Energy & Fuels 2000, 14, 1333
Book Reviews
The Desulfurization of Heavy Oils and Residua, 2nd
Edition. By James G. Speight, Marcel Dekker: New York;
2000. 480 pp. ISBN 0-8247-8921. $175.00.
Considerable progress has been made in the processing of
high-sulfur heavy crude oils and residues over the past twenty
years; therefore, the second edition of James Speight’s 1981
book on desulfurization is a welcome volume. The title is
actually quite misleading, because Speight’s definition of
desulfurization includes any process that changes the sulfur
content of the product streams relative to the feed. Conse-
quently, the subject area is much broader than the title would
suggest, including an introduction to refinery distillation,
visbreaking, and coking processes. Similarly, the discussion
ranges over process concepts for both distillate fractions and
residues, contrary to what the title would indicate. Much of
the flowsheet of a modern refinery is covered, with the
exception of process steps such as alkylation and reforming.
Although sulfur is a major theme, a more accurate title to
indicate the full scope of this book would be along the lines of
“refinery processes for heavy distillates and residues”.
The overall intent of the book is to provide an introduction
to refinery processes, with an emphasis on the underlying
chemistry of the feed stocks and the process transformations.
The opening chapter reviews the history and general terminol-
ogy, followed by a section on the characterization of petroleum
fractions, including elemental analysis, physical properties and
molecular weight. A chapter on feedstock composition covers
the chemical constituents of petroleum fractions, including a
useful discussion of molecular weight-solubility parameter
maps for understanding class fractionation of crude oils and
residues. A disappointment in this section was the brief
coverage of the chemistry of the sulfur species in distillate and
petroleum fractions. The past twenty years has seen significant
advances in understanding the steric factors that control
reactions of thiophenic compounds, the distribution of sulfur
between thiophenic and thioether forms, and the structure of
sulfur in asphaltenes. Steric effects in hydrotreating are men-
tioned in a subsequent chapter, but the importance of the
nature of the sulfur species and the tools for differentiating
them is not mentioned. This gap is surprising given the
importance of thioethers and disulfides in achieving modest
levels of sulfur removal in processes such as visbreaking and
thermal cracking of heavy residues in the presence of hydro-
gen.
Given Speight’s broad definition of desulfurization, the
chapter on desulfurization chemistry (Chapter 4) actually
includes considerable valuable discussion of thermal and
catalytic cracking and coke formation, as well as hydrotreating
reactions of sulfur compounds. The chapter on the desulfur-
ization process (Chapter 5) focuses on catalytic hydropro-
cesses: hydrotreating in fixed-bed reactors and hydroconver-
sion in ebullated-bed reactors. The relationships between the
process variables such as temperature, hydrogen pressure,
residence time and hydrogen consumption are presented well,
although the role of hydrogenation of aromatic carbon in
increasing hydrogen consumption is not discussed. The chem-
istry and characteristics of the industry-standard catalysts are
described effectively, with a brief summary of current views
of the active sites of Ni/Mo and Co/Mo sulfide catalysts. The
section on plugging of catalyst beds is confusing in that two
distinct problems are combined interchangeably, i.e., plugging
of packed-bed hydrogenation reactors by particulates such as
iron sulfide, and deposition of coke and vanadium sulfide
within the porous structure of supported-metal catalysts. The
introductory section on the key process variables and charac-
teristics is then followed by an interesting and effective
discussion of the role of feedstock properties in altering process
and catalyst performance (Chapter 6).
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The next chapter is possibly the most unusual, following as
it does Speight’s definition of desulfurization processes. Chap-
ter 7, on desulfurization during refining, includes coverage of
processes where alterations in sulfur content are strictly
secondary objectives. These process steps include distillation,
fluid catalytic cracking, visbreaking, and coking. Confusing
this classification is coverage of hydroprocessing and deas-
phalting in this chapter, even though these steps are covered
in much more detail in subsequent chapters. The organization
of this section would be improved by moving the coverage of
these topics to subsequent chapters.
The unwary reader will be thoroughly confused by the usage
of the term “hydrocracking” in this text. Unfortunately, this
term is used to describe both thermal cracking processes that
use a catalyst to control coke formation during conversion of
residues, and processes for converting distillates into gasoline
and diesel fractions using bifunctional metal-zeolite catalysts.
Speight uses both definitions interchangeably, in some cases
in the same section. For example, in section 7.6, hydrocracking
is first defined as thermal decomposition with hydrogen and
catalyst to remove heteroatoms and mitigate coke formation.
Further down the same page, hydrocracking is described as
useful for cycle oils and straight run naphtha, then subse-
quently as a one- or two-stage process for making gasoline or
middle distillates from a heavy vacuum gas oil. The latter
applications are for the bifunctional catalyst types which
require careful control of nitrogen content. Luckily, much of
the discussion of hydrocracking is on residue feeds, rather than
zeolite-based catalysis of cracking.
The final chapters on process technologies give summary
descriptions of a wide range of processes for processing residue
fractions, including thermal cracking, fluid catalytic cracking,
deasphalting (Chapter 8) and hydrogen-based processes (Chap-
ter 9). These sections provide an excellent quick reference for
brief descriptions of proprietary process technologies. The
processes are all from the recent literature, therefore, these
chapters capture the current thinking in the design of pro-
cesses for heavy residue fractions. The only minor concern with
this section is that a reader who is new to the field may not
realize that while some of the processes are widely used, some
are only at the pilot or demonstration stage. Speight clearly
points out this issue on the opening remarks in Chapter 9,
but some additional remarks as to which processes are widely
used would be helpful.
The final chapter of the book is a useful discussion of various
technologies for hydrogen production, including partial oxida-
tion, gasification and steam reforming. Unfortunately, the
material on cleanup of refinery gases and the environmental
effects of sulfur containing gases, which was promised in the
preface to the second edition, seems to have been omitted. This
oversight is unfortunate, because after all of the discussion
on desulfurization it would be ideal to consider the fate of the
hydrogen sulfide that is liberated. Finally, the book concludes
with a valuable glossary of refining and petroleum chemistry
terms. This feature is particularly welcome in an introductory
text.
Overall, “The Desulfurization of Heavy Oils and Residua,
2nd Edition” by James G. Speight is a welcome addition to
any reference collection on petroleum processing. It is par-
ticularly aimed at readers who are new to the field, and it
succeeds in providing both factual content and a summary of
the trends and unresolved issues in processing of heavy oil
and residue materials.
Murray R. Gray, Department of Chemical and
Materials Engineering, University of Alberta
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