Petroleum Derived Carbons

484 Pages·1976·12.27 MB·English

by  Marvin L. Deviney and Thomas M. O'Grady (Eds.)

Petroleum Derived Carbons
Marvin L. Deviney, EDITOR
Ashland Chemical Co.
Thomas M. O'Grady, EDITOR
Standard Oil Co. (Indiana)
A
the Division of Petroleum
Chemistry, Inc. and the
Division of Industrial and
Engineering Chemistry at
the 169th Meeting of the
American Chemical Society,
Philadelphia, Penn.,
April 9-11, 1975
21
ACS S Y M P O S I U M SERIES
AMERICAN CHEMICAL SOCIETY
WASHINGTON, D. C. 1976
In Petroleum Derived Carbons; Deviney, M., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1976.
Library of Congress CIP Data
Petroleum derived carbons.
(ACS symposium series; 21, ISSN 0097-6156)
Includes bibliographical references and index.
1. Carbon—Congresses. 2. Petroleum coke—Con
gresses. 3. Carbon black—Congresses.
I. Deviney, Marvin L.. 1929- . II. O'Grady,
Thomas M., 1929- . III. American Chemical Society.
Division of Petroleum Chemistry. IV. American Chemical
Society. Division of Industrial and Engineering Chemis
try. V. Series: American Chemical Society. ACS sympo
sium series; 21.
TP245.C4P44 661'.06'81 75-37671
ISBN 0-8412-0305-9 ACSMC 8 18 1-463
Copyright © 1976
American Chemical Society
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PRINTED IN THE UNITED STATES OF AMERICA
In Petroleum Derived Carbons; Deviney, M., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1976.
ACS Symposium Series
Robert F. Gould, Series Editor
In Petroleum Derived Carbons; Deviney, M., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1976.
FOREWORD
The ACS SYMPOSIUM SERIES was founded in 1974 to provide
a medium for publishing symposia quickly in book form. The
format of the SERIES parallels that of the continuing ADVANCES
IN CHEMISTRY SERIES except that in order to save time the
papers are not typeset but are reproduced as they are sub
mitted by the authors in camera-ready form. As a further
means of saving time, the papers are not edited or reviewed
except by the symposium chairman, who becomes editor of
the book. Papers published in the ACS SYMPOSIUM SERIES
are original contributions not published elsewhere in whole or
major part and include reports of research as well as reviews
since symposia may embrace both types of presentation.
In Petroleum Derived Carbons; Deviney, M., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1976.
PREFACE
/~\ver the past 35 years the industrial carbon and graphite fields have
expanded greatly both in the technology available and in the vol
ume of production. Not only has modern technology demanded major
improvements in the properties of older, more conventional manufactured-
carbon products, but the great advances in nuclear, aerospace, and
medical sciences have required the development and continued improve
ment of new carbon and graphite materials. Over the past decade or
so, the use of precursors fro
manufacturing has grown rapidly. Two reasons for this growth are
1. the plentiful (until very recently) supplies of heavy ends or
residua from refineries geared to a gasoline-type economy and operating
with emphasis on catalytic cracking
2. the recent development and commercial availability from refin
eries of selectively manufactured carbon precursors, particularly petro
leum pitches, of well defined, reproducible qualities.
The manufacture of carbon and graphite is not only scientifically
interdisciplinary but can be improved only through close cooperation
and understanding between raw material suppliers, industrial fabricators,
and end-product users. The latter two groups have worked closely
together for many years. However, the very important role of the raw
material producer perhaps has been less fully appreciated, especially by
the producer himself. In the past, almost all carbon precursor suppliers
—whether from the coal, petroleum, wood, or paper areas (and the
expected-to-emerge synthetic crude area should be included here, also)
—have considered these raw materials to be mainly by-products to be
processed at as low a cost as possible, subjected to a minimum of quality
control, and sold as inexpensive commodity materials.
In the past decade, however, new factors have required a réévalua
tion of these previous concepts. One reason for this reassessment has
been, of course, the stringent quality and end-use performance demands
associated with recent developments in the general nuclear and aerospace
areas and in certain specialty areas (e.g., electronics, biomedical, and
electrical discharge machining). A second reason, rapidly becoming
more important, is the changing situation regarding raw material availa
bility. Both the increased demands for higher quality carbon and graphite
precursors and the petroleum shortage (especially in the United States)
vii
In Petroleum Derived Carbons; Deviney, M., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1976.
directly affect the refiner. Thus, it was very appropriate that the Division
of Petroleum Chemistry of the American Chemical Society decided to
sponsor this state-of-the-art symposium.
The 31 papers in this volume deal predominantly with carbon and
graphite derived from petroleum, but some overlap with carbons derived
from coal is not only inevitable but desirable for comparing the proper
ties of intermediate and final products (e.g., the several papers dealing
with mesophase and coke formation, electrode performance, fabrication
of carbon-carbon composite materials, machined fabricated products,
and high pressure impregnation technology).
The main objective of this symposium was to obtain papers which
would cover the full scope of the current field of petroleum-derived
carbons. The papers roughly fall into eight groupings as summarized
below.
1. Introductory chapter
costs and the anticipated supply and demand situation (Stokes) and
an overview of the entire field by a well known senior scientist, engineer,
and author with many years of experience in the carbon and graphite
field (Mantell).
2. Refinery processes, particularly coke manufacturing (Metrailer,
Gotshall), production of a new type of high quality petroleum pitch
carbon precursor (Newman) and its analytical characterization (Smith),
preparation of activated carbon from acid sludge (Messman), and the
mechanisms of adsorption with activated and impregnated charcoal
(Magee).
3. Fabrication and manufacturing techniques: large volume prod
ucts, e.g., electrodes and refractories, and specialty products, such as
brushes, nozzles, vanes, dies, seals, bearings, and brakes (Shobert);
aluminum production anodes prepared from petroleum pitch (Pendley);
machine fabrication of carbon and graphite (Corah); specialty (particu
larly nuclear grade) graphites from special green cokes (Home) and
by high pressure impregnation and carbonization techniques (Burns,
Chard); characterization of the structure of graphites prepared for ex
treme thermal shock (Bradshaw); experimental design techniques used
for preparing graphites for thermostructural (ballistic reentry) applica
tions (Pratt); pyrolytic infiltration techniques in the preparation of
carbon-carbon composite materials (Gebhardt); factors affecting the
mechanisms of formation of pyrolytic carbons (Cullis); and pyrolytic
carbon coatings in medical and bioengineering applications (Boleros).
4. Mesophase transformations and properties and their industrial
relevance (Marsh, White). Although the sequence leading to graphitiza-
tion covers a wide temperature range, ultimately reaching nearly 3000°C,
the plastic mesophase region ( comprising only a few percent of the total
temperature span ) is the critical region in which the molecular processes
take place which govern the morphology and microstructure of the final
graphite product.
viii
In Petroleum Derived Carbons; Deviney, M., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1976.
5. Methods of fabricating carbon fibers (Diefendorf) and tech
niques for modifying their surface chemistry to improve adhesion in
plastic composite applications (Ehrburger).
6. Carbon black formation mechanisms (Lahaye, Cullis), micro-
structure and morphology (Ban), and applications of a special type pre
pared from petroleum coke (Gotshall). In terms of both volume pro
duced and total sales revenue, carbon black is one of the most important
chemical products manufactured in the United States. Ninety-four per
cent of carbon black production is consumed by the rubber industry.
Most of this is used in tires where carbon black enhances a number of
rubber physical properties (great improvement in tread abrasion resist
ance being the most important).
7. Electrical and thermal properties of carbon and graphite, with a
comprehensive review (Woollam) and a discussion of the use of inter
calation techniques to increase greatly the electrical conductivity of
graphites, particularly fibers (Vogel, Fischer).
8. Recent developments in the coal derivatives field (Joseph, Kim-
ber), to provide recognitio
area as well as in the field of the upgrading and finding new uses for
petroleum derived carbons.
Finally, many acknowledgments should be extended to several scien
tists and organizations without whose assistance the symposium and this
book would not have been possible. An expression of appreciation is
due to Ashland Chemical Co. and Ashland Oil, Inc., particularly to
James E. Lewis, for encouragement and permission to undertake the
duties of symposium co-chairman and principal editor. The advice and
counsel of Joe W. Hightower, John S. Ball, and Robbin C. Anderson are
also acknowledged. Likewise, appreciation is also extended for the im
portant contributions of the symposium co-chairman, Thomas M.
O'Grady. Finally, special gratitude is expressed to the following industrial
organizations for providing support which made it possible for three
overseas scientists to make presentations at the Philadelphia symposium.
These sponsoring corporations include: Airco Speer, AMOCO, ARCO,
Ashland Chemical, Cabot, Cities Service, Continental Carbon, FMC,
J. M. Huber, Mobil, Pfizer, SOHIO, Stackpole Carbon, Sun Oil, and Union
Carbide.
Ashland Chemical Co.
Columbus, Ohio
October 6, 1975 MARVIN L. DEVINEY
ix
In Petroleum Derived Carbons; Deviney, M., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1976.
1
Manufacture of Industrial Carbons from Petroleum
Raw Materials
CHARLES A. STOKES
Charles A. Stokes Consulting Group, Princeton, N. J. 08540
This paper is concerned with an important but little known
group of highly useful material
purity industrial carbons
industrial carbons for convenience. We are not dealing with the
final end use products that are made from highly pure carbons.
Rather, we are dealing with the forms of carbon that serve as key
components in the manufacture of such end use items as tires,
plastic building materials, amorphous and graphitized electrodes,
and the literally hundreds of very essential small volume items
made from carbon. It is the purpose of this paper to place in
perspective for you these various forms of industrial carbons
indicating not only the opportunities for their growth but the
problems that will be encountered in maintaining adequate
supplies of proper quality source materials for their manufacture
The problems that are now surfacing present both a continuing
technical challenge and a continuing opportunity to enterprising
companies who may want to maintain or improve their competitive
position in the making of such carbons or their raw materials.
It is appropriate to examine the several industrial carbons
as a group because they not only come largely from petroleum
sources but also, to a very considerable extent, they stem from
the same limited part of the barrel of refined oil. If this part
of the barrel finds other uses or becomes too small to take care
of demand, problems could arise quickly that would be felt
throughout a large segment of industry.
We are not concerned wit;h the technical details of processes
to manufacture carbons nor with the small nuances in product
quality resulting from raw material changes. Instead, we are
concerned with the broad raw material supply/demand picture and
the economic effects of a raw material shortage should one occur
in the near future.
Definitions
While we have to be to some degree arbitrary in defining an
1
In Petroleum Derived Carbons; Deviney, M., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1976.
2 PETROLEUM DERIVED CARBONS
Industrial carbon, the definition is nonetheless necessary and
useful in setting apart a certain distinct class of materials
from what will be merely solid carbon or a highly carbonaceous
material of little if any value other than for fuel. The mate
rials under consideration here are often difficult to make and
require careful control for a useful level of properties. This
paper is mainly concerned with industrial carbons made from petro
leum source materials, but It is recognized that similar materials
can be and are made from coal tars or various kinds of !,syn
crudes" that may be made in the future from coal, tar sands, and
the like. With these 11ml tat ions in mind, we can define an indus
trial carbon as:
(1) Essentially pure carbon, i.e. approximately
9*5% or more carbon content on an ash, sulfur,
nitrogen, oxygen, and moisture-free basis.
(2) Normally a solid at room temperature but, in
some cases, containin
liquéfiable a
(3) In the case of liquéfiable materials, the end
use is normally to make solid carbon by elim
ination of practically all volatiles at the
first stage of chemical conversion or altera
tion in the end use process. That is, the
liquéfiable carbon is tailored so that it
will convert easily to solid carbon as nearly
quantitatively as possible on heating, usually
to the extent of at least 50% and often up to
60 to 70%.
(4) Sulfur content usually under 2% and desirably
much lower down to a few tenths of one percent.
Occasionally, materials of 3 - 5% sulfur are
included because of shortages of lower sulfur
carbons.
(5) Non-combustible residue below 0.1%, but in some
cases a few tenths can be tolerated.
(6) Metallic contaminants usually less than 0.01%
for each separate constituent.
This definition excludes carbonaceous materials in which the
carbon can be used chemically without regard to a reasonable
amount of contaminants that do not interfere with the chemical
function of the carbon or the chemical composition of the end
product. Thus, we exclude, for examples, coke designed for blast
furnace use (which isn't made from petroleum anyway), and the
petroleum coke used to make calcium carbide. Included in our def
inition are such Important materials as:
(1) Carbon black.
(2) Selected petroleum coke, green or calcined.
(3) Needle coke, green or calcined.
(4) Electrode pitch.
In Petroleum Derived Carbons; Deviney, M., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1976.
1. STOKES Industrial Carbons from Petroleum Raw Materials 3
(5) Pitch for structural carbon manufacture
including graphite shapes for atomic
reactors.
(6) Carbonaceous reducing agent for the new
Alcoa primary aluminum process.
(7) Activated carbon.
This list is not necessarily an all inclusive one.
As pointed out earlier, industrial carbons are, in general,
raw materials for further conversion rather than the manufactured
or fabricated article itself.
Some of the carbon materials listed above are by-products,
and some are products made deliberately and to carefully con
trolled specifications. However, all of them are either petro
leum refinery by-products or they are made from petroleum
refining by-products. This is a very important point as will be
brought out in the discussion to follow
We will not dwell
materials as the volum
Further, activated carbon is made from many other raw materials
which dominate the field relegating petroleum to a relatively un
important position as yet. Activated carbon is an important
material and will become more so. However, raw material supply
poses no critical problems for this field. The subject of
activated carbon is well covered in other papers by specialists
in this field.
Carbon Black
In total value, probably our most important industrial
carbon is carbon black. We have to say "probably" because it is
so difficult to get accurate figures on the physical volumes and
dollar values of some of the industrial carbons. World output
value of carbon black will cross the $1 billion mark well before
1980. Carbon black is better than 99% carbon. It is an ex
tremely finely divided material with the unique property of dis
persing readily in elastomers to produce a highly strengthened or
"reinforced" end product. About 95% of its use is in rubber. The
largest single rubber use is tires; the use in replacement tires
is about 80% or more of the total consumption for tires, a factor
lending stability to the market.
The carbon black process is essentially a carefully con
trolled partial combustion of heavy aromatic oils in a refractory
lined and insulated furnace. All processes in use are highly
proprietary and therefore cannot be discussed here. For esti
mating raw material requirements, it is satisfactory to multiply
the weight of the carbon black by two. In Figure 1, we show the
raw material requirement for carbon black arrived at by doubling
the expected consumption of carbon black. The needs of the Com
munist countries are almost surely understated as reliable infor
mation is not available.
In Petroleum Derived Carbons; Deviney, M., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1976.