Preface to First Edition

Petrochemicals in general are compounds and polymers derived directly or indirectly from petroleum and used in the chemical market. Among
the major petrochemical products are plastics, synthetic fibers, synthetic
rubber, detergents, and nitrogen fertilizers. Many other important chemical industries such as paints, adhesives, aerosols, insecticides, and pharmaceuticals may involve one or more petrochemical products within
their manufacturing steps.
The primary raw materials for the production of petrochemicals are
natural gas and crude oil. However, other carbonaceous substances such
as coal, oil shale, and tar sand can be processed (expensively) to produce
these chemicals.
The petrochemical industry is mainly based on three types of intermediates, which are derived from the primary raw materials. These are the
C2-C 4 olefins, the C6-C8 aromatic hydrocarbons, and synthesis gas (an
H2/CO 2 mixture).
In general, crude oils and natural gases are composed of a mixture of
relatively unreactive hydrocarbons with variable amounts of nonhydrocarbon compounds. This mixture is essentially free from olefins.
However, the C2 and heavier hydrocarbons from these two sources (natural gas and crude oil) can be converted to light olefins suitable as starting materials for petrochemicals production.
The C6-C8 aromatic hydrocarbons--though present in crude oil~are
generally so low in concentration that it is not technically or economically feasible to separate them. However, an aromatic-rich mixture can be
obtained from catalytic reforming and cracking processes, which can be
further extracted to obtain the required aromatics for petrochemical use.
Liquefied petroleum gases (C3-C4) from natural gas and refinery gas
streams can also be catalytically converted into a liquid hydrocarbon
mixture rich in C6-C8 aromatics.
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Synthesis gas, the third important intermediate for petrochemicals, is

generated by steam reforming of either natural gas or crude oil fractions.
Synthesis gas is the precursor of two big-volume chemicals, ammonia
and methanol.
From these simple intermediates, many important chemicals and polymers are derived through different conversion reactions. The objective of this book is not merely to present the reactions involved in such
conversions, but also to relate them to the different process variables and
to the type of catalysts used to get a desired product. When plausible, discussions pertinent to mechanisms of important reactions are
included. The book, however, is an attempt to offer a simplified treatise
for diversified subjects dealing with chemistry, process technology, polymers, and catalysis.
As a starting point, the book reviews the general properties of the raw
materials. This is followed by the different techniques used to convert
these raw materials to the intermediates, which are further reacted to produce the petrochemicals. The first chapter deals with the composition and
the treatment techniques of natural gas. It also reviews the properties, composition, and classification of various crude oils. Properties of
some naturally occurring carbonaceous substances such as coal and tar
sand are briefly noted at the end of the chapter. These materials are targeted as future energy and chemical sources when oil and natural gas are
depleted. Chapter 2 summarizes the important properties of hydrocarbon
intermediates and petroleum fractions obtained from natural gas and
crude oils.
Crude oil processing is mainly aimed towards the production of fuels,
so only a small fraction of the products is used for the synthesis of olefins
and aromatics. In Chapter 3, the different crude oil processes are
reviewed with special emphasis on those conversion techniques
employed for the dual purpose of obtaining fuels as well as olefinic and
aromatic base stocks. Included also in this chapter, are the steam cracking processes geared specially for producing olefins and diolefins.
In addition to being major sources of hydrocarbon-based petrochemicals, crude oils and natural gases are precursors of a special group of
compounds or mixtures that are classified as nonhydrocarbon intermediates. Among these are the synthesis gas mixture, hydrogen, sulfur, and
carbon black. These materials are of great economic importance and are
discussed in Chapter 4.
Chapter 5 discusses chemicals derived directly or indirectly from
methane. Because synthesis gas is the main intermediate from methane,
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it is again further discussed in this chapter in conjunction with the major

chemicals based on it.
Higher paraffinic hydrocarbons than methane are not generally used
for producing chemicals by direct reaction with chemical reagents due to
their lower reactivities relative to olefins and aromatics. Nevertheless, a
few derivatives can be obtained from these hydrocarbons through oxidation, nitration, and chlorination reactions. These are noted in Chapter 6.
The heart of the petrochemical industry lies with the C2-C4 olefins,
butadiene, and C6-C8 aromatics. Chemicals and monomers derived from
these intermediates are successively discussed in Chapters 7-10.
The use of light olefins, diolefins, and aromatic-based monomers for
producing commercial polymers is dealt with in the last two chapters.
Chapter 11 reviews the chemistry involved in the synthesis of polymers,
their classification, and their general properties. This book does not discuss the kinetics of polymer reactions. More specialized polymer chemistry texts may be consulted for this purpose.
Chapter 12 discusses the use of the various monomers obtained from
a petroleum origin for producing commercial polymers. Not only does it
cover the chemical reactions involved in the synthesis of these polymers,
but it also presents their chemical, physical and mechanical properties.
These properties are well related to the applicability of a polymer as a
plastic, an elastomer, or as a fiber.
As an additional aid to readers seeking further information of a specific subject, references are included at the end of each chapter. Throughout
the text, different units are used interchangeably as they are in the industry. However, in most cases temperatures are in degrees celsius, pressures
in atmospheres, and energy in kilo joules.
The book chapters have been arranged in a way more or less similar to
From Hydrocarbons to Petrochemicals, a book I co-authored with the
late Professor Hatch and published with Gulf Publishing Company in
1981. Although the book was more addressed to technical personnel and
to researchers in the petroleum field, it has been used by many colleges
and universities as a reference or as a text for senior and special topics
courses. This book is also meant to serve the dual purpose of being a reference as well as a text for chemistry and chemical engineering majors.
In recent years, many learning institutions felt the benefits of one or
more technically-related courses such as petrochemicals in their chemistry and chemical engineering curricula. More than forty years ago,
Lewis Hatch pioneered such an effort by offering a course in "Chemicals
from Petroleum" at the University of Texas. Shortly thereafter, the ter
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"petrochemicals" was coined to describe chemicals obtained from crude

oil or natural gas.
I hope that publishing this book will partially fulfill the objective of
continuing the effort of the late Professor Hatch in presenting the state of
the art in a simple scientific approach.
At this point, I wish to express my appreciation to the staff of Gulf
Publishing Co. for their useful comments.
I wish also to acknowledge the cooperation and assistance I received
from my colleagues, the administration of KFUPM, with special mention
of Dr. A. A1-Arfaj, chairman of the chemistry department; Dr. M. Z. E1Faer, dean of sciences; and Dr. A. A1-Zakary, vice-rector for graduate
studies and research, for their encouragement in completing this work.

Sami Matar, Ph.D.

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