are probably additional coke properties or anode fabrication variables that are not constant in the cokes or anodes being studied. Consequently, this paper will address calcined coke quality from the refining and calcining viewpoint. There have been a significant number of papers defining the effect of calcining conditions on calcined coke quality (2, 3, 4) but limited literature information on the effect crude quality has on calcined coke quality (5 & 6). This is unfortunate since crude oil composition is probably the largest factor affecting a calcined coke's potential structure, it's sulfur content, and some metal impurities.

There is no one property that can be singled out to identify a good quality calcined coke. Instead there are many properties taken together that describes the quality of calcined coke. How these properties are achieved is also a trade off. That is, improving one calcined coke property in a desired direction often reduces the

quality of another property. For example, reducing the resid cut point or increasing the coker recycle ratio reduces the coke's vanadium and nickel content but the resulting calcined coke's particle strength and sizing can be reduced. Typically, calcined coke quality is not a major factor in refinery crude selection and design.

Calcined Coke Specifications & Controlling Production Factors

Specification

Real Density

Bulk & Apparent Density

Impurities: Sulfur/NickelNanadium

Iron

Silicon Calcium

Sodium Sizing

Air Reactivity

C02 Reactivity

Major and minor factors

Calcination temperature and time.

Crude, Volatile content of green coke and calcination heat up rate.

Crude, vacuum cut point, and coking conditions

Crude, crude desalting, coke handling systems

Coke handling and storage

Water quality (coking, calciner cooling, & other water systems)

Water quality (coking, calciner cooling, & other water systems), and crude desalting

Crude, vacuum cut point, coking conditions, handling systems and segregation

Water quality (coking and cooling etc.), metal content, calcining conditions

Crude sulfur content, surface contaminants such as sodium.

The refinery's primary concern is to process the most costeffective available crude that matches refinery design capability and maximizes the value of the products produced. In general, this equates to maximizing liquid yield. This paper will address how the following operational choices affect various calcined coke quality parameters and how refinery economics will affect calcined coke quality.

PETROLEUM CRUDE OIL QUALITY (coke's sulfur, nickel, vanadium. iron. bulk density, C02 Reactivity, Air Reactivity, and sizing)The quality of the resulting calcined coke starts with the choice of crude oil or crude oil blend being refined.

Given a choice, most anode manufacturers would chose to have a zero ash, zero metals, high bulk density, medium 2% to 2.5% sulfur coke consisting of a consistent supply of over 30% +4 mesh calcined coke supply to make anodes. This combination of properties is not possible because many of these properties come from conflicting crude properties. In order to have a high bulk density coke, the crude needs to contain a significant amount of asphaltenes. Asphaltenes are complex polyaromatic compounds which contain essentially all the nickel, vanadium and iron found in the crude oil. However different crudes can have asphaltenes with different levels of metals associated with the asphaltenes. This can be seen in the data presented in Table 1 by dividing the total nickel and vanadium content by the asphaltene content. There is a general relationship that calcined coke made from higher asphaltene containing resid (also higher vanadium and nickel) will also have higher bulk density.

A coker feed stock that has essentially no asphaltenes and no vanadium, nickel or iron is clarified oil that is obtained from a fluid catalytic cracker. Coke made from this highly aromatic feed stock makes a needle coke which is used to make electrodes for the electric steel industry. Although calcined needle coke has many desirable properties for aluminum anodes such as low reactivity and very low thermal expansion, it also has very undesirable properties such as, low bulk density, high porosity, very poor particle strength and size. Anodes made from this coke would require unusually high pitch content and result in very lowdensity anodes with poor structural strength.

In general, as the asphaltene content of crudes increase, the resulting coke's bulk density, particle strength as well as its vanadium and nickel content increases. Crudes that have too many asphaltenes tend to make shot coke and contain very high levels of nickel and vanadium. A paper by Ellis and Bacha on shot coke (5) suggested that shot coke formed when pentane insolubles (asphaltenes) of the coker feed are above 13.5%. The author's experience is that higher asphaltene content increases shot coke production but the chemistry and molecular weight of the other resid components also affects shot coke production. If the other resid components are highly aromatic and the asphaltenes are medium molecular weight, significantly higher

asphaltene containing resids can be coked without shot coke production. For example, Alaskan North Slope resid with asphaltenes above 16% makes a good high bulk density coke.

Table 1 lists some crude, resid assay data and predicted green coke quality data from an ARCO coker model. The green coke quality is calculated for a refinery sending relatively deep cut resid to a coker with a low recycle ratio. These are the conditions most refineries would choose if they only wanted to maximize liquid yield with little concern for green coke quality.

The crudes listed in Table 1 are chosen from different geographical parts of the world. Crudes are often characterized by where they are produced. Crudes from various locations in the world tend to have similar quality. For example, crudes from Venezuela and Mexico are heavy, highly aromatic, having high sulfur and high asphaltene content. Crudes from this area produce mostly isotropic very dense and often shot coke. Crudes from the Middle East tend to be slightly less heavy but contain significant sulfur and metal levels. Whereas crudes from Indonesia are very waxy (parrafinic) with very low sulfur and metals content. These crudes produce low metal and sulfur calcined coke but with low bulk density and poor sizing properties. Crudes from North Africa, West Africa and the North Sea have relatively low sulfur and metal contents as well as low asphaltene content. These crudes make low metal and sulfur cokes but with lower bulk density.

The green coke data in the table indicates the very high metal content (vanadium 1377 ppm to 1800 ppm) of coke obtained from Venezuelan and Mexican crudes. The predicted green coke quality for Venezuelan crude was verified in a study commissioned by the state owned Venezuelan oil company made by R&D Carbon (7).

The choice of crudes processed in a refinery is strongly affected by crude logistics, refinery metallurgy and refinery design, and is normally independent of coke quality considerations. That is, refineries are normally designed to process a given crude type. The choice of crudes to feed a refinery is based on the most costeffective crude available during refinery start up. One of the first considerations is the location of crude relative to the refinery. Crudes processed in Europe often come from North Africa, West Africa and the North Sea. These relatively sweet crudes (less than 1 % sulfur) are processed in European refineries and Southeast Asia refineries with metallurgical capabilities of processing these relatively easy to refine crudes. Refineries in Texas and Louisiana process crudes from Texas, Oklahoma and Louisiana and other fields around the Gulf of Mexico. Since most of these crudes are more sour (higher sulfur content) than the African crudes, most of the refineries in the Gulf States have a more sophisticated metallurgy capability of processing these crudes. The waxy crudes from Indonesia which are refined in Indonesia and Southeast Asia produce a high volatile content green coke which produces a coke with poorer sizing and lower bulk density.

REFINING PROCESS

The typical coker refinery flow scheme is depicted below:

Desalting

The first refining process that affects the quality of calcined coke is the desalting of the crude oil. Crude oil coming from the ground is a mixture of petroleum hydrocarbons, salt water and suspended solids. Before distilling the petroleum hydrocarbons, the salt, water and suspended solids need to be separated from the oil. This is done in a desalter where the crude oil is mixed with fresh water to wash out the salt content (mostly sodium chloride). The efficiency of this desalting step depends on the crude quality. Some crudes contain surfactants which help form an emulsion that is difficult to break. However, this first step of the refining process is needed to remove the sodium and chlorides associated with the crude oil. Chloride is a major corrosion catalyst and if not removed will significantly corrode the pipes and refinery units the oil is processed through. Low sodium content coker feed results in smoother coker operation by reducing the coker heater fouling (8). Although desalting the crude is done to protect the refinery piping and reduce coker tube fouling, removing the chlorides

reduces the iron content that finds its way into the coker feed and eventually the coke.

DISTILLATION

After desalting the crude oil, the petroleum hydrocarbons are separated by distillation. Distillation is the refiner's most common unit operation. Coker feedstock is produced in refineries by distillation of crude oil. The basic principle of distillation is to separate a mixture of liquid components by their different boiling points. Crude oil is a mixture of hydrocarbon compounds which range in boiling points from 0-800+°C. Crude oil in the modern refinery is distilled under atmospheric pressure, followed by distillation under vacuum. These processes yield finished and intermediate products that are sent to catalytic units to produce high-octane gasoline blending components, jet fuel, diesel fuel, and liquefied petroleum gas. The heaviest product generated in vacuum distillation is the coker feedstock (or resid).

COKER OPERATION

Figure 2 - Schematic of Coker Operation

Delayed Coker

A coker usually comprises one distillation tower (often referred to as a "fractionation tower"), one heater and 2, or more coking drums. The primary feed to the coker is the resid from the distillation units. Some refineries will include ancillary streams in the coker feed. They may include thermal tars (from thermal crackers or visbreakers), decant oils (from fluid catalytic crackers) or aromatic discharges (from lubricating oil processing). Warm resid (coker feed) is fed to the fractionation tower, then pumped to a coker heater where it is heated to approximately 500° C before entering the coking drum. At this temperature, cracking and polymerization reactions take place. Great care is taken to insure coke is not deposited in the heater tubes or in the transfer piping leading from the heater to the coking drum. Refiners minimize coking in these areas by running high velocities in the furnace tubes, and minimizing the distance between the coker heater and the coke drums. A common industry practice is to inject high-pressure steam into the heater tubes to control velocity. When the hot resid enters the large diameter coke drum, the velocity is drastically reduced.

Figure 1 - Simplified Coking Refinery

Controlling the velocity of the process to insure coking in the drum and delay coking in the heater tubes and transfer piping has given this process its name: "delayed coker".

Inside the coke drum, a complex mixture of cracking and polymerization reactions take place. The overall process is endothermic (absorbs heat), but exothermic (generates heat) reactions also take place. The irreversible transition of liquid hydrocarbons into solid coke is not fully understood, however, an intermediate phase termed "mesophase" has been identified. A similar phase transformation takes place for the binder during anode baking.

The vaporized cracked products from the reaction in the drum flow overhead and are returned to the fractionation tower. From the fractionation tower, gas and intermediate product streams are separated and routed to catalytic units. Virtually all the metals in the coker feed end up in the coke while the sulfur is distributed throughout the liquid products and coke.

Delayed coking is a semi-batch process. After a drum has been filled with coke, it is cooled down by steam, followed by water. The top and bottom heads of the drum are then removed and a drilling process commences. First, a pilot hole is drilled in the center of the drum from top to bottom followed by cutting of the coke by high pressure (about 3000 psi) water jets. This cutting starts at the top, and as coke breaks lose and falls down through the pilot hole onto a concrete pad below.

After the drum is emptied, the heads are put back on and hot hydrocarbons are passed through to preheat the drum prior to the introduction of resid. While all this is taking place, another drum is being filled.

EFFECT

OF COKER OPERATION PROCESS

Resid Cut Point (coke vanadium, nickel & sulfur, bulk densitv)

The resid (coker feed) cut point has a significant effect on the sulfur and metal content of the resulting green coke. If the resid is cut deeper the asphaltene content will increase. As discussed in the crude section, this will increase the coke's bulk density and metals content. Choosing a lower resid cut point results in more heavy gas oils being sent to the coker. Since the heavy gas oils do not contain vanadium or nickel, the coke made from these gas oils will reduce the coke's overall vanadium and nickel content.

The resid cut point can have an effect on the coke's sulfur content. For crudes that are very low in sulfur content such as Indonesian and North Sea crudes, the resid cut point has very little effect on the sulfur content of coke. For crudes that are higher in sulfur content, the sulfur content usually increases in the heavier cuts. For these more sour crudes, increasing the resid cut point will increase the sulfur content of the resulting coke.

From Light Metals

Recycle Ratio (coke vanadium, nickel. and particle strength)

Recycle ratio is the volume flow ratio between the heater feed and the vacuum resid feed. The heaviest cracked hydrocarbons returned to the coker fractionation tower are "recycled" to the coke drum, thus making the volume flow through the coking drum higher than the coker vacuum resid alone. At recycle ratio of one, no recycle takes place ("once-through operation"). Some refer to recycle ratio as "combined feed ratio" (CFR), or "throughput ratio" (TPR).

As the recycle ratio is increased, the coke yield is increased which reduces the coke's nickel and vanadium content and increases the anisotropy (ordering) for the calcined coke. As indicated earlier, coke made from high asphaltene content resid can be isotropic. As additional heavy aromatic gas oil is recycled to the coker, the green coke will yield a more anisotropic calcined coke. Increasing the recycle ratio also can reduce the particle strength of the resulting coke if the coking temperature is not increased appropriately.

The refinery's choice ofresid cut point and recycle ratio depends on the type of units the refinery uses to process heavy gas oils. Some units such as fluid catalytic crackers can economically process very heavy gas oils but hydrocrackers can not due to components from the heaviest gas oils poisoning the hydrocracker's catalyst. Varying a cokers resid cut point and recycle ratio to optimize the different heavy gas oil cracker units can increase or decrease a coke's vanadium or nickel content by 20%to 30%.

Coker Heater Outlet Temperature (Bulk Density. coke particle strength. Shot coke content)

Coking temperature will affect the resulting calcined coke's physical properties such as porosity, bulk density, sizing and particle strength. High temperature reduces green coke VM (volatile matter) content and HGI. This results in a calcined coke with higher VBD and lower porosity. If the coke temperature is too high, it becomes difficult to remove the coke from the drum and could increase the shot coke content. One method to reduce the shot coke content is to reduce the coker heater outlet several degrees. If the coking temperature is too low, the coke comes out of the drum as a tarry goo which requires no drilling.

At the 1992 Australasian Smelting Workshop a correlation between coker drum temperature and green coke volatile content was presented (ref 14 page 184). This correlation was obtained from pilot plant coker studies. Although this correlation is valuable for understanding what affects green coke volatile content, using this approach in commercial cokers is much more complicated. The inside drum temperature of commercial cokers is not monitored or controlled and will change due to other factors affecting coker operations. While the coker heater outlet temperature significantly affects the inside coke drum temperature other factors such as resid cut point, resid recycle ration, coker pressure etc. will also affect the inside drum temperature. Crude and resid composition also will affect the green coke volatile content since the chemistry of the resid will affect the ratio of exothermic and endothermic reactions occurring in the coke drum.

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The resolutions of 1798 will be found in the book devoted to political platforms. So highly were these esteemed by the Republicans of that day, and by the interests whose support they so shrewdly invited, that they more than counterbalanced the popularity acquired by the Federals in their resistance to France, and by 1800 they caused a rupture in the Cabinet of Adams.

In the Presidential election of 1800 John Adams was the nominee for President and C. C. Pinckney for Vice-President. A “Congressional Convention” of Republicans, held in Philadelphia, nominated Thomas Jefferson and Aaron Burr as candidates for these offices. On the election which followed the Republicans chose 73 electors and the Federalists 65. Each elector voted for two persons, and the Republicans so voted that they unwisely gave Jefferson and Burr each 73 votes. Neither being highest, it was not legally determined which should be President or Vice-President, and the election had to go to the House. The Federalists threw 65 votes to Adams and 64 to Pinckney. The Republicans could have done the same, but Burr’s intrigue and ambition prevented this, and the result was a protracted contest in the House, and one which put the country in great peril, but which plainly pointed out some of the imperfections of the electoral features of the Constitution. The Federalists proposed to confess the inability of the House to agree through the vote by States, but to this proposition the Republicans threatened armed resistance. The Federalists next attempted a combination with the friends of Aaron Burr, but this specimen of bargaining to deprive a nominee of the place to which it was the plain intention of his party to elect him, really contributed to Jefferson’s popularity, if not in that Congress, certainly before the people. He was elected on the 36th ballot.

The bitterness of this strife, and the dangers which similar ones threatened, led to an abandonment of the system of each Elector voting for two, the highest to be President, the next highest VicePresident, and an amendment was offered to the Constitution, and fully ratified by September 25, 1804, requiring the electors to ballot separately for President and Vice-President.

Jefferson was the first candidate nominated by a Congressional caucus. It convened in 1800 at Philadelphia, and nominated Jefferson for President and Burr for Vice-President. Adams and

Pinckney were not nominated, but ran and were accepted as natural leaders of their party, just as Washington and Adams were before them.

Downfall of the Federal Party.

This contest broke the power of the Federal party. It had before relied upon the rare sagacity and ability of its leaders, but the contest in the House developed such attempts at intrigue as disgusted many and caused all to quarrel, Hamilton having early showed his dislike to Adams. As a party the Federal had been peculiarly brave at times when high bravery was needed. It had framed the Federal Government and stood by the powers given it until they were too firmly planted for even newer and triumphant partisans to recklessly trifle with. It stood for non-interference with foreign nations against the eloquence of adventurers, the mad impulses of mobs, the generosity of new-born freemen, the harangues of demagogues, and best of all against those who sought to fan these popular breezes to their own comfort, It provided for the payment of the debt, had the courage to raise revenues both from internal and external sources, and to increase expenditures, as the growth of the country demanded. Though it passed out of power in a cloud of intrigue and in a vain grasp at the “flesh-pots,” it yet had a glorious history, and one which none untinctured with the better prejudices of that day, can avoid admiring.

The defeat of Adams was not unexpected by him, yet it was greatly regretted by his friends, for he was justly regarded as second to no other civilian in the establishment of the liberties of the colonies. He was eloquent to a rare degree, possessed natural eloquence, and made the most famous speech in advocacy of the Declaration. Though the proceedings of the Revolutionary Congress were secret, and what was said never printed, yet Webster gives his version of the noted speech of Adams, and we reproduce it in Book III. of this volume as one of the great speeches of noted American orators.

Mr. Jefferson was inaugurated the third President, in the new capitol at Washington, on the 4th of March, 1801, and Vice-President

Burr took his seat in the Senate the same day. Though Burr distinctly disavowed any participancy in the House contest, he was distrusted by Jefferson’s warm friends, and jealousies rapidly cropped out. Jefferson endeavored through his inaugural to smooth factious and party asperities, and so well were his words chosen that the Federalists indulged, the hope that they would not be removed from office because of their political views.

Early in June, however, the first question of civil service was raised. Mr. Jefferson then removed Elizur Goodrich, a Federalist, from the Collectorship of New Haven, and appointed Samuel Bishop, a Republican, to the place. The citizens remonstrated, saying that Goodrich was prompt, reliable and able, and showed that his successor was 78 years old, and too infirm for the duties of the office. To these remonstrances Mr. Jefferson, under date of July 12th, replied in language which did not then, as he did later on, plainly assert the right of every administration to have its friends in office. We quote the following:

“Declarations by myself, in favor of political tolerance, exhortations to harmony and affection in social intercourse, and respect for the equal rights of the minority, have, on certain occasions, been quoted and misconstrued into assurances that the tenure of office was not to be disturbed. But could candor apply such a construction? When it is considered that, during the late administration, those who were not of a particular sect of politics were excluded from all office; when, by a steady pursuit of this measure, nearly the whole offices of the United States were monopolized by that sect; when the public sentiment at length declared itself, and burst open the doors of honor and confidence to those whose opinions they approved; was it to be imagined that this monopoly of office was to be continued in the hands of the minority? Does it violate their equal rights to assert some rights in the majority also? Is it political intolerance to claim a proportionate share in the direction of the public affairs? If a due participation of office is a matter of right, how are vacancies to be obtained? Those by death are few, by resignation none. Can any other mode than that of removal be proposed? This is a painful office; but it is made my duty, and I meet it as such. I proceed in the operation with deliberation and inquiry, that it may injure the best men least, and effect the purposes

of justice and public utility with the least private distress, that it may be thrown as much as possible on delinquency, on oppression, on intolerance, on ante-revolutionary adherence to our enemies.

“I lament sincerely that unessential differences of opinion should ever have been deemed sufficient to interdict half the society from the rights and the blessings of self-government, to proscribe them as unworthy of every trust. It would have been to me a circumstance of great relief, had I found a moderate participation of office in the hands of the majority. I would gladly have left to time and accident to raise them to their just share. But their total exclusion calls for prompter corrections. I shall correct the procedure; but that done, return with joy to that state of things when the only questions concerning a candidate shall be: Is he honest? Is he capable? Is he faithful to the constitution?”

Mr. Adams had made few removals, and none because of the political views held by the incumbents, nearly all of whom had been appointed by Washington and continued through good behavior. At the date of the appointment of most of them, Jefferson’s Republican party had no existence; so that the reasons given in the quotation do not comport with the facts. Washington’s rule was integrity and capacity, for he could have no regard for politics where political lines had been obliterated in his own selection. Doubtless these officeholders were human, and adhered with warmth to the administration which they served, and this fact, and this alone, must have angered the Republicans and furnished them with arguments for a change.

Mr. Jefferson’s position, however, made his later conduct natural. He was the acknowledged leader of his party, its founder indeed, and that party had carried him into power. He desired to keep it intact, to strengthen its lines with whatever patronage he had at his disposal, and he evidently regarded the cause of Adams in not rewarding his friends as a mistake. It was, therefore, Jefferson, and not Jackson, who was the author of the theory that “to the victors belong the spoils.” Jackson gave it a sharp and perfectly defined shape by the use of these words, but the spirit and principle were conceived by Jefferson, who throughout his life showed far greater originality in politics than any of the early patriots. It was his acute sense of just what was right for a growing political party to do, which led him to

turn the thoughts of his followers into new and popular directions. Seeing that they were at grave disadvantage when opposing the attitude of the government in its policy with foreign nations; realizing that the work of the Federalists in strengthening the power of the new government, in providing revenues and ways and means for the payment of the debt, were good, he changed the character of the opposition by selecting only notoriously arbitrary measures for assault—and changed it even more radically than this. He early saw that simple opposition was not progress, and that it was both wise and popular to be progressive, and in all his later political papers he sought to make his party the party favoring personal freedom, the one of liberal ideas, the one which, instead of shirking, should anticipate every change calculated to enlarge the liberties and the opportunities of citizens. These things were not inconsistent with his strong views in favor of local self-government; indeed, in many particulars they seemed to support that theory, and by the union of the two ideas he shrewdly arrayed political enthusiasm by the side of political interest. Political sagacity more profound than this it is difficult to imagine. It has not since been equalled in the history of our land, nor do we believe in the history of any other.

After the New Haven episode, so jealous was Jefferson of his good name, that while he confided all new appointments to the hands of his political friends, he made few removals, and these for apparent cause. The mere statement of his position had proved an invitation to the Federalists in office to join his earlier friends in the support of his administration. Many of them did it, so many that the clamorings of truer friends could not be hushed. With a view to create a new excuse, Jefferson declared that all appointments made by Adams after February 14th, when the House began its ballotings for President, were void, these appointments belonging of right to him, and from this act of Adams we date the political legacies which some of our Presidents have since handed down to their successors. One of the magistrates whose commission had been made out under Adams, sought to compel Jefferson to sign it by a writ of mandamus before the Supreme Court, but a “profound investigation of constitutional law” induced the court not to grant the motion. All commissions signed by Adams after the date named were suppressed.

Jefferson’s apparent bitterness against the Federalists is mainly traceable to the contest in the House, and his belief that at one time they sought a coalition with Burr. This coalition he regarded as a violation of the understanding when he was nominated, and a supposed effort to appoint a provisional office he regarded as an usurpation in fact. In a letter to James Monroe, dated February 15th, speaking of this contest, he says:

“Four days of balloting have produced not a single change of a vote. Yet it is confidently believed that to-morrow there is to be a coalition. I know of no foundation for this belief. If they could have been permitted to pass a law for putting the government in the hands of an officer, they would certainly have prevented an election. But we thought it best to declare openly and firmly, one and all, that the day such an act passed, the Middle States would arm, and that no such usurpation, even for a single day, should be submitted to.”

It is but fair to say that the Federalists denied all such intentions, and that James A. Bayard, of Delaware, April 3, 1806, made formal oath to this denial. In this he says that three States, representing Federalist votes, offered to withdraw their opposition if John Nicholas, of Virginia, and the personal friend of Jefferson, would secure pledges that the public credit should be supported, the navy maintained, and that subordinate public officers, employed only in the execution of details, established by law, should not be removed from office on the ground of their public character, nor without complaint against their conduct. The Federalists then went so far as to admit that officers of “high discretion and confidence,” such as members of the cabinet and foreign ministers, should be known friends of the administration. This proposition goes to show that there is nothing very new in what are called our modern politics; that the elder Bayard, as early as 1800, made a formal proposal to bargain. Mr. Nicholas offered his assurance that these things would prove acceptable to and govern the conduct of Jefferson’s administration, but he declined to consult with Jefferson on the points. General Smith subsequently engaged to do it, and Jefferson replied that the points given corresponded with his views and intentions, and that Mr. Bayard and his friends might confide in him accordingly. The opposition of Vermont, Maryland and Delaware was then immediately withdrawn, and Mr. Jefferson was made

President. Gen’l Smith, twelve days later, made an affidavit which substantially confirmed that of Bayard. Latimer, the collector of the port of Philadelphia, and M’Lane, collector of Wilmington, (Bayard’s special friend) were retained in office. He had cited these two as examples of his opposition to any change, and Jefferson seemed to regard the pledges as not sacred beyond the parties actually named in Bayard’s negotiations with Gen’l Smith.

This misunderstanding or misconstruction of what in these days would be plainly called a bargain, led to considerable political criticism, and Jefferson felt it necessary to defend his cause. This he did in letters to friends which both then and since found their way into the public prints. One of these letters, written to Col. Monroe, March 7th, shows in every word and line the natural politician. In this he says:

“Some (removals) I know must be made. They must be as few as possible, done gradually, and bottomed on some malversation or inherent disqualification. Where we shall draw the line between all and none, is not yet settled, and will not be till we get our administration together; and perhaps even then we shall proceed ā talons, balancing our measures according to the impression we perceive them to make. This may give you a general view of our plan.”

A little later on, March 28, he wrote to Elbridge Gerry:

“Officers who have been guilty of gross abuses of office, such as marshals packing juries, etc., I shall now remove, as my predecessor ought in justice to have done. The instances will be few, and governed by strict rule, not party passion. The right of opinion shall suffer no invasion from me.”

Jefferson evidently tired of this subject, and gradually modified his views, as shown in his letter to Levi Lincoln, July 11, wherein he says:

“I am satisfied that the heaping of abuse on me personally, has been with the design and the hope of provoking me to make a general sweep of all Federalists out of office. But as I have carried no passion into the execution of this disagreeable duty, I shall suffer none to be excited. The clamor which has been raised will not provoke me to remove one more, nor deter me from removing one less, than if not a word had been said on the subject. In the course of the summer, all

which is necessary will be done; and we may hope that, this cause of offence being at an end, the measures we shall pursue and propose for the amelioration of the public affairs, will be so confessedly salutary as to unite all men not monarchists in principle.” In the same letter he warmly berates the monarchical federalists, saying, “they are incurables, to be taken care of in a madhouse if necessary, and on motives of charity.”

The seventh Congress assembled. Political parties were at first nearly equally divided in the Senate, but eventually there was a majority for the administration. Jefferson then discontinued the custom established by Washington of delivering in person his message to Congress. The change was greatly for the better, as it afforded relief from the requirement of immediate answers on the subjects contained in the message. It has ever since been followed.

The seventh session of Congress, pursuant to the recommendation of President Jefferson, established a uniform system of naturalization, and so modified the law as to make the required residence of aliens five years, instead of fourteen, as in the act of 1798, and to permit a declaration of intention to become a citizen at the expiration of three years. By his recommendation also was established the first sinking fund for the redemption of the public debt. It required the setting apart annually for this purpose the sum of seven millions and three hundred thousand dollars. Other measures, more partisan in their character, were proposed, but Congress showed an aversion to undoing what had been wisely done. A favorite law of the Federalists establishing circuit courts alone was repealed, and this only after a sharp debate, and a close vote. The provisional army had been disbanded by a law of the previous Congress. A proposition to abolish the naval department was defeated, as was that to discontinue the mint establishment.

At this session the first law in relation to the slave trade was passed. It was to prevent the importation of negroes, mulattoes and other persons of color into any port of the United States within a state which had prohibited by law the admission of any such person. The penalty was one thousand dollars and the forfeiture of the vessel. The slave trade was not then prohibited by the constitution, nor was the subject then generally agitated, though it had been as early as 1793, when, as previously stated, an exciting sectional debate

followed the presentation of a petition from Pennsylvania to abolish the slave trade.

Probably the most important occurrence under the first administration of Jefferson was that relating to the purchase and admission of Louisiana. There had been apprehensions of a war with Spain, and with a view to be ready Congress had passed an act authorizing the President to call upon the executives of such of the states as he might deem expedient, for detachments of militia not exceeding eighty thousand, or to accept the services of volunteers for a term of twelve months. The disagreement arose over the southwestern boundary line and the right of navigating the Mississippi. Our government learned in the spring of 1802, that Spain had by a secret treaty made in October, 1800, actually ceded Louisiana to France. Our government had in 1795 made a treaty with Spain which gave us the right of deposit at New Orleans for three years, but in October, 1802, the Spanish authorities gave notice by proclamation that this right was withdrawn. Excitement followed all along the valley of the Mississippi, and it was increased by the belief that the withdrawal of the privilege was made at the suggestion of France, though Spain still retained the territory, as the formalities of ceding it had not been gone through with. Jefferson promptly took the ground that if France took possession of New Orleans, the United States would immediately become allies of England, but suggested to Minister Livingston at Paris that France might be induced to cede the island of New Orleans and the Floridas to the United States. It was his belief, though a mistaken one, that France had also acquired the Floridas. Louisiana then comprised much of the territory west of the Mississippi and south of the Missouri.

The Federalists in Congress seized upon this question as one upon which they could make an aggressive war against Jefferson’s administration, and resolutions were introduced asking information on the subject. Jefferson, however, wisely avoided all entangling suggestions, and sent Monroe to aid Livingston in effecting a purchase. The treaty was formed in April, 1803, and submitted by Jefferson to the Senate in October following. The Republicans rallied in favor of this scheme of annexation, and claimed that it was a constitutional right in the government to acquire territory—a doctrine widely at variance with their previous position, but

occasions are rare where parties quarrel with their administrations on pivotal measures. There was also some latitude here for endorsement, as the direct question of territorial acquisition had not before been presented, but only hypothetically stated in the constitutional disputations then in great fashion. Jefferson would not go so far as to say that the constitution warranted the acquisition to foreign territory, but the scheme was nevertheless his, and he stood in with his friends in the political battle which followed.

The Federalists claimed that we had no power to acquire territory, and that the acquirement of Louisiana would give the South a preponderance which would “continue for all time (poor prophets they!), since southern would be more rapid than northern development;” that states created west of the Mississippi would injure the commerce of New England, and they even went so far as to say that the “admission of the Western World into the Union would compel the Eastern States to establish an eastern empire.” Doubts were also raised as to the right of Louisianians, when admitted to citizenship under our laws, as their lineage, language and religion were different from our own. Its inhabitants were French and descendants of French, with some Spanish creoles, Americans, English and Germans—in all about 90,000, including 40,000 slaves. There were many Indians of course, in a territory then exceeding a million of square miles—a territory which, in the language of First Consul Napoleon, “strengthens forever the power of the United States, and which will give to England a maritime rival that will sooner or later humble her pride”—a military view of the change fully justified by subsequent history. Napoleon sold because of needed preparations for war with England, and while he had previously expressed a willingness to take fifty million francs for it, he got sixty through the shrewd diplomacy of his ministers, who hid for the time their fear of the capture of the port of New Orleans by the English navy.

Little chance was afforded the Federalists for adverse criticism in Congress, for the purchase proved so popular that the people greatly increased the majority in both branches of the eighth Congress, and Jefferson called it together earlier for the purpose of ratification. The Senate ratified the treaty on the 20th of October, 1803, by a vote of

24 to 7, while the House adopted a resolution for carrying the treaty into effect by a vote of 90 to 25. Eleven million dollars of the purchase money was appropriated, the remaining four millions being reserved for the indemnity of American citizens who had sustained losses by French assaults upon our commerce—from which fact subsequently came what is known as the French Spoliation Bill.

Impeachment trials were first attempted before the eighth Congress in 1803. Judge Pickering, of the district court of the United States for New Hampshire, was impeached for occasional drunkenness, and dismissed from office. Judge Chase of the U. S. Supreme Court, and Judge Peters of the district court of Pennsylvania, both Federalists, were charged by articles proposed in the House with illegal and arbitrary conduct in the trial of parties charged with political offenses. The Federalists took alarm at these proceedings, and so vehement were their charges against the Republicans of a desire to destroy the judiciary that their impeachments were finally abandoned.

The Republicans closed their first national administration with high prestige. They had met several congressional reverses on questions where defeat proved good fortune, for the Federalists kept a watchful defence, and were not always wrong. The latter suffered numerically, and many of their best leaders had fallen in the congressional contest of 1800 and 1802, while the Republicans maintained their own additions in talent and number.

In 1804, the candidates of both parties were nominated by congressional caucuses. Jefferson and Clinton were the Republican nominees; Charles C. Pinckney and Rufus King, the nominees of the Federalists, but they only received 14 out of 176 electoral votes.

The struggle of Napoleon in Europe with the allied powers now gave Jefferson an opportunity to inaugurate a foreign policy. England had forbidden all trade with the French and their allies, and France had in return forbidden all commerce with England and her colonies. Both of these decrees violated our neutral rights, and were calculated to destroy our commerce, which by this time had become quite imposing.

Congress acted promptly, and on the 21st of December passed what is known as the Embargo Act, under the inspiration of the Republican party, which claimed that the only choice of the people lay between the embargo and war, and that there was no other way to obtain redress from England and France. But the promised effects of the measure were not realized, and so soon as any dissatisfaction was manifested by the people, the Federalists made the question a political issue. They declared it unconstitutional because it was not limited as to time; that it helped England as against France (a cunning assertion in view of the early love of the Republicans for the cause of the French), and that it laid violent hands on our home commerce and industries. Political agitation increased the discontent, and public opinion at one time turned so strongly against the law that it was openly resisted on the eastern coast, and treated with almost as open contempt on the Canadian border. The bill had passed the House by 87 to 35, the Senate by 19 to 9. In January, 1809, the then closing administration of Jefferson had to change front on the question, and the law was repealed on the 18th of March. The Republicans when they changed, went all the way over, and advocated full protection by the use of a navy, of all our rights on the high seas. If the Federals could have recalled their old leaders, or retained even a considerable portion of their power, the opportunity presented by the embargo issue could have brought them back to full political power, but lacking these leaders, the opportunity passed.

Democrats and Federals.

During the ninth Congress, which assembled on the second of December, 1805, the Republicans dropped their name and accepted that of “Democrats.” In all their earlier strifes they had been charged by their opponents with desiring to run to the extremes of the democratic or “mob rule,” and fear of too general a belief in the truth of the charge led them to denials and rejection of a name which the father of their party had ever shown a fondness for. The earlier dangers which had threatened their organization, and the recollection of defeats suffered in their attempts to establish a government anti-federal and confederate in their composition, had been greatly modified by later successes, and with a characteristic cuteness peculiar to Americans they accepted an epithet and sought to turn it to the best account. In this they imitated the patriots who accepted the epithets in the British satirical song of “Yankee Doodle,” and called themselves Yankees. From the ninth Congress the Jeffersonian Republicans called themselves Democrats, and the word Republican passed into disuse until later on in the history of our political parties, the opponents of the Democracy accepted it as a name which well filled the meaning of their attitude in the politics of the country.

Mr. Randolph of Roanoke, made the first schism in the Republican party under Jefferson, when he and three of his friends voted against the embargo act. He resisted its passage with his usual earnestness, and all attempts at reconciling him to the measure were unavailing. Self-willed, strong in argument and sarcasm, it is believed that his cause made it even more desirable for the Republicans to change name in the hope of recalling some of the more wayward “Democrats” who had advocated Jacobin democracy in the years gone by. The politicians of that day were never short of expedients, and no man so abounded in them as Jefferson himself.

Randolph improved his opportunities by getting most of the Virginia members to act with him against the foreign policy of the administration, but he was careful not to join the Federalists, and quickly denied any leaning that way. The first fruit of this faction was to bring forth Monroe as a candidate for President against Madison— a movement which proved to be quite popular in Virginia, but which Jefferson flanked by bringing about a reconciliation between Monroe and Madison. The now usual Congressional caucus followed at Washington, and although the Virginia Legislature in its caucus previously held had been unable to decide between Madison and Monroe, the Congressional body chose Madison by 83 to 11, the minority being divided between Clinton and Monroe, though the latter could by that time hardly be considered as a candidate. This action broke up Randolph’s faction in Virginia, but left so much bitterness behind it that a large portion attached themselves to the Federalists. In the election which followed Madison received 122 electoral votes against 47 for C. C. Pinckney, of South Carolina, and 6 for Geo. Clinton of New York.

Before Jefferson’s administration closed he recommended the passage of an act to prohibit the African slave trade after January 1st, 1808, and it was passed accordingly. He had also rejected the form of a treaty received from the British minister Erskine, and did this without the formality of submitting it to the Senate—first, because it contained no provision on the objectionable practice of impressing our seamen; second,[2] “because it was accompanied by a note from the British ministers, by which the British government reserved to itself the right of releasing itself from the stipulations in favor of neutral rights, if the United States submitted to the British decree, or other invasion of those rights by France.” This rejection of the treaty by Jefferson caused public excitement, and the Federalists sought to arouse the commercial community against his action, and cited the fact that his own trusted friends, Monroe and Pinckney had negotiated it. The President’s party stood by him, and they agreed that submission to the Senate was immaterial, as its advice could not bind him. This refusal to consider the treaty was the first step leading to the war of 1812, for embargoes followed, and Britain openly claimed the right to search American vessels for her deserting seamen. In 1807 this question was brought to issue by the desertion of five British seamen from the Halifax, and their enlistment on the

U. S. frigate Chesapeake. Four separate demands were made for these men, but all of the commanders, knowing the firm attitude of Jefferson’s administration against the practice, refused, as did the Secretary of State refuse a fifth demand on the part of the British minister. On the 23d of June following, while the Chesapeake was near the capes of Virginia, Capt. Humphreys of the British ship Leopard attempted to search her for deserters. Capt. Barron denied the right of search, but on being fired into, lowered his flag, Humphreys then took four men from the Chesapeake, three of whom had previously entered the British service, but were Americans by birth, and had been formally demanded by Washington. The act was a direct violation of the international law, for a nation’s ship at sea like its territory is inviolable. The British government disavowed the act of its officer and offered apology and reparation, which were accepted. This event, however, strengthened Jefferson’s rejection of the Monroe-Pinckney treaty, and quickly stopped adverse political criticism at home, Foreign affairs remained, however, in a complicated state, owing to the wars between England and the then successful Napoleon, but they in no wise shook the firm hold which Jefferson had upon the people, nor the prestige of his party. He stands in history as one of the best politicians our land has ever seen, and then as now no one could successfully draw the line between the really able politician and the statesman. He was accepted as both. His administration closed on the 3d of March, 1809, when he expressed great gratification at being able to retire to private life.

Mr. Madison succeeded at a time when the country, through fears of foreign aggression and violence, was exceedingly gloomy and despondent—a feeling not encouraged in the least by the statements of the Federalists, some of whom then thought political criticism in hours of danger not unpatriotic. They described our agriculture as discouraged, our fisheries abandoned, our commerce restrained, our navy dismantled, our revenues destroyed at a time when war was at any moment probable with either France, England or Spain.

Madison, representing as he did the same party, from the first resolved to follow the policy of Jefferson, a fact about which there was no misunderstanding. He desired to avert war as long as possible with England, and sought by skilful diplomacy to avert the dangers presented by both France and England in their attitude with

neutrals. England had declared that a man who was once a subject always remained a subject, and on this plea based her determination to impress again into her service all deserters from her navy. France, because of refusal to accede to claims equally at war with our rights, had authorized the seizure of all American vessels entering the ports of France. In May, 1810, when the non-intercourse act had expired, Madison caused proposals to be made to both belligerents, that if either would revoke its hostile edict, the non-intercourse act should be revived and enforced against the other nation. This act had been passed by the tenth Congress as a substitute for the embargo. France quickly accepted Madison’s proposal, and received the benefits of the act, and the direct result was to increase the growing hostility of England. From this time forward the negotiations had more the character of a diplomatic contest than an attempt to maintain peace. Both countries were upon their mettle, and early in 1811, Mr. Pinckney, the American minister to Great Britain, was recalled, and a year later a formal declaration of war was made by the United States.

Just prior to this the old issue, made by the Republicans against Hamilton’s scheme for a National Bank, was revived by the fact that the charter of the bank ceased on the 4th of March, 1811, and an attempt was made to re-charter it. A bill for this purpose was introduced into Congress, but on the 11th of January, 1811, it was indefinitely postponed in the House, by a vote of 65 to 64, while in the Senate it was rejected by the casting vote of the Vice-President, Geo. Clinton, on the 5th of February, 1811—this notwithstanding its provisions had been framed or approved by Gallatin, the Secretary of the Treasury. The Federalists were all strong advocates of the measure, and it was so strong that it divided some of the Democrats who enjoyed a loose rein in the contest so far as the administration was concerned, the President not specially caring for political quarrels at a time when war was threatened with a powerful foreign nation. The views of the Federalists on this question descended to the Whigs some years later, and this fact led to the charges that the Whigs were but Federalists in disguise.

The eleventh Congress continued the large Democratic majority, as did the twelfth, which met on the 4th of November, 1811, Henry Clay, then an ardent supporter of the policy of Madison, succeeding to the House speakership. He had previously served two short sessions in

the U. S. Senate, and had already acquired a high reputation as an able and fluent debater. He preferred the House, at that period of life, believing his powers better calculated to win fame in the more popular representative hall. Calhoun was also in the House at this time, and already noted for the boldness of his views and their assertion.

In this Congress jealousies arose against the political power of Virginia, which had already named three of the four Presidents, each for two terms, and De Witt Clinton, the well-known Governor of New York, sought through these jealousies to create a division which would carry him into the Presidency. His efforts were for a time warmly seconded by several northern and southern states. A few months later the Legislature of New York formally opened the ball by nominating DeWitt Clinton for the Presidency. An address was issued by his friends, August 17th, 1812, which has since become known as the Clintonian platform, and his followers were known as Clintonian Democrats. The address contained the first public protest against the nomination of Presidential candidates by Congressional caucuses. There was likewise declared opposition to that “official regency which prescribed tenets of political faith.” The efforts of particular states to monopolize the principal offices was denounced, as was the continuance of public men for long periods in office.

Madison was nominated for a second term by a Congressional caucus held at Washington, in May, 1812. John Langdon was nominated for Vice-President, but as he declined on account of age, Elbridge Gerry of Massachusetts, took his place. In September of the same year a convention of the opposition, representing eleven states, was held in the city of New York, which nominated De Witt Clinton, with Jared Ingersoll for Vice-President. This was the first national convention, partisan in character, and the Federalists have the credit of originating and carrying out the idea. The election resulted in the success of Madison, who received 128 electoral votes to 89 for Clinton.

Though factious strife had been somewhat rife, less attention was paid to politics than to the approaching war. There were new Democratic leaders in the lower House, and none were more prominent than Clay of Kentucky, Calhoun, Cheves and Lowndes, all of South Carolina. The policy of Jefferson in reducing the army and

navy was now greatly deplored, and the defenceless condition in which it left the country was the partial cause, at least a stated cause of the factious feuds which followed. Madison sought to change this policy, and he did it at the earnest solicitation of Clay, Calhoun and Lowndes, who were the recognized leaders of the war party. They had early determined that Madison should be directly identified with them, and before his second nomination had won him over to their more decided views in favor of war with England. He had held back, hoping that diplomacy might avert a contest, but when once convinced that war was inevitable and even desirable under the circumstances, his official utterances were bold and free. In the June following the caucus which renominated him, he declared in a message that our flag was continually insulted on the high seas; that the right of searching American vessels for British seamen was still in practice, and that thousands of American citizens had in this way been impressed in service on foreign ships; that peaceful efforts at adjustment of the difficulties had proved abortive, and that the British ministry and British emissaries had actually been intriguing for the dismemberment of the Union.

The act declaring war was approved by the President on the 18th of June, 1812, and is remarkably short and comprehensive. It was drawn by the attorney-general of the United States, William Pinckney, and is in the words following:—

“An act declaring war between the United Kingdom of Great Britain and Ireland, and the dependencies thereof, and the United States of America and their territories.

“Be it enacted, &c. That war be, and the same is hereby declared to exist between the United Kingdom of Great Britain and Ireland, and the dependencies thereof, and the United States of America, and their territories; and that the President of the United States is hereby authorized to use the whole land and naval force of the United States to carry the same into effect, and to issue to private armed vessels of the United States commissions, or letters of marque and general reprisal, in such form as he shall think proper, and under the seal of the United States, against the vessels, goods, and effects, of the government of the United Kingdom of Great Britain and Ireland and the subjects thereof.”

This was a soul-stirring message, but it did not rally all the people as it should have done. Political jealousies were very great, and the frequent defeats of the Federalists, while they tended to greatly reduce their numbers and weaken their power, seemed to strengthen their animosity, and they could see nothing good in any act of the

administration. They held, especially in the New England states, that the war had been declared by a political party simply, and not by the nation, though nearly all of the Middle, and all of the Southern and Western States, warmly supported it. Clay estimated that nine-tenths of the people were in favor of the war, and under the inspiration of his eloquence and the strong state papers of Madison, they doubtless were at first. Throughout they felt their political strength, and they just as heartily returned the bitterness manifested by those of the Federalists who opposed the war, branding them as enemies of the republic, and monarchists who preferred the reign of Britain.

Four Federalist representatives in Congress went so far as to issue an address, opposing the war, the way in which it had been declared, and denouncing it as unjust. Some of the New England states refused the order of the President to support it with their militia, and Massachusetts sent peace memorials to Congress.

A peace party was formed with a view to array the religious sentiment of the country against the war, and societies with similar objects were organized by the more radical of the Federalists. To such an extreme was this opposition carried, that some of the citizens of New London, Conn., made a practice of giving information to the enemy, by means of blue lights, of the departure of American vessels.

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