CMAI Petrochemicals Handbook

Handbook of the World Petrochemical Industry
Handbook of the World

Petrochemical Industry
CHEMICAL MARKET ASSOCIATES, INC.
Headquarters
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Suite 700
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N O R T H A M E R I C A • E U R O P E • A S I A • M I D D L E E A S T
HANDBOOK
OF THE
WORLD PETROCHEMICAL
INDUSTRY
Copyright 2008 by Chemical Market Associates, Inc.
All rights reserved. Reproduction of any part of this work

by any process whatsoever without written permission
of the Copyright owner is expressly forbidden.
Published in Houston, Texas, USA

February 2008
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HANDBOOK OF THE
WORLD PETROCHEMICAL INDUSTRY
TABLE OF CONTENTS
Section Page No.
Introduction 1

Terms & Conditions of Use 3
Explanatory Notes 5
Basic Chemistry 9
Fundamentals of Petrochemicals 25
Conversion Factors 177
Densities 191
Heat Values 193
Glossary 195
Chemistry Terms 196
Contractual Terms 204
Freight Terms 206
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Introduction
1 ~
INTRODUCTION
CMAI is pleased to present the Handbook of the World Petrochemical Industry, a

comprehensive source of information about the petrochemical industry. This handbook begins
with an introduction to basic organic and inorganic chemistry, commercial chemical processes
and the petrochemical product chains. It will also provide a detailed overview of 28 different
petrochemicals that includes: derivative consumption/end-product uses, global market sizes, top
producer lists, process technologies, product yields & conversion factors, densities, heat values
as well as a comprehensive glossary of chemistry and chemical business terms. For easy
reference, conversion factors for metric and standard units are also available.
The recipient of this handbook has been provided a company-unique username and password
to access this study via CMAI’s website at www.cmaiglobal.com. This username and password
may be shared among recipient company employees, as long as each user is an employee of
a company that is at least 60 percent owned by the primary client company, as outlined in the
Terms & Conditions of Use section.
This handbook was completed by a team of Research Associates in CMAI:

Ann Modgling, Catherine Tan, Deepak Veluru, Elena Yip, Felicia Yeoh, Huden Kunz, Javier Ortiz,
Joanne Chin Pascal, Joyce Grigorey, Kristen Holmquist, Marc Laughlin, Ranti Vigo, Rob Taylor,
Salman Siddiqui, Viola Teske and Weili Chen.
We hope you find this handbook to be helpful. If you have any suggestion as to how the next
edition can be improved, we welcome your comments and feedback.
CMAI – Houston
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Fax: 65-6226-5157 Fax: 86-21-5820-7301
[email protected] [email protected]
2 ~
Terms & Conditions of Use
3 ~
TERMS & CONDITIONS OF USE
This handbook is for the exclusive use of the client company and its subsidiaries (60 percent or
more ownership), or for the client company and its parent company if the parent company owns
60 percent or more of the purchasing company. Other consulting firms working on behalf of the
client company are not entitled access to the handbook without prior permission from CMAI.
This handbook is prepared for the sole benefit of the client, and shall not be provided to third parties
without the written consent of CMAI. Any third party in possession of the handbook may not
rely upon its conclusions without written consent of CMAI. Possession of the handbook
does not carry with it the right of publication without the prior written consent of CMAI.
CMAI has conducted and prepared this handbook utilizing reasonable care and skill in applying
methods of analysis consistent with normal industry practice. Others, including government
sources, trade associations or marketplace participants, have provided some of the information
on which the handbook is based. CMAI has utilized such information without verification unless
specifically noted otherwise and accepts no liability for errors or inaccuracies in information
provided by others.
All results are based on information available at the time of publication. Changes in factors upon
which this handbook is based could affect the results. Forecasts are inherently uncertain because
of events or combinations of events that cannot reasonably be foreseen including the actions of
government, individuals, third parties, and marketplace participants. THERE IS NO IMPLIED
WARRANTY OF MERCHANTABILITY OR FITNESS FOR A PARTICULAR PURPOSE.
4 ~
Explanatory Notes
5 ~
EXPLANATORY NOTES
PREFACE
CMAI sincerely hopes and expects that this handbook is prepared for our clients in such a manner
as to prevent any confusion or misinterpretation. This section outlines the general methodology
and assumptions inherent in the development of the data. If questions still arise regarding the
information or use of information in any analysis, tables, or calculations, please contact CMAI at
any of the regional offices.
DATA SOURCES
This handbook contains information obtained from various sources. The basic capacity data has
evolved over a period of years and is continually refined. Generally, this information is verified
through discussions with representatives of the companies that are listed in the capacity tables
during personal visits to their offices or during meetings at other venues. The statistics are mainly
obtained from government sources or trade associations. CMAI has formed opinions by utilizing
industry-based estimates to complement the data for countries that are smaller in market size
or are problematic to analyze. Contact by CMAI personnel around the world is also made with
companies in various regions that are known to have business activities within the areas where
data are difficult to obtain or require further verification. Where there were known or suspected
inconsistencies or errors in published data, corrections were made using CMAI best estimates.
As such, the materials and analysis presented herein are strictly the opinion of CMAI and are
based on information collected within the public sector and on assessments by CMAI staff.
UNITS OF MEASURE
Unless specifically noted, any data measured in units of weight will be presented as standard
metric tons (equal to 1,000 kilograms or 2,204.6 pounds). Any text reference to tonnes or tons
implies standard metric tons unless otherwise noted.
CONVERSION FACTORS
The conversion factors generally used to calculate the equivalent monomers contained in the
various derivative products are shown in the Conversion Factors section. It should be noted
that many derivatives have conversion factors that change with improving technology. It is
also important to note that the conversion factors for each country vary depending upon the
sophistication of the local process technology and operational skills. In these cases, CMAI has
used its best estimates to change the conversion factors to more accurately reflect the actual
situation.
WORLD REGIONS
For purposes of this handbook, CMAI generates summations and analysis for ten major regional
markets: North America, South America, West Europe, Central Europe, CIS & Baltic States,
Africa, Middle East, Northeast Asia, Southeast Asia, and Indian Subcontinent. A listing of the ten
regions and the countries included herein follow:
6 ~
Explanatory Notes
NORTH AMERICA SOUTH AMERICA WEST EUROPE

Canada (CAN) Argentina (ARG) Austria (AUS)
Mexico (MEX) Bolivia (BOL) Belgium (BEL)
United States (USA) Brazil (BRA) Denmark (DEN)
Chile (CHL) Finland (FIN)
CENTRAL EUROPE Colombia (COL) France (FRA)
Albania (ALB) Costa Rica (CRA) Germany (GFR)
Bulgaria (BUL) Cuba (CUB) Greece (GRE)
Czech Rep. & Slovakia (CZS) Dominican Rep. (DOM) Iceland (ICE)
Hungary (HUN) Ecuador (ECU) Ireland (IRE)
Poland (POL) El Salvador (ELS) Italy (ITA)
Romania (ROM) Guatemala (GUA) Luxembourg (LUX)
Former Yugoslavia (YUG) Guyana (GUY) Malta (MAL)
Honduras (HND) Netherlands (NET)
CIS & BALTIC STATES Jamaica (JAM) Norway (NOR)
Russia (RUS) Netherlands Ant. (NAT) Portugal (POR)
Other CIS & Baltic States (CIS) Nicaragua (NIC) Spain (SPA)
Panama (PAN) Sweden (SWE)
AFRICA Paraguay (PAR) Switzerland (SWI)
Algeria (ALG) Peru (PER) United Kingdom (UKG)
Angola (ANG) Suriname (SUR)
Cameroon (CAM) Trinidad (TRN) MIDDLE EAST
Chad (CHD) Uruguay (URU) Bahrain (BAH)
Egypt (EGT) Venezuela (VEN) Iran (IRN)
Ethiopia (ETH) Other So. America (OSA) Iraq (IRQ)
Gabon (GAB) Israel (ISR)
Ghana (GHA) INDIA SUBCONTINENT Jordan (JOR)
Guinea (GUI) Bangladesh (BGD) Kuwait (KUW)
Kenya (KEN) India (IND) Oman (OMN)
Libya (LYB) Pakistan (PAK) Qatar (QAT)
Morocco (MOR) Sri Lanka (SRI) Saudi Arabia (SAR)
Mozambique (MOZ) Syria (SYR)
Nigeria (NIG) SOUTHEAST ASIA Turkey (TUR)
Sierra Leone (SIE) Australia (AST) United Arab Emirates (UAE)
South Africa (SOA) Brunei (BRU) Other Middle East (OME)
Swaziland (SWA) Indonesia (INO)
Tanzania (TNZ) Malaysia (MAY) NORTHEAST ASIA
Tunisia (TUN) Myanmar (MYA) China (CHI)
Zaire (ZAI) New Zealand (NZE) Hong Kong (HON)
Zimbabwe (ZIM) Philippines (PHL) Japan (JAP)
Other Africa (OAF) Singapore (SIN) Korea, North (KON)
Thailand (THA) Korea, South (KOS)
Vietnam (VIE) Taiwan (TAI)
Other SE Asia (OSE)

7 ~
8 ~
Basic Chemistry
9 ~
CMAI Product Coverage
XYLENES TOLUENE BENZENE STYRENE ETHYLENE PROPYLENE BUTADIANE AMMONIA METHANOL CHLORINE CAUSTIC SODA
& DERIVATIVES & DERIVATIVES & DERIVATIVES & DERIVATIVES & DERIVATIVES & DERIVATIVES & DERIVATIVES & DERIVATIVES & DERIVATIVES & DERIVATIVES & DERIVATIVES
MIXED XYLENES TOLUENE BENZENE STYRENE ETHYLENE PROPYLENE BUTADIENE FERTILIZERS METHANOL CHLORINE CAUSTIC SODA
ORTHOXYLENE BENZENE ETHYLBENZENE POLYSTYRENE EDC ACRYLONITRILE ABS UREA DMT EDC PULP & PAPER
PARAXYLENE MIXED ALKYLBENZENE EPS ETHYLENE GLYCOL CUMENE ADIPONITRILE/HMDA UREA RESINS ACETIC ACID VCM ALUMINA
METAXYLENE XYLENES CHLOROBENZENE ABS ETHYLENE OXIDE POLYPROPYLENE NITRILE RUBBER CAPROLACTAM FORMALDEHYDE PVC PROPYLENE OXIDE
DMT PHENOL MALEIC SAN HDPE ACRYLIC ACID POLYBUTADIENE ACRYLONITRILE MMA EPICHLOROHYDRIN EPICHLOROHYDRIN
TPA TDI ANHYDRIDE SB LATEX LDPE BUTANOLS POLYCHLOROPRENE MTBE PROPYLENE OXIDE ORGANICS
PET CAPROLACTAM ANILINE SB RUBBER LLDPE 2-ETHYLHEXANOL SB LATEX MDI INORGANICS
FIBER CHIP BENZOIC ACID CUMENE UNSATURATED PE EPDM ISOPROPANOL SB RUBBER TDI SODIUM CHLORATE
FILM RESIN TNT ETHANOL NONENE THERMOPLASTIC TiO2 KOH
PHTHALIC ANHYDRIDE ALPHA OLEFINS DODECENE ELASTOMERS METHYL CHLORIDE
PBT VINYL ACETATE PROPYLENE OXIDE METHYLENE CHLORIDE
ISOPHTHALIC ACID ETHYL CHLORIDE ACRYLIC FIBER CHLOROFORM
PET RECYCLE ETHYLBENZENE ACRYLAMIDE CARBON TETRACHLORIDE
PTT TRICHLOROETHYLENE
10
PERCHLOROETHYLENE
PULP & PAPER
HYDROCHLORIC ACID
POLYESTER CYCLOHEXANE& PHENOL POLYPROPYLENE

BUTYLENES SODA ASH
FIBERS DERIVATIVES & DERIVATIVES FIBER
TEXTILE/APPAREL CYCLOHEXANE PHENOL NONWOVENS BUTYLENE GLASS

INDUSTRIAL CAPROLACTAM BISPHENOL A MTBE/TAME STPP
CARPET ADIPIC ACID PF RESINS BUTENE–1
NYLON RESINS CAPROLACTAM BUTYL RUBBER
ALKYLPHENOL POLYISOBUTYLENE
POLYCARBONATE RAFFINATE 1 & 2
EPOXY RESINS
NYLON FIBERS ACETONE
TEXTILE/APPAREL
INDUSTRIAL
CARPET
ENGINEERING RESINS
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BASIC CHEMISTRY
INORGANIC & ORGANIC CHEMISTRY DIFFERENCES
Before 1830, the term organic chemistry was applied to anything living. With the ability to
synthesize biological molecules, organic chemistry came to mean the chemistry of the compounds
of carbon. Organic compounds are found in almost every aspect of everyday life, ranging from
the packaging on cereal boxes and milk jugs to the plastic housing your computer monitor, the
dashboard of your car, and the cushioning materials in your shoes.
The chemistry of carbon is complex and integral to modern life. In fact, it is considered the
chemistry of life and is known as “organic chemistry.” Carbon easily links with itself, which is
why there are so many organic chemicals. Because of this, hydrocarbons can be manipulated
into any number of formations, each with its own properties, characteristics, and end uses. The
American Chemical Society maintains a registry of chemical substances of which 90 percent
are carbon based. The remaining 10 percent is divided between alloys and other inorganic
compounds.
As already mentioned above, organic chemicals consist mainly of carbon and hydrogen atoms,
but also other elements such as oxygen, nitrogen, halogens (e.g. chlorine), and sulfur are often
incorporated. In contrast to organic chemistry, inorganic chemistry is considered to be the
chemistry of non-living materials including the water we drink, the air we breathe, and all of the
everyday items made of glass, ceramic, clay, and metal. Inorganic chemicals are in general made
of all available elements except carbon, although some carbon-containing compounds such as
carbon monoxide, carbon dioxide, carbonates, and cyanides are considered as inorganic.
Typically, however, organic and inorganic compounds differ in structure. The literally thousands
of organic compounds are created by manipulating and combining a small number of elements
in many different ways. The great variety is further increased by the ability of the molecules to
link with each other in order to form complex chain structures consisting of a high number of
repeating units. Inorganic chemistry, on the other hand, achieves its variety in a different way
due to the high number of different elements considered. Rather than being built of molecular
chains, these compounds are generally smaller clusters of atoms. The characteristics of inorganic
chemicals are defined by the kind of atoms incorporated as well as by the way the atoms are
combined with each other. Inorganic compounds are results of reactions that are based on
electro negativities.
Hydrogen & Carbon Elements
All atoms contain positively charged nuclei consisting of protons and neutrons. Negatively
charged electrons orbit the nucleus. The number of electrons balances the positive charge of
the nucleus. The ability of an atom to bond with other atoms is a direct result of the number and
placement of the electrons in the atom.
The sharing of electrons results in the formation of chemical bonds. With the formation of bonds
comes the ability to join and manipulate atoms to produce molecules with desired characteristics.
Since organic chemistry is the chemistry of carbon, it is not surprising that carbon has an
unrivaled ability to link with itself. Carbon has a void of 4 electrons available for bonding while
hydrogen has one. The combination of carbon atoms with hydrogen atoms result in the formation
of hydrocarbons.
11 ~
Basic Chemistry
Atoms and chemical materials are more stable when their electric charge is neutral. Atoms
can either contribute an electron to another atom to form an ionic bond or share an electron
between atoms, forming a covalent bond. With one electron available for bonding, hydrogen has
a strong tendency to form covalent bonds or to share electrons. Therefore, a combination of four
hydrogen and/or carbon atoms will join to form a stable hydrocarbon molecule. The molecule
is said to be saturated if all four electron voids are filled by a carbon or hydrogen atom. Carbon
chains form in specific patterns of varying lengths as can be seen in the picture below.
H H H
H C H H C C H
H H H
SINGLE CARBON BONDED HYDROCARBON

ELEMENT
These hydrocarbon chains have specific names consisting of a prefix referring to the number
of carbon atoms (meth, eth, prop, but, pent, etc.) and a suffix indicating the number of bonds
between the atoms (single, double, and triple bonds possible). Multiple bonds are formed when
the carbon atoms are not completely saturated with hydrogen. The molecule is referred to as
an “olefin” if it contains at least two unsaturated carbons connected by one double bond. The
presence of a double bond is denoted by use of the suffix “ene” rather than “ane”. Thus ethane
becomes ethylene, propane becomes propylene.
Alkanes Alkenes
Methane
Ethane Ethylene
C C C C
Propane Propylene
C C C C C C
Butane Butylene
C C C C C C C C
A double bond causes the hydrocarbon to be more reactive, making compounds easier to
manipulate into useable chemical compounds such as ethylene and propylene, which are the
main petrochemical feedstocks used to produce, plastics and resins.
12 ~
Basic Chemistry
ORGANIC CHEMISTRY BASICS
Organic chemicals fall into the broad categories of petrochemicals, polymers, and fine
chemicals.
Petrochemicals (natural gas (C1), olefins, aromatics)
The petrochemicals industry is broadly defined as industrial activity which uses petroleum or
natural gas (methane) as a source of raw materials and whose products are neither fuels nor
fertilizer. The petrochemical industry begins with oil refineries and extracting plants that remove
ethane and higher hydrocarbons from natural gas streams. The three main categories of
petrochemicals include natural gas (C1s), chemicals derived from methane, a gas consisting of a
carbon molecule and four hydrogen atoms, olefins, specifically ethylene (two carbons), propylene
(three carbons) and butadiene (four carbons), and aromatics such as benzene, toluene, mixed
xylenes, styrene, and paraxylene, all characterized by the same cyclic basic structure of six
carbon atoms.
Polymers (derivatives of petrochemicals)
Polymers are long chains of molecules. For instance, polyethylene is a type of polymer. It is
made from literally thousands of repeating units of ethylene “monomer,” or single chemical unit.
Similarly, polypropylene is a polymer of propylene.
Polymers are the “useful” forms of petrochemicals. They are molded, extruded, and reacted into
various objects that can be used by consumers. For example, polyethylene is used to make films
like those used in garbage bags. A major use of polypropylene is woven fabric.
Fine Chemicals (soaps, pesticides, pharmaceuticals, dyes)
Also known as “specialty” chemicals, this branch of the chemical industry is a somewhat
arbitrary grouping of several specific industries, all of which are characterized by the synthesis of
specific desired compounds from the raw materials provided by the petrochemical industry (and
sometimes other sources). These products are often valuable and produced in small quantities.
General product categories in the fine chemicals industry include pharmaceuticals, dyes and
pigments, pesticides, and soaps. More specific product groupings include analytical reagents
and photographic chemicals.
13 ~
Basic Chemistry
INORGANIC CHEMISTRY BASICS
Inorganic chemicals are differentiated by the large number of atoms and molecules and the
conditions in which they are joined. In contrast to that, organic chemicals are composed of only
a few elements but can be arranged in thousands of different patterns, making thousands of
different compounds. As a consequence, inorganic chemicals make up less than 10 percent of
the total number of registered chemical substances.
Even though inorganic chemicals are less numerous than organic, they are still important
compounds and account for about half of total U.S. chemical production. From an industrial
standpoint (products and markets), inorganic chemicals can be categorized as gases, alkali,
acids, and nitrogen-based chemicals (explosives and fertilizers).
Gases
Industrial gases include nitrogen, argon and oxygen. Although each of these three gases is
found in abundance in nature (nitrogen makes up 78 percent of the earth’s atmosphere), gas
separation technology is necessary to separate these gases into their pure forms. As pure
gases, these three have many industrial applications. The primary use for nitrogen is to create
an oxygen-deficient atmosphere. Examples of nitrogen industrial uses include fire and explosion
prevention, food storage and transportation, and to prevent oxidation of metals (rust). Oxygen
is the second most heavily consumed industrial gas, following nitrogen. Oxygen’s primary use
is to enhance combustion. Things tend to burn better in the presence of pure oxygen so it is
consumed in the steel industry. Other industrial sectors that use oxygen are chemical production,
water treatment, glass production, as well as pulp and paper manufacture. Argon is an inert gas
(not very reactive as are all of the noble gases), giving it properties that allow it to be used to flush
out other gases and impurities. Argon is used extensively in steel production and is becoming
increasingly useful in semi-conductor manufacturing.
The Alkali Industry
The alkali industry includes the production of useable industrial chemicals from naturally occurring
minerals, such as salt or limestone. Historically, alkali salts were widely used in making soap,
glass and textile bleaches. They were produced by leaching plant ash with large quantities
of water until the 1780s, when the LeBlanc process for producing caustic soda from salt was
developed. This process gave rise to the modern chlor-alkali industry and was one of the first
industrial chemical sectors to be developed.
Soda ash and cement, made from a powdered mixture of limestone, sand (silica), a clay or shale
containing aluminum, and iron oxide, are common products of the alkali industry. The chlor-alkali
industry refers to the production of chlorine gas and caustic soda from salt. Chlorine has many
industrial uses, but by the far the largest is as a feedstock for vinyls. Caustic soda is used heavily
in the production of pulp and paper, other inorganic and organic chemicals, and in the production
of alumina from bauxite.
14 ~
Basic Chemistry
The Acid Industry
Acids are familiar as corrosive substances often used in separating or removing chemicals. They
are defined as substances which increase the hydrogen ion concentration when added to water
(opposed to alkalis decreasing the concentration of hydrogen ions). Acids have a myriad of
industrial applications due to their ability to separate or remove chemicals. Almost all industrial
processes use acids in one form or another including chemical production, auto making, semi-
conductor manufacture, paper production, textiles and garments, and on and on.
The most common industrial acid is sulfuric followed by hydrochloric acid. Today, most of
the sulfuric acid produced in North America is used in the manufacture of fertilizers (about 70
percent). Metals recovery, petroleum refining, and chemical manufacturing each account for
another 5 percent; the remaining 15 percent has many smaller uses. Hydrochloric acid (HCl) is
produced as a by-product of almost all processes that involve chlorine such as the production of
vinyls. HCl has many industrial applications including chemical manufacturing, steel production,
oil and gas well acidization, and food processing.
Nitrogen Based Chemicals
Nitrogen based chemicals such as ammonia, fertilizers, and explosives are derived by the
combination of nitrogen with other elements (mainly oxygen, hydrogen, and carbon). One
nitrogen atom combined with three hydrogen atoms provides ammonia. This is the familiar
“household ammonia”, used in domestic cleaning and disinfecting. More concentrated solutions
are used in the chemical laboratory.
Nitrogen combined with oxygen is responsible for the characteristic properties of explosives
(mainly organic compounds) and fertilizers (mainly inorganic compounds). Interestingly, the first
explosives are known to the Western world date since medieval times as early as 1350 AD.
Today, nitrogen is used in the manufacture of common explosives such as nitroglycerine and
TNT. By far, the largest end use for nitrogen based compounds is in fertilizers. The use of
fertilizers increases crop yield and land productivity, providing necessary food for the world’s
population. Ammonia based chemicals, fertilizers and explosives, account for about one quarter
of total inorganic chemical production.
15 ~
Basic Chemistry
COMMERCIAL CHEMICAL PROCESSES
Over 90 percent of the world’s production of organic chemicals is from crude oil and natural gas.
In fact, many of the processes in the chemical industry have evolved from the refining industry.
There are literally thousands of chemicals that can be obtained from crude oil and natural gas,
using a combination of “physical” and “chemical” processes. Physical processes involve the
separation or re-combination of chemicals, such as distillation/fractionation, extraction (typically
using solvents) and blending processes. This is different from the chemical processes like
reforming, cracking and polymerization, where new chemicals are formed via reaction. Physical
and chemical processes are often combined to manufacture chemicals.
The following processes describe in general terms the processes involved with the vast majority
of all commercial chemical operations.
Heating and Cracking

STEAM CRACKING OF ETHYLENE
Feedstock
Ethylene
Naphtha Furnace Quench Primary Distillation

Ethane Boiler Fractionator Columns
(heating) Propylene
Propane (cooling) (separation) (separation)
Steam Butadiene
Butylene
Boiler feed
water
“Cracking” is the process by which various fractions of refinery processes are broken down into
smaller molecules by high temperatures (“thermal” cracking) or by using catalysts (“cat” cracking).
Thermal cracking (steam cracking) uses heat to break the chemical bonds in feedstocks. This
process usually occurs in the presence of steam and temperatures are in the range of 800-850°C.
Catalytic cracking takes place at lower temperatures and pressures using a catalyst to promote
the reaction. Both processes are very energy intensive, requiring large amounts of fuel.
Steam cracking is the most common method to manufacture the olefin feedstocks used in
petrochemical production. Steam crackers are the basis for integrated petrochemical complexes.
They produce various olefin feedstock streams and feed them into derivative units for further
processing. For example, the ethylene from a steam cracker is converted to polyethylene while
the propylene is converted to polypropylene. The recent trend is for steam crackers to be larger
and larger in order to achieve economies of scale. With the large capital investment that is required
to build these units, complex feedstock and product sharing or equity sharing arrangements are
becoming more common in the U.S. Steam crackers can be identified by the tall (over 200 feet
generally), cylindrical furnaces which are used to do the chemical separation. There are typically
3-5 furnace stacks in a series. Steam cracker capacity can easily be incrementally increased by
adding another furnace stack.
Various feedstocks can be fed to steam crackers, and the corresponding quantity and purity
of the olefin streams (ethylene, propylene, and butadiene/butylene) varies depending on the
feedstock. Steam crackers are designed and operated to maximize the relative price spreads
between feedstocks and olefins.
16 ~
Basic Chemistry
Fractional Distillation FRACTIONAL DISTILLATION
Light End
High Boiling Point
Mixed Component
Stream
Heavies
Low Boiling Point
Heat
Fractional distillation is used to separate the various components of a stream. This process
makes use of the difference in boiling point of different components, or “fractions” in the
feedstock stream, to separate the input stream into fractions. The most familiar example of
fractional distillation is distilling water from alcohol to make alcoholic spirits. The most common
fractional distillation process in the petrochemical industry is the separation of crude oil into many
components that are then further purified and have separate end uses such as motor gasoline,
lube oils, petrochemical feedstocks, etc.
Reacting
CHEMICAL REACTION
Chemical
Feedstocks
Reactor Finished Product
Catalyst (Resin)
By-Products
Reacting processes are those by which a new chemical (or chemicals) is (are) formed. Cracking
is technically a reacting process, because ethane becomes ethylene and hydrogen in the
process. However, this term more commonly refers to those processes that take two materials
and combine them into one or more products via a chemical reaction. A chemical reaction is, for
example, when methane (natural gas) and water (steam) are mixed and combine to a methanol
molecule, or when ethylene and chlorine react to form ethylene dichloride (EDC).
Reactions can be batch processes or continuous processes. Batch processes involved combining
the materials in set quantities and removing the finished products following the reaction. A more
efficient and common process involves continuous reactions where, as the name implies, the
chemicals are continuously fed into a reactor and drawn off the finished process as the reaction
occurs. The speed or efficiency with which a chemical reaction takes place can be enhanced
by the use of a catalyst. A catalyst is a substance that promotes or accelerates the chemical
reaction while remaining virtually unchanged itself.
17 ~
Basic Chemistry
Polymerization
POLYMERIZATION
M
M
M
M
M
M Reactor M
M M
M M M M
M M M
M
M
M
M
Monomers Polymers
Polymerization is the process used to make polymers. Polymers are organic compounds whose
structure consists of repeated small chemical units (molecules called “monomers”). As already
mentioned, polyethylene is a type of polymer. It is mainly made from thousands of repeating
units of ethylene monomer. Similarly, polypropylene is a polymer of propylene.
Blending
Blending is a physical process where products are mixed. In the chemical industry, this can
be done to prepare a feedstock for reaction, to generate a more readily handled product, or to
introduce catalysts in a reaction, among other reasons. Blending can employ batch processes,
which use one vessel to mix the products, or continuous processing, where mixing takes place
without pausing for completion of a batch. A good example of a chemical blending process is
the combination of styrene and butadiene monomers before polymerization to ensure a well-
distributed and random mixture. Factors to consider in blending operations include physical form
(solid, gas, liquid), temperatures, and chemical compatibility of the components.
18 ~
Basic Chemistry
OVERVIEW of ORGANIC CHEMISTRY NOMENCLATURE & PRODUCT CHAINS
As the chemical industry became an international phenomenon, the need for definitive rules
describing its products became important. In 1957, the Council of the International Union of Pure
and Applied Chemistry (IUPAC) issued these rules in its Journal “Pure and Applied Chemistry.”
Today, all chemical substances are named and known to the global chemical industry according
to IUPAC definitions.
“Alkanes” are hydrocarbon molecules in their most basic structure. They are named according
to the number of carbons in the molecule. Methane, ethane, propane, and butane are part of the
alkane family. They contain one, two, three, and four carbons, respectively. The carbons are
linked together by “single bonds,” which can be thought of as direct connections between carbon
atoms. Pentane and hexane have five and six carbon molecules. Cyclohexane has six carbons,
but these are configured in a “ring”.
“Alkenes” are also hydrocarbon molecules, but differ from alkanes in that they have at least one
“double-bond” per molecule. A double-bond is a carbon-to-carbon linkage where there are two
direct connections. This can only be achieved in a stable fashion by removing one hydrogen atom
from each of the linked carbons. Ethylene, propylene, and butylene are alkenes containing two,
three, and four carbons, respectively. Alkenes containing two double bonds are called “dienes,”
with butadiene, a four-carbon molecule with two double bonds, being an example. The presence
of a double bond makes these compounds less stable and more reactive. Therefore, they are
suitable feedstocks for other petrochemical processes and enable the production of a variety of
other chemical compounds (so-called derivatives).
In the petrochemical industry, alkenes are often called “olefins”. The family of “olefins” includes
ethylene, propylene, and the C4 olefins, butylene, and butadiene, but also C5s and hexene.
Hydrocarbon molecules with the basic structure of benzene, which is characterized by a ring of
six carbons and three double bonds, are members of the “aromatics” family (which is far more
extensive than can be mentioned here).
For C4 and other hydrocarbons with more than three carbon atoms, it is possible to manufacture
“isomers.” Isomers are molecules with the same number and type of atoms (same molecular
weight), but different in arrangement or configuration. Carbons connected in a straight chain are
said to be “normal” such as normal butane. If the molecule is branched it is referred to as “iso”,
such as iso-butane. If a molecule has a ring structure (with no double bonds) it is cyclic, such as
cyclohexane.
19 ~
Basic Chemistry
OLEFINS
Light Olefins, consisting of ethylene, propylene and C4s, make up almost half of the global chemical
market. They are used as feedstocks for familiar products such as plastics and polymers, vinyls,
and synthetic rubber. Ethylene is by far the dominant olefin, making up about 60 percent of
total olefin demand. It is followed by propylene with 35 percent of demand and C4s with only 6
percent.
Olefins are produced in steam crackers, which are operated primarily to produce ethylene,
since demand is highest for ethylene and its derivatives. Propylene and butadiene/butylenes
are produced as co-products. The amount produced of each olefin stream is dependent on the
feedstock used, with higher ethylene concentrations coming from ethane streams. Producers
choose feedstock streams to optimize production costs and product slates depending on relative
feedstock and product prices and derivative needs. Many olefin producers are integrated into
downstream derivative production. For example, many of the U.S. polyethylene producers are
also ethylene producers. Ethylene and the other olefin feedstocks are commodities, making it
difficult for producers to realize competitive advantages other than integration into downstream
derivatives.
Others
Polyester
Ethylene Soft Drink Bottles,
9%
Clothing, VCR Tapes 13%
30%
57%
Vinyls 14%
Pipe, Building
Materials Polyethylene
7% Shrink Wrap, Auto Parts,
Styrene Milk Jugs
Coffee Cups
Others 27%
56%
Steam
Steam Propylene
Polypropylene
Thermal Underwear,
Acrylonitrile
Cracker 16%
Acrylic Fibers
11% Caps & Closures, Woven
Materials
6%
Cumene
Polycarbonates for Eyeware
& Auto Glass
Others
Adiponitrile 14%
Nylon Fibers 30% SBR
7% Tires
ABS 9%
Molded Parts
12%
28%
C4s
C4s SBL
Paper coating & PBR
10% Carpet backing Tires
Pygas
C4s
23%
Fuels
C4s
21%
20 ~
Basic Chemistry
AROMATICS
The aromatics mainly discussed here due to their high importance for the petrochemical industry
are benzene, toluene, and the three isomers of xylene. A stream consisting of these components
is often referred to as a “BTX” stream. All aromatics discussed here are structural related to
benzene which is probably the most common member of this product group and characterized by
a ring structure of six carbons and the system of three alternating double bonds. Aromatics make
up about 15 percent of the global chemical market. They are used as components in gasoline
or as feedstocks for petrochemical derivatives such as styrene for take out food containers,
polycarbonate resins in eyeglasses, and polyester for fibers and films found in clothing, carpeting,
video tapes, and X-rays. BTX streams are split fairly evenly with benzene, toluene and xylenes
each providing about one third of the total volume.
Aromatics streams are produced in refineries (in reforming operations) or in small quantities from
olefins production. Many of the large refining companies are involved in aromatics and derivative
production because they have access to the aromatic feedstocks. Aromatics production is mostly
dependent on refinery operations and is thus heavily concentrated in North America, account for
more than 25 percent of total world capacity. Another region with significant aromatics production
is Northeast Asia. Aromatics production is primarily driven by the need to produce xylenes
feedstock for the large polyester textiles and garments industry in Asia.
Others
Aniline
Polyurethanes
9%
8%
Cyclohexane
Nylon
12%
52% Styrene
C6+ Packaging and
Benzene Insulation, Coffee
Raffinate 19% Cups
12% 16% Cumene Toluene

Polycarbonates for Diisocyanate
Eyewear and Auto
Polyurethane Foam
Glass
5%
Xylenes / Solvents
Reforming Unit Extraction &
Toluene Benzene
in Refinery Distillation 39% 25%
35%
18%
13%
C9 +
Aromatics Xylenes Gasoline
Benzene
3% 34%
Solvents 13% 76%

Industrial Uses
Paraxylene
Polyester Film, Fiber
Others 9% and Resin, Carpet
2% and Garments,
Orthoxylene
Plasticizer
for Plastics
21 ~
Basic Chemistry
POLYMERS
Products made of polymers encompass everything from polyethylene grocery bags to the
synthetic rubber used in tires and golf balls. “Poly”, the Greek word for many, refers to the many
small units or “mers” combined to form polymers. Over the last 30-40 years, polymers have
become integral to our lifestyle as substitutes for glass and paper in packaging. The widespread
use of polymers has resulted in fresher food and less waste, the light-weight foam for seats and
padding that allows for more fuel-efficient cars, and long-lasting hygienic materials for medical
applications.
Product
Product Markets
Markets
LDPE
LDPE Freezerand
Freezer andBread
BreadBags,
Bags,
PlasticCoasting
Plastic Coastingfor
forPaper
Paper
LLDPE
LLDPE Shrinkand
Shrink andStretch
StretchWrap,
Wrap,Container
ContainerLids
Lids
HDPE
HDPE Milk Bottles, Grocery Bags, Auto Parts
Milk Bottles, Grocery Bags, Auto Parts
Polypropylene
Polypropylene PackagingFilm,
Packaging Film,Sacks,
Sacks,Carpets
Carpets
Polybutylene
Polybutylene Pipes,Adhesives,
Pipes, Adhesives,Blends
Blends
Polybutadiene
Polybutadiene Tires,Plastic
Tires, PlasticModification
Modification
Polystyrene
Polystyrene Packaging,Toys,
Packaging, Toys,Cups,
Cups,Cutlery
Cutlery
SBR/SBL
SBR/SBL Tires,Carpets,
Tires, Carpets,Footwear,
Footwear,Molded
MoldedGoods
Goods
Urethanes
Urethanes Foams, Insulation
Foams, Insulation
PVC
PVC Pipe,Building
Pipe, BuildingMaterials,
Materials,Auto
AutoUpholstery
Upholstery
Selected Global Polymer Capacity

Based on 2007 Annual Capacities - 245 Million Metric Tons
Polyethylene
31% Polypropylene
20%
Synthetic Rubber
2%
PVC
Polystyrene 17%
6%
Polyester
24%
22 ~
Basic Chemistry
Polyolefins, polymers made from ethylene and propylene, include high density (HDPE), low
density (LDPE), and linear low density polyethylene (LLDPE), and polypropylene. Polyolefins
account for about 50 percent of the polymer industry. Polyethylene is used in food packaging,
such as freezer bags and bread bags, caps and closures for plastic containers, auto parts and
milk bottles. Polypropylene is used in caps and closures, carpet backing, carpet yarn, food
packaging (potato chip bags), thermal underwear, car seats, and plastic food containers, such
as catsup and syrup bottles. Polyolefins are relatively low-cost polymers with a wide range of
applications.
PVC, which is made by polymerization of vinyl chloride, is found in siding and windows for
buildings, pipe for infrastructure such as water and sewage lines, and shower curtains. Polyester
is used in packaging, such as water bottles, textiles and garments, and video and X-ray films.
Polystyrene is most familiar as the material used in disposable coffee cups, but it has uses in
electronics as well. Synthetic rubbers are found in tires, golf balls, adhesives, and conveyor
belts.
Polymer production is concentrated in North America, West Europe and Northeast Asia. The
developed olefins and refining industry in North America provides low-cost feedstock for polymers
while the high concentration of people in these regions provides the market for polymers.
23 ~
Basic Chemistry
CHLOR-ALKALI
Chlor-alkali refers to the production of chlorine and caustic. The raw material for chlor-alkali
production is salt, which is a naturally occurring compound composed of sodium and chlorine
(used in everyday life as table salt). Separately, chlorine is an extremely toxic gas and sodium
is a mineral. These chemicals form salt, which is typically found in vast, underground collections
called salt domes. When electricity is applied to an aqueous solution of sodium chloride, the
sodium and chlorine ions start to separate and form new chemical species. Chlorine is recovered
as a gas and caustic soda as aqueous solution. The chlor-alkali process produces chlorine and
caustic soda in specific ratios. There is always 1.0 unit of chlorine and 1.1 dry units of caustic
soda. The combination of 1.0 chlorine unit plus 1.1 dry caustic soda units is referred to as an
electrochemical unit, or ECU.
Chlor-alkali production is centered in North America and West Europe, where it supported chlor-
alkali consuming industries, such as vinyls and pulp and paper; North America also previously
has low-cost power sources. Growing demand in Asia has resulted in this region becoming the
largest producing region, even though it does not have the lowest cost.
Soaps &
Detergents
6% Others
40%
Inorganic
Chemicals
Caustic
Chlorine 15%
Soda
Organic
Chemicals
13%
Salt Pulp & Paper
Salt Chlor
Chlor Alumina
1.0 unit chlorine & 8% 18%
Alkali
Alkali 1.1 dry units of
Electricity
Electricity Unit
Unit caustic soda
Pulp and Paper

6% Others
Solvents 38%
4%
Chlorine
Isocyanates
Soda 6%
Epichlorohydrin
5%
Propylene Oxide
7%
Vinyls
34%
24 ~
Fundamentals of Petrochemicals
25 ~
ETHYLENE
C C
Ethylene is also known as ethene. At ambient conditions it is a colorless, flammable gas of the
same density as nitrogen with a slightly sweet odor. It is the lightest olefinic hydrocarbon and the
largest volume building block in the organic chemical industry. Due to the highly reactive nature
of its double bond, ethylene makes an excellent precursor to many different derivatives including
plastics, glycols, pharmaceuticals, fibers and coatings, among many others. Through growth
in its many derivatives, ethylene demand has and will continue to grow at a faster rate than the
economy at large. Ethylene can be produced from many different feedstocks ranging from oil
derivatives (naphtha and gasoil) to gas liquids (ethane, propane, butane and condensates).
Downstream/Derivative Consumption
1. Polyethylenes – LLDPE, LDPE and HDPE
2. Ethylene oxide and glycol
3. Ethylene dichloride
4. Alpha olefins
5. EB/styrene
End-Use Products
Producers rarely invest in ethylene capacity simply for manufacture and sale, but rather as
part of either an overall business strategy aimed at establishing integration for core derivative
businesses and/or leveraging an advantaged feedstock position in a regional market. Regional
merchant markets for ethylene are relatively small when compared to the overall capacity for
consumption, which has inevitable resulted in a highly integrated business.
26 ~
World
2007 Ethylene Demand By Region
Southeast Asia
6%
North America
Northeast Asia 27%
24%
Indian
Subcontinent
3% South America
4%
Middle East
11% West Europe
20%
Africa
1% CIS & Baltic Central Europe
States 2%
2%
Total Demand = 114.0 Million Metric Tons
World
2007 Ethylene Capacity By Region
Southeast Asia
6%
North America
Northeast Asia
28%
22%
Indian
Subcontinent
3%
South America
Middle East 4%
12%
Africa
West Europe
1%
19%
CIS & Baltic Central Europe
States 2%
3%
Total Capacity = 125.2 Million Metric Tons
27 ~
World
2007 Ethylene Demand By Sector
Ethylene Oxide
14%
HDPE
EDC 26%
12%
Ethylbenzene
7%
Alpha Olefins
3%
Others
4% LDPE
17%
Vinyl Acetate
1% LLDPE
16%
Ethylene
Top Producers By Shareholder
2007
Share
Owner
% of World Capacity
Dow 8.23%
SABIC 6.68%
Exxon Mobil Corp. 6.43%
Royal Dutch/Shell 5.20%
SINOPEC 4.05%
Lyondell 3.89%
Ineos 3.61%
Formosa Group 2.84%
Total 2.84%
NOVA Chemicals 2.40%
Total 46.17%
28 ~
PRODUCTION TECHNOLOGIES
• Steam cracking
• Methanol to Olefins (MTO)
• Fischer-Tropsch
• Refinery off-gas
KEY PROCESS – STEAM CRACKING
Fuel Gas
Expander
Demethanizer
Hydrogen
Depropanizer
Cracking
Furnace Ethylene
Compressor
Ethylene
Splitter
Cracking
Furnace
Ethane Quench
Ethane
Propane System
Recycle
Deethanizer
Debutanizer
Butane
Cracking
Fuel Mixed Propylene
Propylene
Naphtha Oil C4's
Splitter
Furnace
Condensate Mixed C4
Gasoil Sales Propane to
Recycle
Pyrolysis
Fractionation
Cracking Gasoline Benzene
Furnace Refined Butadiene
Extraction Aromatics
Butadiene
Extraction Toluene
Raffinate 1
Polyisobutylene Mixed
MTBE Xylenes
MTBE/PIB/Other
Other
Cracking Pygas Sales
Furnace Pyrolysis
Raffinate 2
Gasoline
Gasoline
Process Description
Steam cracking is the primary process for producing olefins, or basic petrochemicals with a
single reactive double bond. Ethylene is the main product of steam cracking, with co-products of
hydrogen, methane, propylene, butylenes and butadiene, pyrolysis gasoline, and various other
olefinic products. After ethylene, the second largest volume product from an ethylene plant is
typically propylene. The production of propylene from “ethylene” plants is so important that the
name “olefin” plant is often preferred for these manufacturing facilities.
The large-scale production of ethylene (and propylene) is carried out in plants that are among
the most complex and expensive facilities of the global hydrocarbon processing industry. Olefins
plants often form the centerpiece of an entire petrochemical complex. Most of the available
olefin production methods are basically similar, indicating the maturity of the technology. Steam
crackers require significant capital investments to incorporate a large number of unit operations:
catalytic and non-catalytic reactions, absorption and adsorption, fractionation, compression, heat
exchange, and phase separation. The result is a high purity ethylene stream and polymer or
chemical grade propylene stream and various other coproduct streams. Ethylene and propylene
29 ~
are generated commercially by pyrolysis (cracking) of paraffinic hydrocarbon feedstocks including

ethane, propane, butane, natural gasoline, condensate, light crude, and the virgin crude oil
fractions of naphtha and atmospheric gas oil. The two most common feedstocks throughout
the world are ethane, primarily due to its high yield of ethylene, and naphtha, because of its
availability and ease of transportation.
Feedstock is first heated in multiple parallel furnaces that have outlet temperatures that approach
850oC or 1,550oF. Thousands of chemical reactions occur in a furnace, but they are typically
initiated by the splitting of carbon-carbon bonds via heat. Other reactions split carbon-hydrogen
bonds. These bond-splitting chemical reactions are commonly referred to as “cracking.”
Molecules recombine forming desired and some undesired products. When this process utilizes
paraffinic feedstocks, the resulting chemical mixture is typically highly olefinic, consisting of double
carbon-carbon bonds, and contains high concentrations of ethylene, propylene, butadiene, and
other olefinic compounds. The co-product yield mix is dependent upon the feedstock and the
furnace cracking severity, a measure of how much of the feedstock molecules are broken apart
in a furnace and how high the temperature reaches within the furnace. Other influences on
yield include time within the furnace, pressures within the furnace, furnace technology, and the
quantity of steam added to the hydrocarbon feedstock within the furnace.
Upon leaving the furnace reaction section as a mixture of olefin gases, the process stream
enters the quench section, where water or heavy oil is used to cool down the gases and quench,
or terminate, the chemical reactions. When the water or oil cools the gases, heat is typically
recovered by producing steam, which is utilized in other parts of the process. At this point, the
hydrocarbon gases need to be liquefied for purification by compressing the gases to very high
pressures and cooling them to very low temperatures. Once the gases are liquefied, they are
moved to the fractionation system and are separated by distillation into the major product streams:
ethylene (C2 olefin), propylene (C3 olefin), crude butadiene (mixed C4 olefins), pyrolysis gasoline
(mixed C5 through C8), and hydrogen/methane fuel gas. Many olefin plants will contain auxiliary
units to further purify some of the co-products, including a propylene splitter to purify propylene,
a butadiene extraction unit to separate 1,3-butadiene and butylenes, and an aromatics extraction
unit to recover benzene, toluene, and xylenes.
30 ~
LOW DENSITY POLYETHYLENE
C C
C C C
C C
C C C C C C C C C C C C C C
... ...
C C
C C
C C C C
The first commercial polyethylene, low density polyethylene (LDPE), was produced nearly 70 years
ago by the polymerization of ethylene (remember from earlier sections: two carbon atoms connected
with a double bond) at high pressures and temperatures. The random radical reaction takes place in
either stirred autoclaves or long tubular reactors and requires neither catalysts nor solvents. Only small
amounts of oxygen or peroxides are needed as initiators to start the radical polymerization reaction.
The reaction is terminated by addition of chain terminators or by the combination of two chains.
The name low density polyethylene refers to its comparably low density range of 0.910-0.935 grams
per cubic centimeter. It is also often called the “branched” polyethylene because the molecular
structure is characterized by the presence of many unsymmetrical branches (some relatively long)
on the chain of carbon atoms. In addition, LDPE is denoted as “high pressure” polyethylene, which
relates to the higher plant operating pressures associated with its common process technology.
Conventional or high pressure low density polyethylene is generally the softest and least
crystalline of the polyethylenes. It is characterized by being easily processable, as well as having
good mechanical, optical, sealable and electrical properties. Therefore, LDPE is widely used in
applications requiring clarity, flexibility, inertness, processing ease and moisture resistance.
In contrast to the other types of polyethylene, LDPE is usually a homopolymer because only
ethylene monomers are used in the polymerization process. The incorporation of comonomers
carrying functional acetate or acrylate groups into the polymer chain enables a further decrease
in crystallinity and an increase in flexibility.
31 ~
1. Film and sheet
2. Extrusion Coating
3. Injection Molding
End-Use Products
1. Shrink film, agricultural film, rubbish bags and packaging
2. Coating of finished packages (i.e. milk cartons)
3. Medical bottles, closures, housewares, toys and industrial items
32 ~
World
2007 Low Density Polyethylene Demand By Region
Southeast Asia
6%
North America
19%
Northeast Asia
27%
South America
7%
Indian
Subcontinent
2%
Middle East West Europe
4% 24%
Africa
CIS & Baltic Central Europe
3%
States 4%
4%
World
2007 Low Density Polyethylene Capacity By Region
Southeast Asia
5%
Northeast Asia North America

24% 21%
Indian
Subcontinent South America
1% 5%
Middle East
6%
Africa
2%
CIS & Baltic West Europe
States 28%
4% Central Europe
4%
33 ~
World
2007 Low Density Polyethylene Demand By Sector
Others
11%
Wire & Cable
4% Film & Sheet
Blow Molding 66%
1%
Extrusion Coating
10%
Pipe & Extrusion

2%
Injection Molding
6%
Low Density Polyethylene

2007
Share
Owner
% of World Capacity
Dow 8.03%
SINOPEC 5.58%
Access Industries 5.32%
Ente Nazionale Idrocarburi 4.03%
Westlake 3.85%
SABIC 3.58%
Lyondell 3.45%
Total 2.60%
DuPont 2.44%
Total 46.15%
34 ~
• Tubular process (e.g. Basell Lupotech T technology)
• Autoclave process (e.g. ExxonMobil technology)
• Others
KEY PROCESS – CONVENTIONAL HIGH PRESSURE TUBULAR PROCESS

Ethylene
Preheater Reactor
Compressor Compressor
Initiator Solvents
Water
Reactor
Cooler Separator Mixture
Ethylene
Decanter
Wax, Oils
Polymer
Cooler
Ethylene Separator
Water
Solvents
Wax, Oils LDPE
Extruder
Polymer
Process Description
Polyethylene with low densities is produced at high pressures in a random free radical reaction
with oxygen or peroxides acting as initiators. The polymerization reaction takes place in high
pressure reactors which can be either long tubular or stirred autoclave.
In a typical high pressure process the ethylene feed is first mixed with a purified recycle stream. In a
next step the initiator and chain transfer agents are added to the mixture, which is then compressed
to a pressure of approximately 300 bar. Then the feed is further compressed to the polymerization
pressure of about 2,000-3,000 bar in a so called hyper-compressor and then fed to the reactor.
After the reaction has taken place (termination achieved by chain terminators or combination of two
chains) the excess of ethylene is removed at the outlet and recycled in some further steps. Finally,
the liquid polyethylene is fed into an extruder and the product is pelletized for shipment.
Due to their broad molecular weight distribution, tubular reactor resins are extensively used in film
applications whereas autoclave resins are better suited for producing materials used in extrusion
coating applications and in the production of ethylene-vinyl acetate copolymers (EVA).
35 ~
HIGH DENSITY POLYETHYLENE
C C C C C C C C C C C C C C
... ...
C
Hexene comonomer
High density polyethylene (HDPE) was commercially introduced in the U.S. in the mid-1950s. In
contrast to low density polyethylene (LDPE), the polymerization of ethylene monomer is carried
out under less extreme conditions of temperature and pressure in the presence of a catalyst
and some kind of hydrocarbon diluent. For this reason it is also referred to as “low pressure”
polyethylene. The reaction follows a co-ordination type mechanism and usually takes place in a
gas phase or slurry. Beside the homopolymer, copolymers are produced by using alpha olefins
such as butene, hexene, and octene as comonomers. Most HDPEs produced are copolymers
with a comonomer content amounting to about 1 to 2 percent.
The polymer is characterized by a more linear molecular structure and little or no side chain
branching. It is more crystalline and has typical densities in the range of 0.94 and 0.965 gram per
cubic centimeter. The density is influenced by the content of comonomer with the highest density
occurring for the homopolymer. The molecular weight distribution varies from narrow to broad
and can be controlled by the choice of catalysts and the use of multiple reactors.
HDPE is a nonpolar polymer of milky white color. Due to its structure it has characteristic
properties such as chemical inertness, good stress crack and impact resistance, dielectric
strength and a relatively high softening temperature. As the density or crystallinity decreases in
the homopolymer or copolymer, an improvement in impact resistance and flexibility occurs; but
chemical resistance, processable temperature range and resistance to water vapor permeation
are diminished.
36 ~
1. Film and sheet
2. Blow molding
3. Injection molding
End-Use Products
1. Grocery and merchandise bags
2. Milk Bottles, liquid detergent bottles, industrial drums, oil bottles and gas tanks
3. Housewares (pails, totes, crates, baskets, caps and closures)
37 ~
World
2007 High Density Polyethylene Demand By Region
Northeast Asia
26% Southeast Asia
8%
Indian
Subcontinent
4%
Middle East North America
5% 26%
Africa
3%
CIS & Baltic

States
2% South America
West Europe 6%
Central Europe 18%
2%
World
2007 High Density Polyethylene Capacity By Region
Southeast Asia
8%
North America
28%
Northeast Asia
20%
Indian
3% 5%
Middle East
West Europe
12%
16%
Africa Central Europe
2% CIS & Baltic 3%
States
3%
38 ~
World
2007 High Density Polyethylene Demand By Sector
Others
Raffia 9%
3% Film & Sheet
Fiber 24%
2%
Rotomolding
1%
Wire & Cable

1%
Blow Molding
26%
Injection Molding
21%
Pipe & Extrusion

13%
High Density Polyethylene

2007
Share
Owner
% of World Capacity

Ineos 6.27%
Dow 5.45%
SABIC 5.21%
Total 4.27%
Lyondell 3.95%
SINOPEC 3.60%
Formosa Group 3.59%
Chevron Corp. 3.22%
ConocoPhillips 3.22%
Total 50.07%
39 ~
• Gas phase process (e.g. Basell Spherilene technology)
• Ziegler process using Ziegler-Natta catalysts (e.g. Basell Hostalen technology)
• Particle Form (PF) loop process (e.g. Chevron Phillips technology)
• Solution process (e.g. Nova Sclairtech technology)
• Others
KEY PROCESS – CHEVRON PHILLIPS LOOP SLURRY PROCESS
Fresh
Diluent
Treater
Catalyst
Recycle Loop Reactor
To Ethylene
Diluent Recovery
Compressor
Fractionator
Treater Flash Chamber Accum
Ethylene
To Diluent
Recovery
Treater
Co-Monomer Purge Column Bin
Make-up H2 To Flare Vent
Treater Bin
Vent
Pellet Water Pellet
Additives
Blender Classifier
Bulk
Dryer Product
Nitrogen Extruder Bagger Weigh
Feed X Hopper
Hopper X X
Pellet Water
Sump
Bagger
Process Description
Monomer and comonomer are continuously fed with catalyst and diluent into large polymerization
reactors. The reaction takes place in slurry with temperatures ranging between 80oC and 110oC
and pressures below 50 bar. After the reaction the polymer slurry is discharged from the reactor and
sent to a flash tank. Polymer, diluent, and any unreacted ethylene are separated at this stage.
In the next step the polyethylene powder is transferred to an extruder for the incorporation of
additives, melt mixing and subsequent pelletization. Finally, the pelletized product is sent to
storage tanks for blending prior to bagging or hopper car loading.
40 ~
The Chevron Phillips Loop Slurry process is one of the most common processes used to produce
low pressure polyethylene with high densities. Within this process the polymerization of ethylene
is usually carried out in the presence of chromium catalysts with hexane-1 acting as comonomer.
The replacement of chromium by Ziegler catalysts is also possible. It enables an extension of the
grade slate but also causes higher operating costs. The loop slurry process is used extensively
in the production of resins for blow molding and other extrusion applications (i.e. pipe).
41 ~
LINEAR LOW DENSITY POLYETHYLENE
C C
C C
C C C C C C C C C C C C C
... ...
C
As the youngest member in the polyethylene family, linear low density polyethylene (LLDPE)
was first developed in the 1970s and became widely used in the 1980s, especially in the U.S.
It is produced under the same low pressure conditions as high density polyethylene (HDPE)
but using different comonomers and catalysts. Therefore, it is no surprise that a great amount
of LLDPE is produced in so-called “swing plants”, where a switch from one catalyst to another
enables the production of either LLDPE or HDPE.
LLDPE has a linear molecular structure with a comparably high number of short sided chain
branches along the polymer backbone. In comparison to HDPE, the content of comonomers
is larger and amounts to about 8 to 10 percent. As we have seen with LDPE in the previous
section, the density as well as the crystallinity decreases with increasing amounts of incorporated
comonomer. Therefore, LDPE is characterized by densities lower than 0.940 grams per cubic
centimeter. When the density falls below 0.915 grams per cubic centimeter, the material is
classified as very low density (VLDPE) or ultra low density (ULDPE). Due to its regular molecular
structure, LLDPE is more crystalline and therefore harder to process than conventional LDPE of
the same density.
When compared with LDPE, LLDPE resins exhibit significantly improved tensile, impact and tear
properties, as well as excellent low and high temperature characteristics. As a consequence it
has found its way into many film applications for LDPE, replacing the traditional polyethylene.
While LLDPE does not have the clarity of LDPE, blending both these polyethylenes leads to an
improvement in strength, stiffness and puncture resistance while keeping the clarity. ULDPE is
also used as a blending resin and an impact modifier for PP and HDPE.
42 ~
1. Film and sheet
2. Injection molding
3. Rotomolding
End-Use Products
1. Shrink and stretch wrap, trash can liners
2. Housewares, lids, toys
3. Larger items for outdoor uses (park benches, playground and sporting equipment, planters
and trash receptacles)
43 ~
World
2007 Linear Low Density Polyethylene Demand By Region
Northeast Asia
29% Southeast Asia
8%
Indian
Subcontinent
6%
North America
Middle East
25%
4%
Africa
3%
CIS & Baltic South America

States West Europe 6%
<1% Central Europe 18%
1%
World
2007 Linear Low Density Polyethylene Capacity By Region
Southeast Asia
8%
North America
Northeast Asia 29%
20%
Indian
Subcontinent
4% South America
6%
Middle East
13%
West Europe
Africa CIS & Baltic 18%
2% States
<1%
44 ~
World
2007 Linear Low Density Polyethylene Demand By Sector
Others
10%
Rotomolding
3%
Film & Sheet
Wire & Cable 75%
2%
Extrusion Coating
<1%
Pipe & Extrusion

2%
Injection Molding
8%
Linear Low Density Polyethylene

2007
Share
Owner
% of World Capacity
Dow 20.65%
SABIC 6.30%
SINOPEC 5.41%
China National Petroleum Corp. 2.60%
Abu Dhabi Government 2.56%
Ineos 2.54%
Formosa Group 2.39%
Total 61.63%
45 ~
• Gas phase process (e.g. Univation Unipol technology)
• Solution process (e.g. Nova Sclairtech technology)
• Others (e.g. Chevron Phillips loop slurry process)
KEY PROCESS – UNIVATION UNIPOL PROCESS
Catalyst Comonomer
Vent
Catalyst Cooler Separator
Filter
Feed
Tank
Cooling
Water Polymerization Condenser Refrig.
(C.W) Reactor
C.W.
Recycle Blower Cooler
Nitrogen
Oxygen/
Ethylene Water
Removal Product
Cooler Degassing Purge
Heater Tanks
Tower
Comonomer Guard
Bed Nitrogen
Steam
Degasser Cooler Steam

C.W.
Hydrogen Polymer Powder
Process Description
The reactor in a gas phase process can be set up to operate with a variety of catalysts and comonomers
so that different grades of polyethylene can be produced in the same unit. The best performance
of this process is achieved by using butene-1 comonomers and Ziegler (titanium) catalysts which
give linear low density polyethylene as product, but it can also be used to produce high density
polyethylene by changing to hexene-1 comonomers and chromium catalysts (swing process).
The polymerization of ethylene is carried out in a fluidized bed reactor at temperatures in the 80oC
to 90oC range and pressures less than 25 bar. Supported titanium catalyst is continually added
to the reactor as product granules are being continuously withdrawn. In the narrow vertical neck,
an ethylene/comonomer gas stream bubbles up through a bed of growing polymer particles. The
gas stream is recirculated through the external coolers to remove reaction heat and the exiting
granular product is purged of monomers and sent directly to product storage and pelletizing.
46 ~
It was discovered that the fluidizing gas stream could contain a proportion of entrained liquid
droplets without impairing the reaction. This means that the recirculated gas stream can be sub-
cooled below its dew point, greatly increasing the heat removal capabilities of the system. With
that the output of older gas phase reactors was greatly increased (potentially doubled) for a small
capital outlay.
Sub-cooling the reactor feed has also opened up new applications. The sub-cooling allows use
of hexene-1 comonomer without a production penalty. Materials that require a lower reactor
operating temperature can now be made.
47 ~
ETHYLENE OXIDE / ETHYLENE GLYCOL
C C
Ethylene oxide (oxirane) was first prepared by Wurtz in 1859 by the reaction of 2-chloroethanol
(ethylene chlorohydrin) with aqueous potassium hydroxide. Ethylene oxide (EOX) is a highly
reactive, colorless, low-boiling liquid or gas with an ether-like odor. It is miscible in all proportions
with water, alcohol, ether and most organic solvents. EOX is an important intermediate for the
production of ethylene glycols, ethanolamines, glycol ethers and a wide range of surface active
agents (ethoxylates). Due to EOX’s high reactivity and the resulting danger of explosion, many
EOX derivatives are produced at the same site as ethylene oxide. The major exception is the
production of surfactants by independent ethoxylators.
C C
O O
Monoethylene glycol (MEG) is by far the dominant derivative of ethylene oxide. MEG has two
principal applications: polyethylene terephthalate resins for fiber, film and bottle/engineering
resins (PET) and automotive antifreeze/coolant. The latter is a much smaller proportion of overall
EO derivative demand. Monoethylene glycol and co-produced di- and tri-ethylene glycols are
colorless, odorless, high boiling, hydroscopic liquids that are completely miscible with water and
many organic liquids. Ethylene glycols markedly reduce the freezing point of water.
48 ~
1. Ethylene Oxide
2. Monoethylene glycol
3. Ethanolamines
4. Di/Tri/Poly ethylene glycol
5. Glycol Ethers
6. Ethoxylates
7. Polyols
8. Ethylene glycol
9. Antifreeze
10. Polyester Melt
11. Misc. Industrial Applications
End-Use Products
1. Ethanolamines
Used in a wide variety of applications, the largest of which is in aqueous solutions for
scrubbing certain acidic gases.
2. Di/Tri/Poly ethylene glycol

Diethylene glycol is used as a coolant. When added to water the freezing point is lowered and
the boiling point is elevated in the solution. It is also used for a variety of other applications
including hydraulic and brake fluids and personal care products.
Triethylene glycol is used as a plasticizer for vinyl. It is also used in aerosol products as
a disinfectant. As with diethylene glycol, triethylene glycol is used in hydraulic and brake
fluids.
3. Glycol Ethers
The glycol ethers produced using ethylene oxide are typically used as solvents, which are
then dissolved into a wide variety of chemical compounds including oils, resins and grease.
2-Ethoxyethanol is sold under the trademark of Cellosolve.
4. Ethoxylates
5. Polyols
49 ~
World
2007 Ethylene Oxide Demand By Region
Southeast Asia
5%
North America
26%
Northeast Asia
26%
South America
2%
Indian
Subcontinent West Europe
4% 14%
Middle East
19% Central Europe
CIS & Baltic 1%
States
3%
World
2007 Ethylene Oxide Capacity By Region
Southeast Asia
Northeast Asia 5%
26%
North America
Indian 26%
Subcontinent
4%
Middle East
18% South America
2%
CIS & Baltic
States West Europe
3% Central Europe 15%
1%
50 ~
World
2007 Ethylene Oxide Demand By Sector
Polyols Others
2% 1%
Ethoxylates
13%
Glycol Ethers
3%
Ethanolamines
6%
PEG
1%
TEG DEG
1% 6% MEG
67%

Ethylene Oxide
2007
Share
Owner
% of World Capacity
Dow 12.59%
SABIC 9.09%
Formosa Group 6.41%
BASF AG 5.51%
SINOPEC 4.39%
Ineos 4.33%
Reliance Industries 3.42%
Japanese MEG Consortium 2.75%
Kuwait Government 2.47%
Total 57.16%
51 ~
World
2007 Ethylene Glycol Demand By Region
Indian
Middle East Subcontinent
3% 7%
Africa
1% Northeast Asia
CIS & Baltic 51%
States
2%
Central Europe
1%
West Europe
10%
South America
2%
North America
16% Southeast Asia
7%
World
2007 Ethylene Glycol Capacity By Region
Southeast Asia
5%
North America
24%
Northeast Asia
30%
South America
2%
West Europe
8%
Central Europe
Indian 1%
Subcontinent CIS & Baltic
5% States
Middle East 2%
23%
52 ~
World
2007 Ethylene Glycol Demand By Sector
Antifreeze
8%
Industrial & Misc.

4% Polyester Melt
88%

Ethylene Glycol
2007
Share
Owner
% of World Capacity
SABIC 11.81%
Dow 11.57%
Formosa Group 8.10%
SINOPEC 5.28%
Japanese MEG Consortium 3.48%
Kuwait Government 3.28%
BASF AG 2.73%
Ineos 2.60%
Total 58.92%
53 ~
KEY PROCESS – DIRECT OXIDATION
Ethylene Make-up Process Water

Recycle Gas Carbon Dioxide
Oxygen
Carbon Dioxide EG
Removal Feed Tank
Reactor
Steam
EO/Water Mixture
Recycle Water
Hydration Reactor Light Ends
Multiple Stage Evaporator Crude

EG's Vacuum Distillation
DEG &
TEG
Recycle Water Residue
Process Description
Although there are several technologies available for the production of ethylene oxide and
ethylene glycols, the basic technology is similar throughout. The following paragraphs are a
description of an oxygen-based Scientific Design ethylene oxide process with an accompanying
Scientific Design ethylene glycols unit. Many Scientific Design plants do not have EO purification
and are therefore viewed essentially, as ethylene to monoethylene glycol units.
In the Scientific Design EO process, compressed oxygen, ethylene and recycled gas are mixed
and fed to a multi-tubular catalytic reactor. Boiling water in the shell side of the reactor controls
the reaction temperature. From the reactor, the effluent gases, which contain EO, are cooled and
compressed. The cooling is accomplished by cross exchanging the reactor effluent with recycled
gases. The cooled reactor effluent then passes to a scrubber where EO is absorbed as a dilute
aqueous solution. Recycle gas is compressed and returned to the reactor with a portion drawn
off and diverted through a carbon dioxide removal system. Ethylene oxide is steam stripped from
the ethylene oxide-rich absorber bottoms and fed directly to an adjoining ethylene glycols unit or
purified in a fractionation train for merchant sale as EO or into other derivatives production.
In the ethylene glycol production process, ethylene oxide and make-up process water are
mixed with recycled water in the feed tank and pumped through heat exchange to the hydration
reactor. In the glycols reactor, there is no catalyst, but sufficient residence time is provided
to react all of the ethylene oxide with excess water. A mixture of mono-, di-, tri- and higher
substituted glycols is produced and sent on to purification. It should be noted that there have
been recent developments and deployment of a process called Meteor, developed and licensed
by Union carbide. This technology catalytically improves the selectivity of the reaction to MEG
and minimizes the production of higher substituted glycols.
54 ~
The water-glycol mixture from the reactor is fed to the first stage of a multiple stage evaporator,
which re-boils the mixture using high-pressure steam. The remaining stages of the evaporator
separate the water-glycols mixture at successively lower pressures, with the final stage normally
under vacuum. The water out of the evaporator overhead is recovered as condensate and
recycled back to the ethylene glycols feed tank.
The crude glycols solution from the final evaporation stage is then stripped of remaining water
and light ends in the light ends column. The water-free glycols mixture is then fractionated in a
series of vacuum distillation towers to produce purified monoethylene glycol and co-products,
di-ethylene glycol and tri-ethylene glycol.
55 ~
PROPYLENE
C C
Propylene, also known as propene, is a colorless, flammable gas that is typically shipped in a
highly pressurized or refrigerated liquefied form. It has anesthetic properties and is classified as
a simple asphyxiant that can cause unconsciousness. Propylene trades in three forms: refinery
grade (RG; 65-80 percent purity), chemical grade (CG; 94-97 percent purity) and polymer grade
(PG; > 99.5 percent purity). It is one of the largest basic petrochemical intermediates after
ethylene, and is generally produced as either a by-product of ethylene in steam crackers or
from gasoline/distillates in the FCC unit of an oil refinery. The primary end-use is for the polymer
polypropylene, accounting for about 55 percent of the world consumption of propylene. Since
polypropylene demand has grown at high rates due to substitution for other higher cost polymers
and natural materials, propylene demand growth historically outpaced economic growth and
most other major commodity basic chemicals.
1. Polypropylene
2. Acrylonitrile
3. Propylene oxide
4. Cumene
5. Oxo-alcohol
End-Use Products
There is a significant merchant market for propylene globally. Most propylene is transacted based
on long-term (2-4 year) contracts between buyers and sellers. Contract pricing is negotiated
monthly in the U.S. and quarterly in Europe. In order to establish a contract price, most other
regions in the world utilize the U.S. and/or European contract prices along with local spot pricing.
Since propylene is a gas or high-pressure liquid, it is expensive to transport to customers. Most
propylene is consumed by on-site or adjacent derivative plants. Some propylene is transported
by pipeline, ship, barge, railcar and truck.
56 ~
World
2007 Propylene RG Demand By Region
Southeast Asia
4%
Northeast Asia
22%
North America
42%
Indian
Subcontinent
6%
Middle East
2%
Africa
<1%
CIS & Baltic
States South America
1% Central Europe West Europe 5%
2% 16%
World
2007 Propylene RG Capacity By Region
Southeast Asia
3%
Northeast Asia
24%
North America
43%
Indian
Subcontinent
4%
Middle East
2%
Africa
<1%
CIS & Baltic
States
1% South America
Central Europe West Europe
5%
2% 16%
57 ~
World
2007 Propylene RG Demand By Sector
FCC Splitters Cumene

86% 6%
Isopropanol
3%
Oligomers
5%

Propylene: Refinery Grade
2007
Share
Owner
% of World Capacity

Valero 6.07%
BP 5.49%
SINOPEC 4.50%
Total 4.14%
Nippon Petroleum Refining 3.66%
Total 52.82%
58 ~
World
2007 Propylene PG/CG Demand By Region
Northeast Asia Southeast Asia

34% 6%
Indian
Subcontinent
3%
North America
Middle East
23%
4%
Africa
1%
South America
CIS & Baltic 4%
States West Europe
2%
World
2007 Propylene PG/CG Capacity By Region
Southeast Asia
6%
Northeast Asia
28%
North America
26%
Indian
Subcontinent
3%
Middle East South America
5% 4%
Africa
2%
West Europe
CIS & Baltic 21%
Central Europe
States
2%
3%
59 ~
World
2007 Propylene PG/CG Demand By Sector
2-Ethyl Hexanol Butanols

4% 4%
Isopropanol
1%
Cumene
4%
Polypropylene
65%
Acrylonitrile
8%
Acrylic Acid
4%
Others
2%
Propylene Oxide
8%
Propylene: Polymer/Chemical Grade

2007
Share
Owner
% of World Capacity

SINOPEC 5.22%
Total 4.10%
Dow 4.06%
Lyondell 3.70%
Formosa Group 3.40%
Ineos 2.88%
SABIC 2.72%
Total 40.07%
60 ~
• Steam cracking
• FCC unit
• Crude oil refinery
• Propane dehydrogenation
• Metathesis
KEY PROCESS – FCC UNIT

Amine
Wet Gas Treating
Compressor
Dry
A
Riser Gas
b
s
Reactor Refinery
o
r Grade
Separation
Drum b Propylene
e
Flue Gas r
D
e
p
D LPG r
Main e
S Caustic/ o
Light b
Regenerator Frac t Amine p
Cycle u
r Treater a
Oil t
i n
a
p i
n
p z
i
e e
Air z
r r
e
r
Residue Mixed
Gas Oil Feed
Butylenes
Motor
Gasoline/ C4+
Naphtha
Process Description
Almost all propylene is generated by steam crackers or by FCC units in refineries. There are three
grades of propylene that are consumed by the chemical industry: Polymer Grade (99.5+ percent
purity), Chemical Grade (94-97 percent purity), and Refinery Grade (65-80 percent purity).
A steam cracker’s primary function is to make ethylene. Therefore, propylene is considered a by-
product of ethylene. Feedstocks to a steam cracker include ethane, propane, butane, naphtha,
condensate, and gasoil. The two most common feedstocks are ethane and naphtha. Ethylene
and propylene yields (on feed) for ethane feedstock are 78 percent and 3 percent respectively.
Ethylene and propylene yields (on feed) for naphtha feedstock are 32 percent and 16 percent,
respectively. Propylene production from steam crackers is usually either polymer grade or
chemical grade. A world-scale naphtha-based steam cracker has a capacity of 550,000 metric
tons per year of ethylene and 225,000 metric tons per year of propylene, with a capital cost of
about US$600 million.
61 ~
An oil refinery FCC unit’s primary function is to make motor gasoline. Therefore, propylene is
considered a by-product of gasoline. Feedstocks to an FCC units are generally atmospheric
and vacuum gas oils. Gasoline and propylene yields (on feed) for a typical FCC unit are 60
percent and 4 percent, respectively. Certain catalyst additives can be utilized in FCC units to
increase propylene yield while decreasing gasoline yield. Propylene production from an FCC
unit is usually refinery grade. Refineries often consume propylene internally to make alkylate
(a type of motor gasoline) or to make LPG (a saleable heating fuel). Refinery grade propylene
can be upgraded to polymer or chemical grade propylene through the addition of a propylene
purification splitter (distillation column). A world-scale FCC unit has a capacity of 40,000 barrels
per day of gasoil throughput and 75,000 metric tons per year of propylene production, with a
capital cost of about US$200 million.
62 ~
POLYPROPYLENE
C C C C
C
... ...
Polypropylene is a thermoplastic polymer and can be produced as a homopolymer, random

copolymer or heterophasic copolymer. It is characterized by high stiffness, good clarity, low
density, chemical resistance and relatively high temperature resistance; however, it has poor
impact resistance, especially at low temperatures.
Polypropylene homopolymer can be produced in three forms:
• Isotactic polypropylene: has a highly crystalline structure that gives the polymer stiffness,
good tensile strength and resistance to acids, alkalis and solvents.
• Syndiotactic polypropylene: has low crystallinity and is difficult to make. Some syndiotactic
polypropylene has been made recently using a metallocene catalyst; however, no significant
commercial use for this polymer has yet been identified.
• Atactic polypropylene: is a non-crystalline polymer that is too soft and rubbery for most
applications. It is similar in appearance and properties to an uncured elastomer. In its
production, some atactic polypropylene is also made as a by-product. One of the main
objectives in the polypropylene production process is to keep the atactic component of the
polypropylene to a minimum, which has generally been accomplished using high activity
catalysts. Some atactic polypropylene is produced on dedicated lines and is sold for use in
hot melt adhesives, roofing and other specialized applications or incinerated.
Polypropylene random copolymers were developed to improve homopolymer properties for certain
applications. Random copolymers have ethylene molecules inserted, as the name suggests,
randomly between the propylene molecules in the polymer chain. Random copolymers have
higher impact resistance, higher clarity and more flexibility than homopolymers. The ethylene
content is typically 2-4 percent by weight.
Heterophasic copolymers, sometimes referred to as impact copolymers, are composed of a

string of propylene molecules, periodically interrupted by strings of ethylene-propylene rubber or
polyethylene. Impact copolymers have better impact strength at lower temperatures, as well as
higher melting points, than random copolymer.
63 ~
1. Injection molding, fiber and filaments
2. Blow-molding
3. Film and sheet
End-Use Products
1. Production of caps and closures, containers for rigid packaging, appliances, consumer
products, medical products, auto parts and household containers
2. Fabrics and carpets (carpet backing and face yarn) as well as disposable applications and
geotextiles
3. Manufacture of containers
4. Packaging
64 ~
World
2007 Polypropylene Demand By Region
Northeast Asia
34%
Southeast Asia
7%
Indian
Subcontinent North America
5% 17%
Middle East
6%
Africa
3% South America
5%
States Central Europe 19%
1% 3%
World
2007 Polypropylene Capacity By Region
Southeast Asia
8%
Northeast Asia
31%
North America
20%
Indian
Subcontinent
4%
Middle East
South America
6%
5%
Africa
1%
West Europe
CIS & Baltic Central Europe 20%
States 3%
2%
65 ~
World
2007 Polypropylene Demand By Sector
Others
8%
Film & Sheet
Raffia 22%
14%
Fiber
15%
Blow Molding
1%
Extrusion Coating Injection Molding

<1% Pipe & Extrusion 37%
3%
Polypropylene
2007
Share
Owner
% of World Capacity

SINOPEC 7.45%
Total 5.07%
Ineos 5.01%
SABIC 3.70%
Formosa Group 3.49%
Abu Dhabi Government 2.48%
Total 50.61%
66 ~
• Gas phase process
• Liquid/gas phase combination process
• Bulk slurry process with liquid propylene
• Slurry process with saturated liquid hydrocarbon
KEY PROCESS – BASELL SPHERIPOL PROCESS
Comonomer and Donor

Catalyst Polymerization Reactors Monomer
Condenser
Prepolymerizer
Recycle Monomer
Jacket Jacket Recycle

Water Water Hydrogen Cooler
Degasser
Cooler Cooler
Catalyst Ethylene
Injection Pump Pump
Monomer
Recycle
Pump Propylene
Heater To Recovery
PG Propylene Recycle
Pump Vent Purge
Recovery To Flare Impact
Dryer
Hold System Copolymer
Tank Reactor Recycle
Blower
Monomer Recovery
Reactor Compressor
Feed Pump
Condensate Steam
To Waste LP Flash
Nitrogen Drum
Pelletizing Nitrogen
Process Description
The Basell Spheripol process combines the bulk slurry reactor for producing homopolymers
with the fluidized bed gas phase reactor for block copolymers. Catalyst is injected into a pre-
polymerization loop, along with other co-catalysts, to initiate the polymerization process. The
components are mixed in this prepolymerizer and then injected into the polymerization loop
reactors, along with fresh and recycled propylene and hydrogen. The reactors operate at 65oC
to 80oC and at pressures less than 40 bars. Two reactors in series are used for larger capacity
plants. The polymer slurry is withdrawn from the second reactor and flashed into a high pressure
degasser where the polypropylene homopolymer powder is separated from the liquid monomer.
When making impact copolymers, the powder from the degasser, along with ethylene and
additional propylene, is fed into the gas phase fluidized bed reactor that operates at about 70oC
and less than 15 bars. The impact copolymer is recovered from the reactor output by utilizing a
flash system to separate the polymer powder from the monomer. For higher impact copolymers,
67 ~
a second gas phase reactor may be used to raise the level of ethylene in the polymer or ethylene
propylene diene monomer (EPDM) may be blended into the final product. The polymer is then
transferred to finishing for inclusion of additives and pelletizing.
During the finishing step, the reactor product is converted to a wider variety of pelletized resins
tailored for specific applications. Modifications to polymer crystallinity and melt flow can occur
through the use of special additives.
• Peroxide is used to make “controlled rheology” (CR) resins that have increased melt flow, but
with the physical properties of a lower melt flow material such as toughness. CR resins are
used in some injection molding and fibers applications.
• A nucleating agent or additive can be used to improve the stiffness and clarity of the polymers.
Some clarified polypropylene materials are replacing other transparent materials in injection
molding and injection-blow molding parts.
68 ~
BUTADIENE
C C C C
Butadiene is a 4-carbon di-olefin generally produced as a by-product from an ethylene steam

cracker. The butadiene industry began on a commercial scale in the early 1940s, when the U.S.
government built several butadiene-producing plants to feed the developing synthetic rubber
industry. To this day, the majority of butadiene produced globally ends up in the synthetic rubber
industry. It is also used in the production of synthetic latex, synthetic fiber and thermoplastics.
Over 95 percent of global butadiene is produced by the extractive distillation of crude C4 streams
produced as a co-product of ethylene production. The remainder of production is on-purpose via
the dehydrogenation of normal butane or butenes; however, production via the on-purpose route is
less economical than production via extractive distillation.
The crude C4 stream from ethylene production also contains butylenes (4-carbon olefins) and butanes.
After the removal of butadiene from the stream, the remaining stream, called raffinate-1, is used in
the production of gasoline blending components and other chemicals. Rather than extracting the
butadiene from a crude C4 stream, ethylene producers can also co-crack their crude C4 streams, in
other words recycle them as a feed to the steam cracker, or hydrogenate them to produce butane.
1. Synthetic rubber/latex
2. Polybutadiene rubber
3. Nitrile rubber
4. Polychloroprene (neoprene)
5. Adiponitrile
6. Acrlyonitrile butadiene styrene
7. Thermoplastic elastomers
69 ~
End-Use Products
1. Tires
2. Belts
3. Hoses
4. Other rubber parts
5. Synthetic fibers
6. Coated paper
7. Carpet
8. Appliance shells
9. Electronic housings
70 ~
World
2007 Butadiene Demand By Region
Southeast Asia
Northeast Asia 4%
38%
North America
Indian 23%
Subcontinent
1%
Middle East
1%
Africa South America
1% 4%

States 21%
Central Europe
5%
2%
World
2007 Butadiene Capacity By Region
Southeast Asia
2%
Northeast Asia
35%
North America
25%
Indian
Subcontinent
3% South America
3%
Middle East
3%
States 20%
6% Central Europe
3%
71 ~
World
2007 Butadiene Demand By Sector
Others ABS Resins
10% 13%
Adiponitrile
6% Polychloroprene
Rubber
1%
Nitrile Rubber
S.B. Rubber 4%
28%
Polybutadiene
26%
S.B. Latex
12%
Butadiene
2007
Share
Owner
% of World Capacity
Texas Petrochemicals 8.38%

SINOPEC 7.02%
Lyondell 4.67%
Ineos 4.02%
SABIC 3.09%
JSR 2.86%
Formosa Group 2.70%
Total 47.30%
72 ~
• Extractive Distillation
• Dehydrogenation of N-Butane
• Dehydrogenation of N-Butenes
KEY PROCESS – EXTRACTIVE DISTILLATION OF STEAM CRACKER C4S
Butylenes
C4 Acetylenes
Water C3 Acetylenes
1,3 BUTADIENE
MAIN WASHER
DEGASSER
AFTER WASH
RECTIFIER DISTILLATION COLUMNS
Water
1,2 BUTADIENE
& C5
Crude C4's
Heat exchangers
Process Description
There are two sources of butadiene in the world: extractive distillation from crude C4 streams
produced as a co-product of ethylene production, and “on-purpose” production by dehydrogenation
of n-butane or n-butenes.
Roughly 96 percent of the world’s butadiene is produced via extractive distillation. Extractive
distillation technology is highly developed and has been improved over the years to employ new,
more effective solvents which minimize utility requirements and lower capital costs.
The BASF butadiene extraction technology (shown in above schematic) was first commercialized
in 1968. Feedstock for the process is preferably the crude C4 stream from an ethylene steam
cracker. The two-stage extractive distillation process operates at pressures of 4-5 atm and utilizes
aqueous n-methyl-2-pyrrolidone (NMP) as a solvent.
73 ~
The first extractive distillation stage consists of three steps: absorption, rectification, and solvent
regeneration. The overhead stream from the absorption tower consists of butylenes and a very
small amount of butadiene. These streams, designated as raffinate-1 (Raff-1), go on to producers
of polyisobutylene, MTBE or C4 alkylate. The butadiene rich bottoms stream from absorption,
containing some butylenes and acetylenes, goes to a rectification step (stripping column) where
the more volatile butylenes are stripped out and recycled back to the absorption tower. Butadiene
and acetylenes are removed as a side stream from the rectifier and sent to the second stage of
extractive distillation.
The bottoms stream from the rectifier is sent to the third step of the first extractive distillation
stage-solvent regeneration. The regeneration step is operated at low pressure using three
different packed beds within the tower. This process minimizes polymer formation but does
require a compression step of the overhead vapor stream, which is recycled back to the rectifier
as the reboil stream.
74 ~
BENZENE
C C
C C
Benzene was first isolated in 1825 by Michael Faraday and elemental analysis showed that the
compound had a hydrogen to carbon ratio of 1:1. Further work by Eilhard Mitscherlich determined
that the molecular formula for benzene was C6H6 (six carbons and six hydrogens). Benzene is a
colorless, inflammable liquid (at temperatures between 5.5oC-80.1oC) with a sweet paint thinner-
like odor.
Benzene’s physical characteristics make it valuable in the gasoline pool and thus a major
component of gasoline, while benzene’s double bonded nature is susceptible to some useful
chemical reactions to make it a precursor for several other industrial chemicals. Hence, demand
is driven by both the chemical industry and the need to maintain the gasoline pool at a proper
level and composition. It should be noted that concerns over the impact of benzene and heavier
aromatics in the gasoline pool creating more emissions when used as a motor vehicle fuel has
led to the reduction of their use; thus, more molecules are becoming available for use within the
chemical industry.
Prior to World War II the only source of aromatic raw materials such as benzene involved the
fractional distillation of light oils formed as a by-product in the destructive distillation of coal
for coke production. The other four significant sources of benzene are: reformate extraction,
hydrodealkylation of toluene, disproportionation of toluene and extraction from pyrolysis
gasoline.
1. Organics: cumene into phenol, ethylbenzene into styrene, cyclohexane into caprolactam,
nitrobenzene into aniline, and maleic anhydride
2. Others: fuel and solvent markets
End-Use Products
Benzene is used to make fuel and is also a precursor to other chemicals that produce end-
products such as disposable dinnerware, adhesives, fibers (carpet) and translucent media
(compact discs and DVDs).
75 ~
World
2007 Benzene Demand By Region
Northeast Asia
37%
Southeast Asia
Indian 5%
Subcontinent
2%
Middle East
3%
North America
CIS & Baltic 24%
States
3%
Central Europe
2% South America
2%
West Europe
22%
World
2007 Benzene Capacity By Region
Southeast Asia
Northeast Asia 5%
33%
North America
22%
Indian
Subcontinent
3%
Middle East
5% South America
Africa
3%
<1%

States 21%
Central Europe
5%
3%
76 ~
World
2007 Benzene Demand By Sector
Ethylbenzene Maleic Anhydride

53% 2%
Nitrobenzene
8%
Others
2%
Alkylbenzene
3%
Chlorobenzene
1%
Cumene
Cyclohexane 19%
12%

Benzene
2007
Share
Owner
% of World Capacity

SINOPEC 5.04%
Total 4.63%
Dow 4.19%
BP 2.84%
SABIC 2.60%
Lyondell 2.40%
Total 39.65%
77 ~
TECHNOLOGY OVERVIEW FOR AROMATICS
Prior to World War II, the only source of aromatic raw materials involved the fractional distillation
of light oils formed as a by-product in the destructive distillation of coal for coke production.
Technology advancements have since paved the way for production of light aromatic hydrocarbons
– benzene, toluene and xylenes (BTX) – from catalytic reforming of naphtha or from extraction of
pyrolysis gasoline (pygas).
Catalytic reforming produces gasoline components with a high octane number, and the process
is also a major source of hydrogen. During catalytic reformation, dehydrogenation of naphthenes
(aromatization) and cyclization of paraffins create a resultant BTX fraction (reformate) which
consists of significantly more toluene and xylenes than benzene.
A substantial fraction of pygas is produced as a co-product when feeding a naphtha or gas oil
feedstock to the steam cracker of an olefins plant. Within the BTX portion, pygas is normally
much richer in benzene than reformate and considerably less rich in xylenes. In general, pyrolysis
gasoline tends to be richer in total BTX than reformate.
There are also processes which convert one aromatic form to another, such as hydrodealkylation
of toluene where toluene and hydrogen are dealkylated by passing over a catalyst to yield
benzene and methane as well as disproportionation of toluene which converts two molecules
of toluene into one molecule each of benzene and xylene. The majority of mixed xylenes may
be processed further to produce one or more of the individual isomers, and can also be sourced
from transalkylation of heavy aromatics.
Raffinate
Benzene
Product
Benzene
Fract.
Pygas Cyclohexane Cyclohexane
Extraction Clay Unit Product
Treating
C7 - Benzene
Toluene Toluene
Disproportion
Light Unit
Para-Xylene Rich A 8's
Reformate
Splitter
Reformer Para-Xylene P-Xylene
Product
CCR Recovery
C8+ C8+ Isomerization C7- to

Desulfurized Unit Extraction
Naphtha
Clay
Naphtha Treating
Hydrotreater O-Xylene
Product
Clay
Treating Ortho-
Xylenes
Splitter Xylene
Rerun
Naphtha
Heavy
Aromatics
78 ~
CATALYTIC REFORMING
The main reactions of catalytic reforming are shown below:
AROMATICS
Alkylcyclohexane
Pt dehydrogenation
Cycloparaffin
isomerization
ALKYLCYCLO ALKYLCYCLO-
PENTANES HEXANES
Pt, Acid
Platinum (Pt), Acid
ISOPARAFFINS n - PARAFFINS
Paraffin
isomerization
Pt, Acid Pt, Acid
Hydrocracking Hydrocracking
CRACKED
PRODUCTS
Feedstocks of straight-run naphtha and other feeds in the gasoline boiling range are combined
with recycle hydrogen, heated to reaction temperature by heat exchangers and fired heaters
before being charged to the reactors. All reactions that occur during catalytic reforming, except for
isomerization, are moderately to highly endothermic, hence reactions occur at several reactors.
Inter-stage heaters are installed to maintain the desired reaction temperature.
Effluent from the reactors is cooled by heat exchange with cold fresh feed and recycle hydrogen
before being charged into the gas/liquid separator. A portion of the hydrogen gas from the
separator is recycled to the reactors to limit coke formation while the net hydrogen production is
sent to hydrogen users or fuel. The separator liquid is pumped to a product stabilizer (fractionator)
where light hydrocarbons (LPG) are removed from high octane liquid product (the reformate).
Coke laydown, due to the high heat of reaction, on the catalyst is a major concern in the process
because of significantly reduced catalyst activity and process yields. Lower reactor pressures
produce better yields, but increase coking. Reforming has a net production of hydrogen that is
recycled to make up the reactor’s atmosphere in order to further retard coking.
Reforming catalysts consist of Group VII transition metals, usually platinum but sometimes
palladium or a mixture, dispersed on alumina. Rhenium is sometimes mixed with the platinum
(or palladium) to enhance the stability of the catalyst and allow a lower reaction pressure which
increases yields. The alumina is chlorinated to provide acid sites for isomerization.
Reforming processes are classified as continuous, cyclic, or semi-regenerative, based upon the
catalyst regeneration method used following a certain amount of coke laydown. The capital
expense for the three methods decreases in the order presented while operating cost increases
in the order presented.
79 ~
CONTINUOUSLY-REGENERATIVE REFORMING
In this process, the reactors are designed for on-line catalyst regeneration. The pressures (50-175
psig) are substantially lower than either the semi-regenerative or cyclic processes. The severity
can always be maintained at a high level for high aromatic yield. Among the three reforming
processes, continuously-regenerative reforming is by far the most popular process today. No
new semi-regenerative or cyclic units were built over the past 15 years, and all the new reforming
units are continuously-regenerative type licensed by UOP or IFP.
Regenerated Catalyst
Fuel Gas Net Gas
Vent Gas
Chiller
Vent Gas
Regeneration Compressor
Section Reactor
Heater Light Ends
to Recovery
Stabilizer Net
Liquid
Reactor
Feed / Effluent
Exchanger
Spent Catalyst
Recycle Gas
Platformate
Fresh Feed Compressor
80 ~
PYROLYSIS GASOLINE EXTRACTION
While steam cracking of ethane and propane produces light olefins and a small quantity of pygas,
the cracking of heavy feeds such as naphtha and gas oil produces substantial amounts. For
example, a billion pounds per annum ethylene plant that uses gas oil as a feedstock will produce
approximately 10,000 barrels per day of pygas. The following table shows the relationship of
olefin plant feedstocks to benzene yields:
The following table shows the relationship of olefin plant feedstocks to benzene yields.
BENZENE YIELDS IN ETHYLENE PRODUCTION

(Per 1,000 Weight Ethylene Production)
FEED BENZENE
Ethane 4 - 10
Propane 20 - 60
n-Butane 55 - 75
Naphtha 190 - 200
C6-C8 Raffinate 160 - 180
Atmospheric Gas Oil 200 - 235
Yields vary depending on the severity of cracking operations, age of plant, and characteristics
of the feedstock.
Pygas contains large portions of olefins that must be hydrogenated before benzene and toluene
recovery. This is typically accomplished in a two stage process using a low-temperature catalyst
for di-olefin saturation and a high-temperature hydrogenation stage for mono-olefin saturation
and sulfur removal.
Makeup Hydrogen
Off gas
Pyrolysis
Gasoline
Stabilizer
Di-Olefin
Olefin and S-Compound
Hydrogenator
Hydrogenator
To Aromatics
Extraction Unit
81 ~
BENZENE
• Extraction
◦ Extraction from reformate
◦ Extraction from pygas
◦ Mix of reformate/pygas extraction processes
• Hydrodealkylation of toluene (HDA)
• Toluene disproportionation (TDP)
• Coke oven
KEY PROCESSES - SULFOLANE EXTRACTION PROCESS

Raffinate
EXTRACT
Solvent Recovery
Water Wash
Extractor
Stripper
Reformate
Solvent
Light Paraffin Recycle
Solvent & Extract

Solvent
The Sulfolane process combines liquid-liquid extraction with extractive distillation to recover high-
purity aromatics from hydrocarbon mixtures such as reformed naphtha (reformate), pyrolysis
gasoline (pygas), or coke oven light oil. This hybrid combination of techniques takes advantage
of the high contaminate removal (selectivity) from both processes enabling a broader boiling
range of feedstocks than by either process alone. Simultaneous recovery of high-purity C6-C9
aromatics, with individual aromatic components recovered downstream by simple fractionation,
is achieved with one Sulfolane unit.
82 ~
Developed as a solvent in the early 1960s by Shell, Sulfolane is still one of the most efficient
solvents available for aromatics recovery. Since Sulfolane exhibits higher selectivity and capacity
for aromatics than any other commercial extraction solvent, Sulfolane units operate at the lowest
available solvent to feed ratio for any given reformate feedstock. Therefore, these units are less
expensive to build and operate than any other type of extraction unit for reformate applications.
Shell’s Sulfolane process offers good thermal and hydrolytic stability, along with a good balance of
solvent properties. In this process, reformate feed enters the extractor and flows counter-current
to the down-flowing solvent. As the feed flows through the reactor, aromatics are selectively
dissolved in the solvent. The raffinate, very low in aromatics content, is withdrawn from the top
of the extractor and leaves the system after water washing; whereas, the aromatics rich solvent
exits from the bottom and enters the top of the solvent stripper. The stripper removes the non-
aromatic hydrocarbons (light paraffins) from the top while aromatics and Sulfolane exit from the
bottom. The aromatics and Sulfolane mixture enters the solvent recovery column where it easily
separates into an overhead stream (BTX extract) and the bottom stream (solvent). To minimize
solvent temperatures, the recovery column is operated under vacuum. The lean solvent returns
to the extractor as recycle, while the aromatics stream receives a water washing before leaving
as BTX extract. The BTX extract moves to fractionation for separation into benzene, toluene,
and xylenes.
CONVERSION OF TOLUENE INTO BENZENE
The toluene yield from naphtha reforming is two to three times greater than the yield for benzene,
yet the chemical demand for benzene has always been greater than toluene. This demand for
benzene led to the development of technology for the conversion of toluene into benzene which
is the basis for the following section.
Toluene Disproportionation
Toluene disproportionation (TDP) produces roughly equal amounts of benzene and xylene, and
consistently shows more favorable economics for longer periods during the year. In addition to
the reduced loss of carbon to methane, disproportionation has several additional advantages
over hydrodealkylation of toluene (HDA). Two of them are: (1) xylenes and benzene are each
produced in ratios which better reflect the market, and (2) the resultant xylenes have very low
ethylbenzene content.
UOP licenses the Tatoray process that was developed by Toyo Rayon. For a toluene feedstock,
the products are equal amounts of benzene and xylenes whereas for a mixture of feedstock
(C9 aromatics and toluene), the conversion shifts away from the benzene molecule over to
the xylenes molecule. The Tatoray process is capable of processing feedstocks ranging from
100 percent toluene to 100 percent C9 aromatics. The optimal concentration of C9 in the feed
is 40-60 percent. Both disproportionation and transalkylation occur in the Tatoray process. The
predominant reactions in this process, based on type of feed, are:
The maximum level of conversion per pass is limited by equilibrium and feedstock composition.
The Tatoray process is designed to function at a much higher level of conversion per pass
(50 percent for a 50:50 toluene to C9 feed) than other TDP processes. This high level of conversion
minimizes the amount of unconverted material recycled back through fractionation. A smaller
recycle stream reduces the size of the benzene and toluene columns, minimizes the size of the
Tatoray unit and decreases the utility consumption in all of these units. Although most Tatoray
83 ~
CH
TDP REACTIONS CH
3 3
2 +
TOLUENE BENZENE CH
3
AND XYLENES
CH CH
3 3
+ 2
CH
3
CH CH CH
3 3 3
C 's TOLUENE
9
units are designed to run for 12 months between catalyst regenerations, many units have been
operating for several years between regenerations. The catalyst is regenerated in situ using a
simple carbon burn procedure.
Units are designed to run for 12 months between catalyst regenerations, many units have been
operating for several years between regenerations. The catalyst is regenerated in situ using a
simple carbon burn procedure.
TATORAY TOLUENE DISPROPORTIONATION PROCESS

Recycle Hydrogen
Light Ends
Reactor
BENZENE
XYLENES
Makeup
Hydrogen
FRACTIONATION
Separator
Toluene
Clay Treating
Heavy Ends
Recycle Toluene Recycle C9
C9 Aromatics
84 ~
In this process, the fresh feed, toluene and/or C9 aromatics, to the Tatoray unit is first combined
with a hydrogen rich recycle gas, preheated by exchange with the hot reactor effluent, and then
vaporized in a fired heater where it is raised to reaction temperature. The hot feed vapor is then
sent to the reactor, where it is sent down-flow over a fixed bed of catalyst. The reactor effluent
is then cooled by exchange with the combined feed, mixed with makeup gas to replace the small
amount of hydrogen consumed in the Tatoray reactor, and then sent to a product separator.
Hydrogen rich gas is taken off the top of the separator and recycled back to the reactor. A small
portion of the recycle gas is purged to remove accumulated light ends from the recycle gas loop.
Liquid from the bottom of the separator is sent to a stripper column. The C5 overhead from the
stripper is cooled and separated into gas and liquid products. The stripped overhead gas is
typically exported as fuel gas. The benzene and xylenes products, together with the unreacted
toluene and C9 aromatics, are taken from the bottom of the stripper and fractionated into their
respective cuts. This obviously requires an additional tower relative to conventional TDP to
separate the C9 aromatics from the mixed xylenes stream.
85 ~
STYRENE
C C
C C
C C
Styrene is an aromatic organic compound that exists as a clear, colorless, oily liquid under normal
conditions. It is practically insoluble in water, volatile and has a sweet smell. It has virtually
no end-use of its own and can be thought of as purely an intermediate to the production of
derivatives. Styrene is used in the manufacture of synthetic plastics, rubber and resins.
Since the styrene molecule contains the vinyl group, it is unsaturated and is readily polymerized
and co-polymerized. It must be refrigerated to avoid polymerization. During transport, an inhibitor
is mixed in the styrene to avoid polymerization during travel.
Styrene is flammable and toxic and is classified as a possible human carcinogen by the Environmental
Protection Agency (EPA) and by the International Agency for Research on Cancer (IARC). The
main health effects caused by exposure to styrene involve the central nervous system.
1. Polystyrene (PS)
2. Expandable Polystyrene (EPS)
3. Acrylonitrile Butadiene Styrene (ABS)
4. Styrene Butadiene Latex (SBL)
5. Styrene Butadiene Rubber (SBR)
End-Use Products
1. Packaging (food packaging), electronics, toys and appliances
2. Electronics, construction
3. Toys, electronics, appliances, auto parts
4. Paper and textile coatings, carpet backing
5. Tires, automobile parts
86 ~
World
2007 Styrene Demand By Region
Northeast Asia
44% Southeast Asia
5%
Indian North America

Subcontinent 19%
2%
Middle East
2%
South America
Africa 3%
1%
West Europe
CIS & Baltic Central Europe 21%
States 2%
2%
World
2007 Styrene Capacity By Region
Southeast Asia
7%
Northeast Asia
38%
North America
25%
Middle East
4%
Africa
South America
1%
2%
CIS & Baltic
States West Europe
Central Europe 21%
2% 1%
87 ~
World
2007 Styrene Demand By Sector
Polystyrene
Others 40%
Thermoplasitc 6%
Elastomers
2%
S.B. Copolymers
<1%
MBS Copolymers
1%
Unsat. PE Resins
5%
S.B. Rubber
4%
S.B. Latex
6%
SAN Resins Expandable PS
2% 18%
ABS Resins
16%
Styrene
2007
Share
Owner
% of World Capacity

Dow 7.60%
BASF AG 6.88%
Total 6.34%
Lyondell 5.92%
SABIC 3.99%
Formosa Group 3.22%
Ineos 3.18%
Asahi Kasei Corp. 2.77%
Total 52.17%
88 ~
• Conventional
◦ TOTAL/Badger Styrene Process
◦ Lummus/UOP ClassicTM Process
◦ Lummus/UOP SmartTM Process
• Non-conventional
◦ Lyondell PO/SM Process
◦ Arco PO/SM Process
KEY PROCESS – TOTAL/BADGER STYRENE PROCESS
Vent Gas to Aromatics To Condenser

Fuel Recovery
RW
Lean Oil Makeup
Feed/Effluent Steam
Exchangers Lean Oil Purge
Vent Gas
Steam Compressor
Steam Fresh and CW RW
recycle EB
Reheater
Condenser
Dehydrogenation
CW
Reactors Settler
Steam Superheater Stripper
Settling Drum Steam

Process
Condensate
Crude Styrene
to Distillation
Process Description
Badger offers an optional heat recovery scheme that recovers energy from the condensing reactor
effluent stream. Following the recovery of relatively high-level energy from the effluent in the
feed/effluent exchanger, the effluent is further cooled and partially condensed by vaporizing an
ethylbenzene/water azeotrope. In a prescribed ratio, ethylbenzene and water form a minimum
boiling point azeotrope where the boiling point of the mixture is significantly lower than that of the
two pure components. From the azeotropic vaporizer, the reactor effluent is partially condensed,
hence cooling water requirements are also significantly reduced. This heat recovery scheme
reduces energy consumption between 600 and 700 kcal/kg of styrene produced. With ever-
increasing fuel prices, this heat recovery scheme has a very attractive payout time. Currently this
scheme is used in five Badger plants.
89 ~
Additional Notes
Styrene is commonly produced via the catalytic dehydrogenation of ethylbenzene in an

endothermic reversible reaction in the presence of a catalyst. The catalysts utilized are usually
based on Iron (III) oxide, promoted by a certain percentage of potassium oxide or potassium
carbonate. The presence of this potassium based promoter is to discourage coking. Steam is
injected into the reactor feed such that the equilibrium reaction shifts towards the right, favoring
styrene production. The reaction is usually taken place under vacuum conditions such that
higher selectivity is achieved. Main by-products of this reaction are usually Benzene and Toluene
which are easily separated by distillation.
90 ~
POLYSTYRENE
C C
… …
C
C C
C C
Polystyrene (PS) is a polymer made from styrene. Under normal conditions, it exists as a neutral
colored, semi-translucent pellet. In its pure form, polystyrene is hard with limited flexibility. General
purpose polystyrene (GPPS) is a clear crystal polymer that can have different properties, such
as melt flow index and chemical resistance. High impact polystyrene (HIPS) contains about 7
percent of polybutadiene, which is grafted onto the styrene polymer.
PS derivatives are the fabricated products produced from resin pellets. Fabricators and
converters have various methods of melting the pellets and turning them into finished goods. Due
to its versatility and diverse physical properties, PS resin has several key end-use applications
accounting for the majority share of demand. PS is the largest end-use of styrene and its major
end-uses include packaging, electronics and appliances.
1. Packaging
2. Electronics
3. Construction, furniture
End-Use Products
1. Packaging
a. Rigid (non-foam) packaging: cases, closures, deli containers, mugs, pails
b. Rigid (foam) packaging: egg cartons, meat and poultry trays
c. Food service: cups, plates, cutlery, clam shells, bowls
d. Other packaging: film, labels
2. Electronics: appliances, video cassettes, CD cases, power tools
3. Construction, furniture: picture frames, lamps, roofing, siding, panels
91 ~
World
2007 Polystyrene Demand By Region
Northeast Asia
32% Southeast Asia
6%
Indian
Subcontinent
2%
North America
Middle East 24%
5%
Africa
1%
CIS & Baltic

States
South America
3%
5%
3% 19%
World
2007 Polystyrene Capacity By Region

37% 7%
North America
Indian 22%
Subcontinent
3%
Middle East
2%
1% 6%
States 18%
3% Central Europe
2%
92 ~
World
2007 Polystyrene Demand By Sector
Packaging -
single use
40%
Others
32%
Electronics /
Appliances
28%

Polystyrene
2007
Share
Owner
% of World Capacity
Dow 13.69%
Total 9.59%
BASF AG 9.52%
Ineos 4.41%
Chi Mei 4.14%
SINOPEC 3.12%
Formosa Group 2.60%
Denki Kagaku Kogyo 2.32%
Total 57.87%
93 ~
• Mass or bulk
◦ FINA Continuous Mass Polystyrene Process
• Suspension
◦ ARCO Technology Suspension Polystyrene Process
• Solution
The most widely used polystyrene production methods are mass and suspension. The primary
differences in processes involve temperature control of the exothermic reaction, the type of resin
desired, and the use of diluent or catalyst. The polymerization can be initiated by either heat or
a catalyst. The polymerization usually occurs in stages with the temperature increasing at each
stage. When polymerization is complete, the polymer is removed from any diluent and catalyst,
and depending on the process, is washed. The polymer is then extruded and pelletized for
packaging and sale. Schematic diagrams are presented for the CdF/Badger process, the Fina
continuous mass process, as well as the suspension process developed by Arco Technology.
KEY PROCESS – CDF/BADGER POLYSTYRENE PROCESS
Additives
Rubber Polymerization
Tower
Styrene
Feedstock Devolatilizer
Tank
Cooler Dryer
Heated Die Pelletizer
Prepolymerizer
Screen
POLYSTYRENE
94 ~
EXPANDABLE POLYSTYRENE
EPS beads are produced from polystyrene beads made in the suspension process, which
are impregnated under heat and pressure with a light hydrocarbon such as pentane. The light
hydrocarbon will expand the polymer when reheated.
EPS is the raw material used for the moulding of expanded polystyrene products. Expanded
polystyrene is durable and lightweight and can be custom made into various shapes. Its insulating
properties make it a popular choice for building insulation. As a result of these properties, the
main demand for EPS comes from packaging and construction.
1. Packaging
2. Construction/building
End-Use Products
1. Packaging
2. Thermal insulation: packaging of chilled products and perishable foodstuffs
3. Protective packaging: especially of electronic compartments and electrical consumer goods
4. Construction/building: insulation panels in building structures
5. Insulated concrete forms
95 ~
World
2007 Expandable Polystyrene Demand By Region

41% 4%
North America
14%
Indian
Subcontinent
1%
South America
2%
Middle East
3%
Africa
1% West Europe
Central Europe 21%
CIS & Baltic
9%
States
4%
World
2007 Expandable Polystyrene Capacity By Region
Indian
Subcontinent
1%
Middle East Northeast Asia
1% 57%
CIS & Baltic

States
2%
Central Europe
3%
West Europe
19%
South America
3% Southeast Asia
North America 4%
10%
96 ~
World
2007 Expandable Polystyrene Demand By Sector
Packaging
36%
Others
7%
Construction /
Building
57%
Expandable Polystyrene
2007
Share
Owner
% of World Capacity
Loyal Group 11.99%

BASF AG 8.21%
Wuxi Xingda 6.75%
China General Plastics Co. 4.80%
Radnor Holdings Corp. 3.10%
Ineos 2.59%
Jiangyin Ni Jia Xiang 2.40%
Dart Container 2.32%
Ming Dih 2.16%
Total 49.61%
97 ~
CUMENE
C C C
C C
C C
Cumene, also known as isopropylbenzene, is an aromatic hydrocarbon. A flammable, colorless

liquid with a sharp odor, it can be found in crude oil and is a part of processed high-octane
gasoline. It is produced primarily by alkylation of benzene with propylene and is converted
to phenol and acetone by peroxidation. Cumene is also used in the manufacture of cumene
hydroperoxide and dicumyl peroxide which are used as initiators in the polymerization process,
grafting of vinyl monomers onto polymer backbone and curing of resins and rubber.
Cumene technology was first developed early in the 1930s to convert the large amounts of light
olefinic gases from thermal cracking operations into useful products. By the late 1930s UOP
discovered that using a solid phosphoric acid (SPA) catalyst system allowed efficient alkylation of
lower molecular weight aromatics with light olefins to produce a higher molecular weight aromatic.
For decades, the chemical industry had used SPA or aluminum chloride catalysts to synthesize
cumene from benzene and propylene but this changed when new process technologies using
zeolite systems as the catalyst were introduced in the 1990s (e.g. UOP’s Q-Max process in
1996). These new highly selective zeolitic catalysts dramatically increased capacity by 50-100
percent, provided substantial savings on energy and raw materials, improved product quality as
well as eliminated maintenance and catalyst disposal problems associated with older systems.
Consumption of cumene downstream includes phenol and acetone as well as their derivatives
such as bisphenol A and phenolic resins.
End-Use Products
1. Aviation gasoline component that enables the improvement of the octane rating of internal
combustion engines
2. Thinner for paints, enamels and lacquers
3. Manufacture of polymerisation catalysts for acrylic and polyester type resins
98 ~
World
2007 Cumene Demand By Region
Southeast Asia
3%
North America
Northeast Asia 31%
32%
Indian
1% 2%
CIS & Baltic

States
3%
1% 27%
World
2007 Cumene Capacity By Region
Southeast Asia
3%
Northeast Asia North America

29% 35%
Indian
Subcontinent
1%
CIS & Baltic
South America
States
2%
3%
1% 26%
99 ~
World
2007 Cumene Demand By Sector
Others
1%
Phenol
99%

Cumene
2007
Share
Owner
% of World Capacity
Mitsui Chemicals 8.06%

Petróleos de Venezuela 6.84%
Georgia Gulf 6.54%
Ineos 5.96%
Sunoco 5.81%
Dow 5.09%
Koch Industries 4.88%
Compañía Española de Petróleos 4.09%
Total 57.29%
100 ~
• Shaw Group Mobil/Badger process
• UOP Q-Max process
• CDTech CDCumene process
• Monsanto/Lummus Crest process
KEY PROCESS – UOP Q-MAX PROCESS
Recycle Benzene Cumene

Benzene
Propylene
Propane DIPB
(C3 =)
C3 =
Diisopropyl Benzene
Benzene
Cumene
C3 = C3 =
Depropanizer
Alkylation
Reactors Heavies
Transalkylation
Reactor
Process Description
Introduced in 1996, the UOP Q-Max process uses a highly selective and stable zeolite catalyst.
The Q-Max process provides excellent cumene product purity of more than 99.97 weight percent
and high cumene yield of more than 99.7 weight percent. The process flow consists of an
alkylation reactor, a distillation section and a transalkylation reactor. The zeolite catalyst in both
reactors is regenerable, and has a catalyst life of about five years with cycle lengths of 18-36
months. Mild operating conditions and a corrosion-free process environment allow the use of
carbon-steel construction and conventional process equipment.
101 ~
The alkylation reactor is typically divided into four catalyst beds contained in two reactor shells
in series. A mixture of fresh and recycled benzene is charged down-flow through the alkylation
reactors. Fresh propylene feed is split between the sections, and is completely consumed in
each bed. Effluent from the alkylation reactor is sent to the de-propanizer that removes any
propane and water that enter with the feeds. A portion of the reactor effluent is recycled, and
acts like a heat sink to help control the temperature rise in each section due to the exothermic
reactions.
Bottoms from the de-propanizer is sent to the benzene column where un-reacted benzene is
collected overhead and recycled. Bottoms from the benzene column is in turn sent to the cumene
column where cumene is recovered overhead. Diisopropylbenzene (DIPB) and some heavy
aromatic by-products exit the bottom of the cumene column and enter the DIPB column, where
DIPB is recovered overhead and mixes with a portion of the benzene column recycle in route to
the transalkylation reactor where they convert to additional cumene. The effluent then leaves the
reactor and enters the benzene column.
102 ~
PHENOL
C C
C C
Phenol is the second major derivative in the benzene chain behind styrene and is characterized
by a slightly acidic behavior due to the hydroxyl group attached to the phenyl ring. It is typically
a white crystalline solid at room temperature showing a reddish discoloration when exposed to
air for a while. Found naturally in decaying dead organic matter, phenol was originally isolated
from coal tar streams and this remained its main source until World War I when the first synthetic
method of production was devised. Phenol demand has increased with the years and today it is
almost entirely produced synthetically.
Phenol production processes are usually based either on cumene or toluene feed, although the
former is pre-dominant because of the high demand for the by-product acetone. The toluene
based process is technically more complex and requires a catalyst to convert the key precursor
benzoic acid to phenol. A newer technology producing phenol, which is well suited for use
in the production of adipic acid, in a one-step route directly from benzene was developed by
Solutia. In this process, nitrous oxide is used as an oxidant in the presence of zeolitic catalysts.
Nitrous oxide is a by-product of Solutia’s cyclohexanone based adipic acid process. It can also be
produced on purpose from ammonia. The economic advantages of each process are dependent
on the feedstock costs relative to the phenol price.
Phenol is a base chemical in the organic synthesis of:

• Bisphenol A and its derivatives such as polycarbonate and epoxy resins
• Phenolic resins and its derivatives such as adhesives, structural shapes and electrical
laminates
• Caprolactam, an intermediate in the manufacture of nylon
End-Use Products
Phenoplastics (Bakelite), pigments, antioxidants, synthetic tanning agents, see also above.
103 ~
World
2007 Phenol Demand By Region
Southeast Asia
6%
Northeast Asia
31% North America
27%
Indian
Subcontinent
2%
Middle East
1% South America
Africa 2%
<1%
CIS & Baltic
West Europe
States
Central Europe 27%
2%
2%
World
2007 Phenol Capacity By Region
Southeast Asia
3%
North America
Northeast Asia 32%
29%
Indian
Subcontinent
1%
Middle East South America

<1% 2%
CIS & Baltic
States
3% Central Europe West Europe
2% 28%
104 ~
World
2007 Phenol Demand By Sector
Alkylphenol
Others
5% Aniline
10%
1%
Phenolic Resin
27%
Bisphenol A
43%
PPO/Orthoxylenol
2%
Nylon-KA Oil
12%
Phenol
2007
Share
Owner
% of World Capacity
Ineos 17.83%
Sunoco 9.18%
Mitsui Chemicals 8.31%
Formosa Group 4.27%
Compañía Española de Petróleos 4.23%
SINOPEC 3.73%
Dow 3.15%
Mitsubishi Chemical 2.67%
Total 64.91%
105 ~
• Cumene based process
• Toluene based process
• Solutia Alphox process
• Shell benzene+butadiene process
KEY PROCESS – CUMENE BASED PROCESS

Dilute sulfuric
acid
Vent Neutralization
Caustic
Water water
soda
Cleavage reactor
Vent
Oxidation reactor
Concentrator
Cumene
recovery
Compressed Air
Waste water
Cumene
Light
Acetone Hydrogenation products
PHENOL
Caustic
Crude acetone distillation
Caustic soda scrubbing

Heavy-end separation
soda
Acetone purification
Phenol purification
Recovery of cumene
and a-methylstyrene
Phenol recovery
Bottoms Bottoms
Water
Cumylphenol/acetophenone/residues
Process Description
In the cumene based process to produce phenol, cumene is oxidized with compressed air in a
series of multistage reactors. The resultant cumene hydroperoxide stream is separated into gas
and liquid phases. Cumene is recovered from the gas and returned to the oxidation reactor while
the liquid stream is concentrated and sent to the cleavage reactor. In the cleavage reactor, the
cumene hydroperoxide is split into phenol and acetone. The first tower in the distillation section
separates the crude acetone from the crude phenol. There are several distillation towers that
purify the acetone and several more that purify the phenol.
106 ~
NYLON 6,6
C C C C C C N C C C C C C N
... O ...
Nylon was the first major fiber produced from a synthetic polymer. In 1929 Wallace Hume
Carothers initiated the laboratory research and commercialization of nylon and by 1938 the first
nylon 6,6 plant run by DuPont started production in Seaford, Delaware in the United States.
Large-scale production of nylon 6 followed in Germany in 1941.
Nylon 6,6 is made from hexamethylene diamine (HMDA) and adipic acid (ADA).
Nylon 6,6 is physically and chemically similar to nylon 6 and, generally speaking, both are
competitive in most end uses; however, there are some noteworthy individual characteristics that
make one preferred to the other.
One of the greatest differences is in their melting temperatures. Nylon 6,6 has the highest
melting point of all synthetic fibers at 260°C, which is 40°C higher than nylon 6, making it an
excellent material for use in applications requiring heat resistance.
Nylon 6,6 is much less thermally stable than nylon 6, which is undesirable when the polymer is
used for fiber preparation because the gel particles lead to quality defects in spun and drawn
yarns. However, in the production of tire cords, nylon 6,6 is the preferred polymer due to its better
performance and faster processing speeds, but nylon 6 will continue to be used in developing
areas where lower standards are expected, manufacturing costs are lower and spare tire
processing capacity exists.
Although nylon 6,6 is more difficult to dye than nylon 6, its colourfastness property makes it less
susceptible to fading from sunlight; however, both nylon 6 and 6,6 are still sensitive to UV light.
In terms of similarities between the two polymers, both are resistant to chemicals and solvents,
and both have good elastic recovery and fatigue resistance. Special additives can be used in
the production process to improve and/or tailor the properties of the nylon (i.e. UV light resistant,
soil resistant, flame-retardant) based on the desired application, making nylon both a practical
and universal polymer.
The relative cost competitiveness of nylon 6 and 6,6 is highly dependent on the price of benzene,
since nylon 6 uses a greater percentage of benzene as a feedstock than nylon 6,6. Strong
demand for plastics for under-the-hood applications continue to boost 6,6 demand but lower 6
prices would encourage the use of nylon 6 in other end-uses.
107 ~
1. Textile Filament (NTF)
2. Industrial Filament (NIF)
3. Bulk Continuous Fiber (BCF)
4. Staple Fiber (NSF)
5. Engineering Thermoplastics (ETP)
End-Use Products
Nylon fiber is the second largest synthetic fiber after polyester and is the primary end-use for
both nylon 6 and 6,6. The remaining nylon consumption is into engineering resins. Nylon 6,6
engineering resins are primarily used in injection moulding applications for the transportation and
electronics industries.
108 ~
World
2007 Nylon Resin Demand By Region
Indian
Subcontinent Northeast Asia
Middle East 2% 46%
3%
Africa
<1%
CIS & Baltic
States
3%
Central Europe
2%
Southeast Asia
West Europe 4%
22%
North America
South America
15%
3%
World
2007 Nylon Resin Capacity By Region
Southeast Asia
2%
Northeast Asia
38% North America
20%
South America
Indian 2%
Subcontinent
1%
Middle East
1% West Europe
CIS & Baltic 26%
Central Europe
States
4%
6%
109 ~
World
2007 Nylon Resin Demand By Sector
Staple Fiber
2% Bulk Continuous
Filament
9%
Engineering
Resins & Others
41% Textile Filament
Yarn
30%
Industrial
Filamant Yarn
18%
Nylon Resin
2007
Share
Owner
% of World Capacity
BASF AG 8.98%
Rhodia 3.89%
Li Peng 3.77%
DSM 3.74%
DuPont 3.69%
RadiciGroup 3.08%
Formosa Group 2.92%
Honeywell 2.92%
Novanyl NV 2.62%
Total 41.12%
110 ~
World
2007 Nylon Textile Filament Demand By Region
Indian
Subcontinent
4%
Middle East
4%
Africa Northeast Asia
<1% 64%
CIS & Baltic
States
<1%
Central Europe
1%
West Europe
10%
South America
5%
North America
6% Southeast Asia
6%
World
2007 Nylon Textile Filament Capacity By Region
Middle East Indian
4% Subcontinent
2%
Africa
CIS & Baltic 1%
States
2%
Central Europe
3% Northeast Asia
West Europe 65%
8%
South America
4%
North America
6%
Southeast Asia
5%
111 ~
Nylon Textile Filament

2007
Share
Owner
% of World Capacity
Formosa Group 5.48%

Novanyl NV 3.80%
Hualon Chemical & Textile 2.99%
Toray 2.87%
RadiciGroup 2.84%
Hyosung Corp. 2.75%
Nilit 2.59%
Hualon Corp. 2.28%
Chain Yarn 1.76%
Total 30.76%
112 ~
World
2007 Nylon Industrial Filament Demand By Region
Indian
Subcontinent
Middle East 6%
4%
Africa
1%
CIS & Baltic Northeast Asia
States 49%
9%
Central Europe
2%
West Europe
9%
South America
4%
North America
Southeast Asia
10%
6%
World
2007 Nylon Industrial Filament Capacity By Region
Indian
Subcontinent
4%
Middle East
5% Northeast Asia
Africa
48%
1%
CIS & Baltic

States
11%
Central Europe
3%
West Europe
5%
South America
4%
North America Southeast Asia
10% 9%
113 ~
Nylon Industrial Filament

2007
Share
Owner
% of World Capacity
SASA 8.28%
Jiangsu Junma 6.00%
Shenma Group 5.62%
Kingring Group 3.90%
Formosa Group 3.45%
Butler Capital 3.06%
Toray 3.05%
Filamendo Sakti 2.64%
SRF 2.16%
Total 44.10%
114 ~
World
2007 Nylon Bulk Continuous Filament Demand By Region
Southeast Asia
2%
Northeast Asia
5%
Middle East
3%
Africa
1%
CIS & Baltic

States North America
1% 75%
Central Europe
2%
West Europe
11%
Total Demand = 976 Thousand Metric Tons
World
2007 Nylon Bulk Continuous Filament Capacity By Region
Southeast Asia
1%
Northeast Asia
7%
Middle East
1%
Africa
1%
CIS & Baltic North America
States 74%
1%
Central Europe
2%
West Europe
13%
115 ~
Nylon Bulk Continuous Filament

2007
Share
Owner
% of World Capacity

Shaw 19.86%
Mohawk 5.76%
Bonazzi Group 5.03%
Beaulieu Group 4.10%
Belgian Investors 2.71%
Monsanto 2.31%
Solutia 2.09%
Teijin 1.39%
Universal Fiber Systems 1.39%
RadiciGroup 1.39%
Filartois 1.39%
Total 85.71%
116 ~
World
2007 Nylon Staple Fiber Demand By Region
North America West Europe

63% 19%
CIS & Baltic

States
2%
Middle East
1%
Northeast Asia
15%
Total Demand = 354 Thousand Metric Tons
World
2007 Nylon Staple Fiber Capacity By Region
South America
1% West Europe
North America 21%
47%
Central Europe
3%
CIS & Baltic

States
3%
Northeast Asia
25%
Total Capacity = 482 Thousand Metric Tons
117 ~
Nylon Staple Fiber

2007
Share
Owner
% of World Capacity
Shaw 18.36%
Monsanto 15.78%
Solutia 14.28%
Rhodia 7.28%
RadiciGroup 4.87%
Lamato 3.25%
SINOPEC 3.25%
Butler Capital 2.76%
Capron 1.95%
Total 77.47%
118 ~
• Continuous process
• Batch process (autoclave)
KEY PROCESS – NYLON POLYMERIZATION
MIX TANK MIX TANK
40-50 percent SOLIDS
Water Vapor Exit

High Pressure Steam
100-115OC
EVAPORATOR
Condensate Out
240-260 PSIG
230OC Dowtherm In
REACTOR
Dowtherm Out
Dowtherm In
FLASHER
Dowtherm Out
FINISHER
Nylon 6,6 Polymer to Spinning

Nylon 6,6 is manufactured from hexamethylene diamine (HMDA) and adipic acid (ADA) in a
continuous two-stage process.
In the first stage, equimolar mixtures of HMDA and ADA are combined with water in mixing tanks
to form an intermediate product called nylon salt, which is then sent to an evaporator to remove
the excess water. When a solid content of about 60-75 percent is achieved, the nylon salt is fed
to reactor where the polymerization takes place. In this second stage, the mixture resided for
about two hours at 235°C and pressures between 240 and 260 psi. A variety of substances are
normally added before or during polymerization to achieve specific properties for the resultant
polymer.
Finally, the molten nylon 6,6 undergoes a spinning process, after which it is extruded and passed
through a spinneret (a small plate with fine holes). The nylon is then air-cooled to form chips,
also called resin, or further processed into an end-use (i.e. fibers, engineering plastics).
119 ~
NYLON 6
C C C C C C N
Nylon was the first major fiber produced from a synthetic polymer. In 1929 Wallace Hume
Carothers initiated the laboratory research and commercialization of nylon and by 1938 the first
nylon 6,6 plant run by DuPont started production in Seaford, Delaware in the U.S. Large-scale
production of nylon 6 followed in Germany in 1941.
Nylon 6, also referred to as nylon caprolactam, is made from caprolactam, which has six carbon
atoms, hence lending to the name nylon 6.
Nylon 6 is physically and chemically similar to nylon 6,6 and, generally speaking, both are
competitive in most end uses; however, there are some noteworthy individual characteristics that
make one preferred to the other.
One of the greatest differences is in their melting temperatures. Nylon 6 has a 40°C lower
melting point at 215°C in comparison to nylon 6,6, but subsequently has lower energy costs for
processing.
Nylon 6 is more resistant to degradation under prolonged heating, which allows for the nylon to
be held as a melt before being spun. In addition nylon 6 is easier to dye than nylon 6,6. Both of
these characteristics make nylon 6 advantageous in the production of fibers.
In terms of similarities between the two polymers, both are resistant to chemicals and solvents, and
both have good elastic recovery and fatigue resistance. Special additives can be used in the production
process to improve and/or tailor the properties of the nylon (i.e. UV light resistant, soil resistant, flame-
retardant) based on the desired application, making nylon both a practical and universal polymer.
The relative cost competitiveness of nylon 6 and 6,6 is highly dependent on the price of benzene,
since nylon 6 uses a greater percentage of benzene as a feedstock than nylon 6,6. Strong
demand for plastics for under-the-hood applications continue to boost 6,6 demand but lower 6
prices would encourage the use of nylon 6 in other end-uses.
120 ~
1. Textile Filament (NTF)
2. Industrial Filament (NIF)
3. Bulk Continuous Fiber (BCF)
4. Staple Fiber (NSF)
5. Engineering Thermoplastics (ETP)
End-Use Products
Nylon fiber is the second largest synthetic fiber after polyester and is the primary end-use for both
nylon 6 and 6,6. The remaining nylon consumption is into engineering resins. The majority of
nylon 6 engineering resin is consumed in film and sheet, transportation, and wire and cable.
121 ~
• Continuous process
• Batch process (autoclave)
KEY PROCESS – NYLON POLYMERIZATION
Nylon 6 is traditionally produced from caprolactam in a continuous two-stage process.
In the first stage, pure anhydrous caprolactam is mixed with a high quantity of water (water-
catalyzed production) to initialize the reaction. The resulting solution undergoes heating at a high
temperature and high pressure, which breaks the caprolactam ring (formation of aminocaproic
acid) and starts the polymerization process.
In the second stage, both the water concentration and temperature are lowered to achieve a higher
conversion of caprolactam and, hence, a higher degree of polymerization. Caprolactam can be
polymerized without interruption with or without pressure. First, the molten lactam containing
water and acid is fed to a heated elongated spiral polymerization zone. Then, the mixture is fed
to a set of two or more charge vessels that are fitted with agitators at which point the catalyst and
chain regulator are generally added. The temperature of the reactor is controlled to be in the range
of 250-260°C. The monomer feed moves down the reactor and becomes more viscous as the
degree of polymerization increases. Steam is removed via the reflux condenser. Perforated tray-
like plates are installed in the reactor to prevent low viscosity polymer from cascading down into
the higher viscosity polymer prematurely. The reaction time usually amounts to 18-20 hours.
As mentioned in the foregoing section, a variety of substances can be added before or during
polymerization to modify the properties of the resulting polymer. After the polymerization has
taken place, the molten product is passed through a spinneret and either air-cooled to form chips
or further processed into fibers, engineering plastics, etc.
Feedstocks
Feedstocks Intermediates
Intermediates End-Use
End-UseMarkets
Markets
Fibre
Fibre
Adiponitrile
Adiponitrile
Butadiene
() Nylon
HMD Nylon6,6
6,6 Nylon
Nylon6,6
6,6 ••Textiles
Textiles
HMD Salt Resin ••Carpet
Adiponitrile Salt Resin CarpetFibre
Fibre
Acrylonitrile Adiponitrile ••Industrial
IndustrialFibre
Fibre
••Film
Film
ETP ••Filament
Filament
ETP
••Wire
Wireand
andCable
Cable
••ETP
ETPSegments
Segments
Cyclohexane Adipic
AdipicAcid
Acid –– Electro
Fibre Electro
Fibre –– Auto
Auto
–– Industrial
Industrial
–– Consumer
Consumer
Nylon
Nylon66
Phenol Caprolactam
Caprolactam Resin
Resin
ETP
ETP
122 ~
TOLUENE
C C
C C
Toluene is an aromatic hydrocarbon where one hydrogen atom of the benzene ring is substituted
by a methyl group. For this reason it is also referred to as methylbenzene. It was named in
reference to the tolu balsam, an aromatic extract from the tropical Colombian tree myroxylon
balsamum, from which it was first isolated by Henri Etienne Sainte-Claire Deville in 1844.
Today, toluene is primarily produced in a catalytic reforming process, where low-octane naphtha
feed is converted into heavier aromatic yield high-octane reformate by cyclization, dehydrogenation
and aromatization of paraffinic and naphthenic saturates. Typical effective volume yields are
about 70-80 percent of the naphtha charged but is even higher when using the new ultra-low
pressure technology. The remaining volume shows up as a light-ends yield including hydrogen,
methane, ethane, propane and butanes. In the final step, the BTX (Benzene-Toluene-Xylene)
output of the reformer is separated by extraction or distillation. Low purity toluene can also be
produced by direct reformate distillation and as a by-product of styrene production.
Toluene is a clear, colorless liquid with a characteristic smell. It is poorly soluble in water and
highly flammable but less toxic than benzene. Therefore, it is replacing benzene as a solvent in
organic synthesis and also as a blending component in gasoline (low purity toluene is used in
this instance). It is also used as a raw material for toluene diisocynate used in the manufacture
of polyurethanes, but undoubtedly its most famous derivative is trinitrotoluene, better known as
TNT.
1. Organics: benzene, styrene, benzoic acid, trinitrotoluene (TNT), toluene diisocyanate,

saccharine
2. Others: Fuel and solvent markets
End-Use Products
Broadly used as a base chemical and solvent in organic synthesis but also as a component
in glue, varnish, printer’s ink and gasoline blending due to its high octane level and low vapor
pressure.
123 ~
World
2007 Toluene Demand By Region
Northeast Asia
32% Southeast Asia
6%
Indian
Subcontinent
4%
Middle East
6%
North America
Africa 32%
<1%
CIS & Baltic

States
4% West Europe South America
11% 3%
Central Europe
2%
World
2007 Toluene Capacity By Region
Northeast Asia
32%
Indian
Subcontinent Southeast Asia
4% 6%
Middle East
7%
Africa
1%
States 27%
6%
Central Europe
3% West Europe South America
10% 4%
124 ~
World
2007 Toluene Demand By Sector
Gasoline TDI
17% 5%
HAD
11%
TDP
4%
Solvents/Others
26%
TA
Caprolactam 18%
<1%
Benzoic Acid
1% Phenol
<1% STDP/TPX
18%
Toluene
2007
Share
Owner
% of World Capacity

SINOPEC 5.88%
BP 3.66%
Formosa Group 2.78%
Total 2.43%
NPC-Iran 2.41%
Total 37.21%
125 ~
MIXED XYLENES
Meta-Xylene Ortho-Xylene
C C
C C
C C
C C
C
C
C C C C
C
C C C C
C Para-Xylene
C C
Mixed xylenes is a generic term describing a class of C8 aromatics most often produced within
a large-scale refinery during the manufacture of gasoline. As its name suggests, it is literally
a mixture of four different 8-carbon molecules that include a 6-carbon ring structure. Mixed
xylenes and its isomers are flammable, colorless, organic liquids that can be separated from the
gasoline pool and subdivided into its components – paraxylene, orthoxylene, metaxylene and
ethylbenzene. The structure of paraxylene is such that the methyl groups are directly opposite
each other in the benzene ring. The other isomers are orthoxylene (methyl groups are beside
each other), metaxylene (methyl groups are separated with an empty carbon on the ring in
between) and ethylbenzene.
At equilibrium, the mixed xylenes mixture is approximately 50 percent metaxylene, 20 percent

paraxylene, 20 percent orthoxylene and 10 percent ethylbenzene. However, the market demand
for the components is about 86 percent paraxylene, 12 percent orthoxylene and 2 percent
metaxylene with most of the ethylbenzene either isomerized to the other xylenes or dealkylated
to ethane and benzene. A significant amount of the capital equipment and energy in the industry
is spent isomerizing orthoxylene and metaxylene to paraxylene to achieve the proper balance
for the market.
The major source of xylenes is from the reforming of naphtha, a primary processing unit in a
refinery; thus, the vast majority of production is located within refinery operations. In addition,
the manufacture of xylenes results in many by-product fuel streams that are most efficiently and
cost effectively utilized in a refinery. The largest producer globally holds just over 10 percent of
the market while the second largest producer holds less than 6 percent. Since xylenes are a
refinery product, adding capacity to an existing facility is difficult and often part of a much larger
refinery upgrade program.
Nearly 80 percent of all mixed xylenes produced for chemical end-use is converted to paraxylene,
a feedstock in the manufacture of polyester fiber, film and bottle resins. Additionally, both
orthoxylene and metaxylene can be converted (isomerized) to paraxylene to make efficient
use of the available mixed xylenes. Most xylenes are consumed captively in the production of
paraxylene and/or orthoxylene which is then sold to a secondary consumer. However, mixed
xylenes contracts do exist in all major regions of the world where paraxylene producers need to
supplement their own captive production.
126 ~
1. Paraxylene (PX)
2. (Purified) Terephthalic Acid (PTA)
3. Polyester (Fiber and PET)
4. Gasoline
End-Use Products
1. Paraxylene: used in the manufacture of either terephthalic acid or dimethyl terephthalate for
use in the production of polyesters.
2. Orthoxylene: the second largest market; primarily used in phthalic anhydride which is in turn
use in plasticizers and unsaturated polyesters.
3. Metaxylene: primarily used in the production of isophthalic acid which is used in the polyester
coatings and unsaturated polyester industries as well as in the polyester bottle resin industry
as a modifier.
4. Ethylbenzene
127 ~
World
2007 Mixed Xylenes Demand By Region
Indian
Subcontinent
6%
Middle East
Northeast Asia
4%
48%
CIS & Baltic
States
2%
Central Europe
1%
West Europe
9%
South America
1%
North America
Southeast Asia
18%
11%
World
2007 Mixed Xylenes Capacity By Region
Indian
Subcontinent Northeast Asia
Middle East 6% 41%
4%
Africa
1%
CIS & Baltic

States
3%
Central Europe
1%
West Europe
10%
South America
2% Southeast Asia
10%
North America
22%
128 ~
World
2007 Mixed Xylenes Demand By Sector
Ethylbenzene
<1%
Solvent & Others Paraxylene

13% 77%
Orthoxylene
9%
Metaxylene
1%

Mixed Xylenes
2007
Share
Owner
% of World Capacity

SINOPEC 7.62%
BP 4.61%
Total 4.17%
Formosa Group 2.85%
GS Holdings 2.63%
Total 46.66%
129 ~
• Distillation
• Selective Toluene Disproportionation (STDP)
• Transalkylation
• Extraction
KEY PROCESS – DISTILLATION AND STDP
Distillation
Mixed xylenes production via distillation is one of the fastest growing production routes, and
almost all new capacities added after 1990 are based on distillation. Previously, the purity of
the A8 cut native in reformate was not high enough to allow direct isolation of mixed xylenes for
merchant sales to paraxylene producers. Modern advances in xylene isomerization and high-
severity catalytic reforming have now made it possible to produce a high-quality mixed xylene
stream without the need for extraction. Mixed xylenes are cut from a C7- and C9+ stream via
conventional distillation, resulting in much lower capital and operating costs.
Typical cash costs for mixed xylenes production are only about 3-4 cents per gallon (US$9-$12/
ton) over the regional blend value, and have provided a low-investment source of incremental
petrochemical revenue for producers that have a competitive octane source.
Many integrated isomer producers have been isolating mixed xylenes directly by distillation for
some time, as they have recognized the slightly higher paraxylene cash costs do not compensate
for the higher variable and operating costs associated with extraction. This is especially true for
crystallization operations, which are less sensitive to feed non-aromatics content than adsorption-
based units. There are still some producers who, due to high non-aromatic content in their
reformate or other processing constraints, continue to extract paraxylene feed. It should be noted
that most new units are being designed around continuous catalytic reformers in conjunction with
recovery of mixed xylenes via distillation.
130 ~
STDP
Selective toluene disproportionation (STDP) is a variant of conventional TDP which was developed
and licensed by Mobil. The STDP technology converts extracted toluene to high-purity benzene
(99.7 percent) and para-rich xylenes (80 percent PX and higher). In this process, the para-
selective catalyst is pretreated (coked) to increase the selectivity of toluene to paraxylene. The
latest version of STDP is MTPX. The process can produce PX at as high as 90 percent purity.
STDP can also be used for large scale grassroots facilities where significant quantities of
benzene are desired along with paraxylene. Such applications may be limited because of the
large amount of toluene feedstock required, and the byproduct issues associated with such large
benzene production volumes.
Makeup
Recycle Gas
Hydrogen
Purge
Recycle Gas
Compressor
Light Ends
Toluene
&
Recycle to
C6 -
Feed
Toluene
Feed
Feed Heater DeToluenizer
Furnace
STDP
Reactor
CW Separator
Drum
pX-Rich
C8+ Aromatics
131 ~
PARAXYLENE
C C
C C
Paraxylene (PX), also known as 1,4-dimethyl benzene, is a flammable, colorless, organic liquid
with an aromatic odor. The structure of paraxylene is such that the methyl groups are directly
opposite each other in the benzene ring.
Paraxylene is largely a refinery-based process and in most cases is part of a larger refinery complex.
Technology is readily available from numerous sources (many outside the producer base) but
capital requirements are sizeable, exceeding $300 million for a world scale plant. In addition, as
most plants are integrated with a refinery, and as a non-integrated facility is disadvantaged, an
extra dimension is added to the barrier to entry. Roughly 40 producers account for 90 percent of
the world’s total paraxylene capacity with the largest producer accounting for roughly 13 percent
of global capacity. In North America, six producers make up the entire production base.
Paraxylene, like the other mixed xylene isomers, has an octane number in excess of 100 so it is
often left in gasoline. Essentially all paraxylene is used in the manufacture of either terephthalic
acid or dimethyl terephthalate for use in the production of polyesters. PX is easily transported in
bulk quantities under similar shipping conditions as gasoline.
Paraxylene is a global commodity and is relatively inexpensive to ship between regions. Pricing
tends to be fairly comparable globally with differences mainly due to transportation costs.
Paraxylene is the only portion of the polyester chain where there is an alternative use, and that
is to leave the product in gasoline. Downstream consumers have no alternative to paraxylene
and, therefore, gain no power from alternate products. Paraxylene, however, like most major
petrochemical commodities, runs a capacity utilization cycle, where when margins are attractive,
the industry expands capacity well in excess of demand growth, leading to suppressed operating
rates and margins as the market becomes oversupplied. This overcapacity transfers power
to the buyers. The power eventually transfers back to the producers when, after an extended
period of low operating rates and margins, producers rationalize capacity and limit expansion
bringing supply and demand in balance at which point margins return.
132 ~
1. Terephthalic Acid (PTA)
2. Polyester (fibers and PET)
3. Gasoline
End-Use Products
1. Terephthalic Acid: also known as purified terephthalic acid, accounts for 88 percent of PX
consumption. PTA is produced by oxidizing paraxylene to convert the methyl groups to
organic acid groups. PTA is used primarily in the production of polyester polymers for fiber
or plastic use.
2. Dimethyl Terephthalate (DMT): accounts for the remaining 12 percent of paraxylene

consumption. It is generally produced by oxidizing paraxylene to convert the methyl groups
to organic acid groups. Methanol is then added to convert the organic acid groups to a
methyl ester. DMT, like PTA, is also used primarily in the production of polyester polymers
for fiber and plastic use. DMT is also used in the production of polybutylene terephthalate
(PBT). It is the older route to polyester production and is largely being replaced by PTA.
133 ~
World
2007 Paraxylene Demand By Region
Indian
Subcontinent
7%
Middle East
3%
Northeast Asia
CIS & Baltic 54%
States
1%
Central Europe
<1%
West Europe
9%
South America
<1%
North America
15%
Southeast Asia
11%
World
2007 Paraxylene Capacity By Region
Indian
Subcontinent
8% Northeast Asia
Middle East 46%
5%
CIS & Baltic

States
2%
Central Europe
<1%
West Europe
8%
South America
1%
North America Southeast Asia
17% 13%
134 ~
World
2007 Paraxylene Demand By Sector
Terephthalic Acid
93%
Dimethyl
Terephalate
7%
Paraxylene
2007
Share
Owner
% of World Capacity

BP 9.72%
SINOPEC 8.18%
Formosa Group 3.96%
GS Holdings 3.06%
NPC-Iran 2.60%
Chevron Corp. 2.54%
Total 52.73%
135 ~
• Mixed Xylenes Adsorption
• Selective Toluene Disproportionation (STDP) + Adsorption

◦ See Mixed Xylenes section for STDP summary
• Mixed Xylenes Crystallization
KEY PROCESS – MIXED XYLENES ADSORPTION
Process Description
Adsorption is a process which utilizes differences in molecular shape to effect a separation.

The underlying phenomena are similar to chromatography employed widely in analytical labs.
Licensors of this technology include UOP and IFP; UOP owns most of the world licenses for
its trademark Parex process. This technology uses a solid zeolite adsorbent which is selective
for paraxylene. Unlike conventional chromatography, adsorption of paraxylene with these
technologies is continuous and simulates the counter-current flow of a liquid feed over a solid bed
of adsorbent. Feed and products enter and leave the adsorbent bed continuously via a rotary
valve or multiple switch valves, at nearly constant compositions. This technique is referred to as
simulating moving bed separation.
In a typical aromatics complex, the adsorption unit is located downstream of the xylene column
and is integrated with an isomerization unit. The feed to the xylene column consists of the C9+
aromatics product from reforming and sometimes mixed xylenes produced from disproportionation
or transalkylation. The C8 fraction from the overhead of the xylene column is fed to the adsorption
unit, where high purity paraxylene is recovered in the extract. The paraxylene depleted stream,
raffinate, is then sent to the isomerization unit where the remaining C8 aromatic isomers are
converted into additional paraxylene and recycled to the xylene column. The process is typically
designed to recover over 97 wt percent of the paraxylene from the feed in a single pass while
delivering paraxylene product purity of 99.9 wt percent or better.
136 ~
POLYETHYLENE TEREPHTHALATE
O C C O
C C C C O C C O
C C
... ...
Although there are many different kinds of polyester, it is polyethylene terephthalate (PET) that
first became known as fiber grade polyester and was subsequently used for polyester film and
polyester bottle resin. The polymerization process for PET bottle resin and polyester fibers is
identical. The synthesis involves the reaction of a di-alcohol, usually ethylene glycol, with an
organic di-acid, mainly terephthalic acid or dimethyl terephthalate.
PET is odorless and almost clear in color. In resin form it resembles ice and in PET bottles, if left
clear, it resembles glass. Polyester has a variety of appearances in fiber form. For example,
before finishing it typically resembles the color of cotton, but finished goods can range from
looking like cotton to silk.
As mentioned, polyester can be broken down into two major market segments: fibers and bottle
resin (chip approximately 2-3 millimeters in diameter). The fibers market is approximately twice
the size of the bottle resin market. Fiber demand is strongest in Asia where textile mills have
been located to take advantage of low cost labor. Polyester fiber comes predominately in two
forms: filament and staple. Filament products are packaged on a tube, bobbin, cone or beams.
Staple fiber is baled which is then typically wrapped with a synthetic covering to keep the fiber
clean during shipping. Resin, in the form of chip, is shipped in hopper trucks and lined Intermodal
containers and via hopper rail cars (domestic).
Bottle resin demand has grown as PET has replaced glass containers. However, there are a few
remaining glass container applications still to be converted to PET demand.
End-Use Products
1. Fibers: apparel/textile, industrial and carpet applications
2. Bottle resin: soft drink and water containers, and packaging for food and other consumer
products
3. Film
137 ~
World
2007 Polyethylene Terephthalate Demand By Region
Southeast Asia
3%
Northeast Asia
20% North America
29%
Indian
Subcontinent
2%
Middle East
4%
South America
Africa
8%
3%
CIS & Baltic

States West Europe
5%
World
2007 Polyethylene Terephthalate Capacity By Region
Northeast Asia
36%
Indian Southeast Asia

Subcontinent 6%
4%
Middle East
4%
Africa
1%

States 25%
5%
1% 14% South America
4%
138 ~
World
2007 Polyethylene Terephthalate Demand By Sector
Food
Other PET 7%
20%
Beverage
Cosmetics 70%
1%
Pharmaceutical
2%
Polyethylene Terephthalate
2007
Share
Owner
% of World Capacity
Eastman 9.15%
Mossi & Ghisolfi 7.45%
Far Eastern Group 5.08%
Jiangsu Sanfangxiang 5.01%
La Seda de Barcelona 4.81%
Indorama Synthetic 4.34%
Formosa Group 3.88%
Wellman 3.40%
KP Chemical 2.57%
Total 53.08%
139 ~
• Continuous Polycondensation (PTA Route)
• Continuous Polycondensation (DMT Route)

◦ Although there are individual variations depending on the final product (fiber, bottle
resin, film), these are relatively minor from process to process and the details below
are typical of the PTA route to polyethylene terephthalate.
KEY PROCESS – CONTINUOUS POLYCONDENSATION (PTA ROUTE)
Process Description
The PTA process has a number of advantages over starting from DMT and, as a consequence,
a great majority of new plants are based on the PTA route. The PTA process consumes less
energy, has fewer process steps than the process from DMT (a complete esterification in the
esterification stages is not required) and it is also lower in raw material consumption.
The raw materials PTA, MEG, and the required catalysts and additives are fed into the slurry
preparation vessel where the components are well mixed. The slurry is continuously discharged
by the pump into the first esterification reactor that is equipped with a pump stirrer. It is operated
above atmospheric pressure and heated by heat transfer medium (HTM) vapor. Approximately
90 percent of PTA conversion is achieved at this stage. The PET monomer is then fed into the
second esterification reactor, which is a staged reactor, equipped with an agitator and again heated
by HTM vapor. Excess MEG, reaction water and some by-products, together with a part of the
spent MEG from the polycondensation are fed into the process column. Water vapor is removed
overhead. Part of this steam is used to generate the necessary vacuum of the polycondensation
reactors by means of steam ejector units. The process water is condensed and fed to a stripper
for removal of volatile organic matter. The recycled MEG is used for preparing the paste again.
After introduction of additives that are required for the final product, precondensate is pumped via
a prepolymer filter to the first polycondensation reactor.
The two polycondensation reactors both operate under a vacuum and are heated individually by
HTM vapor. In the prepolycondensation reactor the esterification and polycondensation reactions
are allowed to continue until more than 99.5 percent conversion is achieved with a degree of
polycondensation of 20 percent. The polymer is then transferred to a reactor equipped with a
disked cage-type agitator with high surface activity. The final viscosity of the polymer is achieved
by setting the appropriate temperature and vacuum. Short residence time and moderate product
temperature guarantee a high quality product. The excess MEG is removed by evaporation.
Subsequent condensation takes place in the glycol spray condenser systems. The spent MEG
is transferred to a recovery unit. PET melt can be pumped to a chip production unit or to a direct
spinning plant.
140 ~
ETHYLENE DICHLORIDE
C C
Cl Cl
Ethylene dichloride (EDC), also known as 1,2-dichloroethane, is a colorless, heavy, flammable,

toxic liquid with an odor much like that of chloroform. It is somewhat soluble in water and soluble
in most organic solvents. It is prepared by the vapor, or liquid, phase reaction of ethylene and
chlorine in the presence of a suitable catalyst. EDC is primarily used to produce vinyl chloride
monomer (VCM), which is in turn used to produce polyvinyl chloride (PVC). It is also used in the
production of chlorinated solvents. It was first produced in 1794.
The global EDC industry is dominated by a relatively small group of producers, most of whom
are back-integrated to chlorine and/or ethylene, which are the primary feedstocks in the EDC
production process. Some EDC producers are also forward integrated to VCM and PVC. EDC
is considered an intermediate product required for the production of VCM. EDC production offers
a method for chlorine producers to ship chlorine internationally.
1. Vinyl chloride
2. Chlorinated solvents
End-Use Products
1. Paints, coatings, and adhesives
2. Solvent bonding of polycarbonate products
3. Solvent extraction of seeds, pharmaceutical materials
4. Film manufacturing
141 ~
World
2007 Ethylene Dichloride Demand By Region
Southeast Asia
5%
Northeast Asia
29%
Indian North America

Subcontinent 27%
3%
Middle East
4%
Africa
1% South America
CIS & Baltic 4%
States
2% Central Europe
3% West Europe
22%
World
2007 Ethylene Dichloride Capacity By Region
Southeast Asia
4%
North America
Northeast Asia 31%
27%
Indian
Subcontinent
2%
South America
Middle East 4%
5%
Africa
1% CIS & Baltic West Europe
2% 3%
142 ~
World
2007 Ethylene Dichloride Demand By Sector
Others
Chlorinated 1%
Solvents
<1% Vinyl Chloride
99%

Ethylene Dichloride
2007
Share
Owner
% of World Capacity
Occidental 10.58%
Dow 9.03%
Formosa Group 8.46%
Solvay 4.52%
TOSOH 4.36%
Georgia Gulf 4.08%
LG Group 2.72%
Arkema 2.66%
Ineos 2.56%
Shin-Etsu 2.37%
Total 51.33%
143 ~
PRODUCTION TECHNOLOGY
• Direct chlorination
KEY PROCESS – DIRECT CHLORINATION
Process Description
The major use for ethylene dichloride is the production of VCM. The majority of EDC plants in the
world are integrated with VCM facilities. Plants do exist, however, which produce EDC solely for
the merchant market. Therefore, stand-alone EDC production is of interest in the vinyls picture.
The crude EDC produced in the direct chlorination reactor is washed and neutralized with caustic,
and dried by distillation. For applications requiring pure EDC, the liquid phase reactor uses the
heat of the reaction to distill the EDC to pure cracking grade (99.99 percent).
In Direct Chlorination, chlorine (liquid or vapor) is reacted with ethylene in a solvent and in the
presence of a catalyst. The solvent is typically EDC, and the catalyst is ferric chloride or a
derivative of ferric chloride, such as ammonium or sodium tetrachloroferrate. The catalyst can be
added to the reactor or generated in situ by corrosion of sacrificial reactor internals or the vessel
itself. The desired reaction follows an ionic pathway, and thus, inhibitors are sometimes added
to help mitigate free radical reactions that result in co-product formation.
The exothermic reaction can be operated at a variety of temperature and pressure conditions
depending upon the overall energy balance of the facility. In cases when the overall energy
balance of the facility results in a surplus of steam, the low temperature process may be preferred.
Here the temperature of the reaction is controlled using water or some other heat transfer medium
circulating in cooling coils inside the reactor, the product EDC is removed as a liquid, washed to
remove the homogeneous catalyst, and distilled. The low temperature process makes the best
use of the feedstocks (it is highly efficient) but does not recover significant amounts of useful
energy from the reaction. Alternatively, the reaction can be run at higher temperatures in a boiling
reactor. In this mode, the product EDC is recovered as a vapor and a washing or neutralizing
step is not required. The efficiency of the high temperature process is slightly lower than that of
the low temperature process, but the energy of the reaction can be captured and utilized to purify
the product EDC as well as EDC from other sources. This is accomplished to different degrees
depending upon the technology employed. In many cases, the value of this chemical energy
more than offsets the slight reduction in feedstock utilization efficiency.
Details of EDC production are available in the Process Description for Vinyl Chloride Monomer
production technology.
144 ~
VINYL CHLORIDE MONOMER
C C
Cl
Vinyl chloride monomer (VCM) is the basic material from which PVC is made via polymerization.
VCM is a highly flammable gas made almost exclusively for use in the production of PVC. It is a
known human carcinogen for which low limits are imposed at the workplace. VCM is manufactured
by the heating of ethylene dichloride (EDC) to around 700oF in the presence of oxygen.
VCM is a highly volatile molecule that exists as an easily liquefiable gas at standard temperature
and pressure. The smell of VCM is described as sweet, although the presence of VCM is not
detectable at safe levels of exposure. Essentially all VCM produced is used in the manufacture
of PVC. VCM is transported via pipeline, railcar or in specialized gas container ships.
Global VCM production is dominated by a relatively small group of producers, most of whom are
at least partially back-integrated into EDC. Most VCM producers are also forward integrated into
PVC production, as more than 95 percent of VCM production is associated with PVC demand.
Dow Chemical is a notable exception in that they are the world’s largest producers of VCM but do
not produce PVC. Dow has a strategic relationship with Shintech, the largest producer of PVC
in North America.
1. Polyvinyl chloride (PVC)
2. Chlorinated solvents
145 ~
World
2007 Vinyl Chloride Monomer Demand By Region
Northeast Asia
41% Southeast Asia
5%
Indian
Subcontinent
3%
North America
Middle East 21%
2%
Africa
1%

States West Europe 4%
3%
World
2007 Vinyl Chloride Monomer Capacity By Region
Northeast Asia
Middle East Indian 45%
3% Subcontinent
Africa 2%
1%
CIS & Baltic

States
2%
Central Europe
3%
West Europe
Southeast Asia
16%
4%
South America
3% North America
21%
146 ~
World
2007 Vinyl Chloride Monomer Demand By Sector
Others
1%
Polyvinyl Chloride
99%
Vinyl Chloride Monomer

2007
Share
Owner
% of World Capacity
Formosa Group 6.73%

Occidental 6.71%
Dow 5.39%
TOSOH 3.54%
Georgia Gulf 3.42%
Solvay 3.34%
LG Group 2.96%
Ineos 2.42%
Arkema 2.41%
Shin-Etsu 2.25%
Total 39.18%
147 ~
• Balanced oxychlorination
• Catalytic addition of hydrogen chloride (HCl) to acetylene
KEY PROCESS – BALANCED OXYCHLORINATION PROCESS
HCI Recycle H2
Acetylene
Hydrogenation
O2 or air O2 or air Catalytic

Oxy Oxidation
Chlorination HCI Recycle
light and
C2H4 heavy ends
H2 O To WWT
EDC EDC VCM VCM
Purification Cracking Purification
EDC Recycle
CI 2
Direct
Chlorination
Process Description
The so-called balanced process, based on ethylene, is the most common method used to
produce VCM on both a total capacity and number of facilities basis. There are three core unit
operations in the balanced VCM process. These are (1) the direct addition of chlorine to ethylene
(Direct Chlorination), (2) EDC Pyrolysis to produce VCM and HCl (Cracking), and (3) the catalytic
reaction of ethylene, HCl, and oxygen to produce EDC (Oxychlorination). In addition, there are
purification trains for both EDC and VCM. Environmental regulations and prudent practices also
require the use of systems to handle liquid chlorinated co-products, waste water, and vent gases.
An overview of the 7th Generation OxyVinyls VCM process is given in the diagram above.
The development and commercialization of the oxychlorination process was the keystone to the
commercial development of the balanced process. Since the cracking of EDC produces one
molecule of HCl for every molecule of VCM, an economical use for this HCl was needed for the
ethylene route to VCM to be viable. The oxychlorination process utilizes the HCl produced in the
cracking of EDC to VCM to produce additional EDC. Thus, the overall process was “balanced”
in terms of HCl generation (in cracking) and consumption (in oxychlorination). It is important to
note that the process need not be (and often is not) operated in the balanced mode. Based on
local economics or other considerations, some producers will import or export EDC and/or HCl
from/to other facilities and processes. For example, it has become increasingly common for MDI/
TDI producers to ship their co-product HCl by pipeline to oxychlorination reactors associated with
VCM production facilities.
148 ~
EDC is converted to VCM and HCl by means of thermal pyrolysis, or cracking. The cracking
reaction involves a free radical chain mechanism, and thus, it can be accelerated by use of
promoters and retarded by use of inhibitors. The cracking is carried out at temperatures around
500°C. Technologies exist to feed either liquid EDC (which is vaporized in the cracking furnace)
or vapor EDC (vaporized external to the furnace). Most current technologies employ various
means of recovering the excess heat from the furnace stacks and/or effluent streams. Typically,
about half of the EDC is cracked to HCl and VCM in the furnace, and the balance is recycled
through a purification train. Higher levels of conversion can be achieved at higher temperatures
or by means of cracking promoters, but these may lead to the acceleration of coke formation and
reduced furnace run life. The furnace effluent is quenched and then separated into HCl, which is
recycled to the oxychlorination section, VCM product, and recycle EDC by means of distillation.
The recycle EDC contains co-products of the cracking process and requires further purification
by either a separate distillation column or by combining it with the crude EDC from the direct
chlorination and oxychlorination units.
In the oxychlorination process, ethylene, HCl and oxygen are combined to produce EDC and
water. The reaction is carried out in the vapor phase over a heterogeneous catalyst that is
usually comprised of copper chloride and proprietary additives on a support matrix. Both fixed-
bed and fluid-bed technologies exist. The source of oxygen may be air, oxygen enriched air, or
pure oxygen. When purified oxygen is employed, it is common to recycle the reactor effluent
gases back to the reactor after condensing out the product EDC and water. In such recycle
operations, care must be taken in the design and operation of the units to prevent the buildup of
a flammable mixture of oxygen and fuel in the recycle gas stream. The oxychlorination reaction
is highly exothermic and the heat of the reaction is typically used to produce steam.
149 ~
POLYVINYL CHLORIDE
C C
...
Cl ...
Polyvinyl chloride (PVC) was first discovered in 1872 by the German chemist Eugen Baumann,
but it was not patented until several years later by another German, Friedrich Klatte in 1913.
Even then, it was not considered a useful product until 1926 when Waldo Lonsbury Semon of the
B.F. Goodrich Company invented plasticized PVC.
PVC is a large polymer chain of repeating units of vinyl chloride monomer. It can be either rigid
or flexible, depending on the additives used. These additives, called plasticizers, can leak out of
vinyls products and have caused some to question the use of PVC from an environmental safety
and human health perspective.
Regardless, PVC is one of the largest volume thermoplastic polymers consumed in the world
today and may be the most versatile plastic. The diversity of PVC is exemplified by the wide
variety of its end-use applications. Examples of PVC based products include: water and sewer
pipes, wire and cable insulation and jacketing, door and window frames, toys, packaging, furniture
and blood bags. In its many years of use, PVC has developed a high level of market penetration
in the more industrialized regions of the world.
The PVC industry is dominated by a relatively small group of global producers, most of whom
are at least partially back-integrated into vinyl chloride monomer (VCM) and ethylene dichloride
(EDC). VCM and EDC are two key feedstocks necessary for the production of PVC. Some
producers are also forward integrated from PVC and produce either PVC compounds or end-use
PVC products such as PVC pipe or vinyl film and sheet.
1. Calendering: flooring and textiles
2. Coatings: flooring, textile and paper coatings, protective coatings and adhesives
3. Rigid pipes and tubing
4. Other extrusions: wire and cable, film and sheet (packaging and non-packaging), siding and
windows and doors
5. Moldings: bottles and fittings
6. Paste/plastisols
150 ~
World
2007 Polyvinyl Chloride Demand By Region
Northeast Asia
38% Southeast Asia
5%
Indian
Subcontinent
4% North America
19%
Middle East
5%
2% 5%
CIS & Baltic
States Central Europe West Europe
3% 2% 17%
World
2007 Polyvinyl Chloride Capacity By Region
Northeast Asia
43%
Southeast Asia
5%
Indian
Subcontinent
North America
3%
20%
Middle East
2%
1% 4%
2% 3%
151 ~
Polyvinyl Chloride
2007
Share
Owner
% of World Capacity
Shin-Etsu 7.65%
Formosa Group 7.33%
Occidental 4.75%
Georgia Gulf 3.52%
Solvay 3.45%
Ineos 3.26%
LG Group 2.69%
Arkema 2.25%
SINOPEC 2.13%
Norsk Hydro 1.89%
Total 38.93%
152 ~
• Suspension polymerization
• Emulsion (microsuspension) process
• Mass (bulk) process
KEY PROCESS – SUSPENSION POLYMERIZATION PROCESS
De-ionized Water, Agent, Catalyst
Vinyl Chloride
Centrifuge
VCM RECOVERY
STRIPPER
VCM TANK
SILO
Waste Water
Dryer
Reactor
Screen PVC
Process Description
The suspension method is so named because vinyl chloride is combined with water in the
presence of a suspension agent in a stirred reactor to form a suspension of vinyl chloride in
a continuous water phase, but at a much more reduced level than in emulsion polymerization.
Once mixed, this suspension is stable until polymerization begins, which occurs when the vinyl
chloride monomer (VCM) soluble initiator is added to the mixture. Since the initiator is water
insoluble, each suspended droplet acts as a miniature bulk polymerizer.
The formulation of polyvinyl chloride (PVC) from VCM involves the breaking of the double carbon
bond by a free radical and then reaction with other VCM molecules. When water and vinyl
chloride are mixed with vigorous agitation, a suspension is formed of small VCM droplets (10-150
micron in diameter) in water. This suspension is stable only with agitation, as the two liquids
are immiscible. If this mixture were allowed to react, the resulting PVC particles would tend to
agglomerate into very large particles (up to the size of the reactor). For this reason, a suspending
agent (also referred to as a protective colloid or emulsifier) is added initially to the water and VCM
before the initiator is charged. The emulsifier is a non-ionic water-soluble polymer. When mixed
with water and vinyl chloride, the emulsifier surrounds each VCM droplet and forms a protective
153 ~
barrier. This barrier is effective because when two droplets collide, the polymers are compressed.
This compression is essentially an increase in the concentration of the emulsifier polymer, and
as such, results in an increase in osmotic pressure at the point of collision. To counteract this
increase in pressure, water diffuses into the area of contact and pushes the droplets apart.
The emulsifier polymers have both a VCM soluble component and a VCM insoluble component.
The VCM insoluble component serves to anchor the emulsifier on the surface of the vinyl chloride
droplet to avoid desorption during droplet collisions.
Various emulsifier agents are used in the process. The most prevalent are polyvinyl alcohol
(PVA) of different levels of hydrolysis, methyl cellulose and polyoxyethylene sorbitan monolaurate.
Each of these substances provides varying levels of colloidal protection for the droplets. A PVA of
88 percent hydrolysis provides a high level of protection. The resin particles produced by using
this emulsifier generally have a smoother surface (less aggregation with colliding particles) and
lower porosity than those made with a lower hydrolysis PVA. The lower percent hydrolyzed PVA,
namely 72.5, 55 and 45, provide less colloidal protection, but are more efficient in their ability
to coat particles. Hence, the initial monomer droplets are smaller. This combination of smaller
droplets with less colloidal protection allows for a final product that is an aggregate of many
original VCM droplets.
The initiator is charged as a water dispersion composed of small droplets, less than 10 um, of
initiator suspended in the aqueous phase by an emulsifier. Once charged to the polymerizer, it
is absorbed by the VCM droplets. The PVC polymer chains then begin to grow and terminate.
When about 50 of these have formed, they agglomerate. As a number of these PVC chain
agglomerates form, they too agglomerate into small particles called primary particles. The
primary particles are less than one um in diameter and are formed at less than two percent
conversion. It is during this period that a graft copolymerization of PVC and the polyvinyl alcohol
colloid starts to form.
The primary particles remain discrete particles for a short time and continue growing within each
droplet. During the range of 3-10 percent conversion, the primary particles then agglomerate
into a floc arrangement. This agglomeration step is considered the critical one for determining
the morphology of the resin particles. The spatial configuration into which these primary particles
form determines the level of porosity in the final resin grain. Loosely stacked packing provides a
porous resin particle while close packing results in a more solid resin particle.
Both reaction temperature and agitation have a tremendous influence on grain structure
because of this stacking. It has been found that as agitation increases, the primary particles
tend to be more loosely packed. Increasing reaction temperature tends to create a more
tightly packed arrangement and, therefore, lower porosity. Once the primary particles
have agglomerated in the 3-10 percent conversion range, no further primary particles are
formed.
It has also been found that another agglomeration occurs on a larger scale over the 5-30 percent
conversion range. This is actual VCM droplet or grain agglomeration. The polymerizing VCM
droplets get quite sticky and will readily adhere to one another in the early stage of polymerization;
hence, the need for a protective colloid (emulsifier). However, as previously noted, during the
early stages, the protective colloid is undergoing a graft copolymerization with the growing PVC
chains to form a protective membrane. During this copolymerization period, more emulsifier is
required on the surface of the droplet and is obtained from the water phase.
154 ~
CHLORINE
Cl Cl
Chlorine was first discovered in 1774 by Swedish pharmacist Carl Wilhelm Scheele and is a
pale green gas at standard temperature and pressure. Because it is highly reactive, chlorine is
usually found in nature bound with other elements such as sodium, potassium and magnesium
as organochlorine compounds and salts. Today, chlorine is used in many industries as well
as household products and can be easily recognized by its pungent odor, which is like that of
bleach.
Chlorine is found in abundance and has extremely desirable properties, such as its extraordinary
ability to extend a chemical bridge between various elements and compounds that would
not otherwise react with each other. Such chlorine chemistry has been especially useful in
synthesizing organic compounds and is critical to the manufacture of products used in everyday
life, such as vinyl siding, windows, plumbing pipes, upholstery, microprocessors, computer disks
and toys.
The basis of industrial chlorine production involves a salt crystal, usually sodium chloride,
dissolved in water with an electric current passed through the solution (brine) between immersed
conductors. The positive sodium ions (Na+) move toward the negative electrodes (cathodes),
and negative chlorine ions (Cl-) move toward the positive electrodes (anodes). At the electrodes,
the ions lose their molecular charges and neutral molecular products are released. The
decomposition process continues as long as the current flows.
NaCl + H2 O NaOH + ½ Cl2 + ½ H2
Sodium Water Sodium Chlorine Hydrogen

Chloride Hydroxide
(Salt) (Caustic Soda)
Due to the various physical properties and the chemical nature of the reaction, there is a definite
ratio of products from the reaction. Chemically equivalent amounts of products will always be
produced. In other words, in making 1.0 unit of chlorine, 1.1 dry units of sodium hydroxide
(caustic soda) will be produced. The combined volume of 1.0 unit of chlorine and 1.1 units of
sodium hydroxide is called an Electro Chemical Unit, or ECU.
The electrolysis process can also be used for producing chlorine and potassium hydroxide (KOH)
from potassium chloride. In this case, the ratio is 1.54 dry units of KOH per 1.0 unit of chlorine.
155 ~
1. Organics: propylene oxide, epichlorohydrin, and the phosgene chemicals (MDI/TDI/

polycarbonates)
2. Chlorinated Intermediates: chloroform, methylene chloride, methyl chloride, perchloroethylene,

carbon tetra chloride, 1,1,1-trichloroethane, and trichloroethylene
3. Inorganics: titanium dioxide and bromine
4. Others: water treatment chemicals, agricultural chemicals, hydrochloric acid, bleach and
chlorobenzenes
End-Use Products
1. Organics: paints & varnishes, cosmetics and flavoring extracts
2. Chlorinated Intermediates: pharmaceuticals, refrigerants and semi-conductors
3. Inorganics: catalyst, electrical components and synthetic gemstones
4. Others: drinking water disinfection and waste & sewage treatment
156 ~
World
2007 Chlorine Demand By Region
Indian
Subcontinent
Middle East 3%
3%
Northeast Asia
Africa 42%
1%
CIS & Baltic

States
3%
Central Europe
2%
Southeast Asia
West Europe 2%
18%
South America
North America
3%
23%
World
2007 Chlorine Capacity By Region
Northeast Asia
41% Southeast Asia
3%
Indian
Subcontinent
4%
Middle East North America

3% 21%
Africa
1%
States 3%
3% West Europe
Central Europe 18%
3%
157 ~
World
2007 Chlorine Demand By Sector
Others
28%
Water Treatment
5%
Pulp & Paper

2%
Vinyls
Inorganics 37%
2%
Chlorinated
Intermediates
6%
Polycarbonates MDI
1% 4% TDI
3% Propylene Oxide
Epichlorohydrin 7%
5%
Chlorine
2007
Share
Owner
% of World Capacity
Dow 9.47%
Occidental 5.33%
Formosa Group 3.37%
Solvay 2.77%
PPG 2.75%
Bayer 2.46%
Olin 2.13%
Asahi Glass 1.66%
Akzo Nobel 1.65%
TOSOH 1.58%
Total 33.17%
158 ~
CAUSTIC SODA
- +
H O Na
“Caustic soda”, also known as sodium hydroxide (NaOH) or lye, is a widely used base material.
The name caustic soda is derived from its corrosive action upon contact with human tissue. It is
one of the oldest man-made chemicals and can be traced back as far as ancient Egyptian times.
Pure caustic soda is a brittle, white solid, which comes in a variety of forms including granules,
flakes and pellets. It readily dissolves in water to form a strong alkaline solution and is most often
used in this form.
Caustic soda is produced as a co-product alongside the production of chlorine in the ‘chlor-
alkali’ process. It is created by combining a salt solution (also known as brine) with an electric
current (electrolysis). Caustic is produced in a ratio of 1.1 units per 1.0 unit of chlorine. The
employment of large amounts of electricity makes this a very ‘energy hungry’ process. This
contributes substantially to the production costs of caustic soda.
It is a very versatile chemical and is used in a wide range of processes including: pulp & paper
production, alumina production, soap & detergent production, textile production and water
treatment, to name but a few. It is also one of the most widely used base chemicals in the
laboratory due to its favorable acid neutralization properties.
1. Pulp & paper
2. Alumina
3. Soaps & detergents/textiles
4. Water treatment
5. Organic chemicals: TDI, MDI, and polycarbonate resins
6. Inorganic chemicals: Titanium dioxide and sodium chlorate
7. Others: Propylene oxide and epichlorohydrin
159 ~
End-Use Products
Wood Pulp Sulfate process. Pulp goes into paper & rayon cellulose plastics
Detergents Cationic surface-active agents
Water Treatment Industrial water treatment to neutralise pH, ion exchange regen.
and on site regeneration of sodium hypochlorite
Alumina Used in Bayer process to ‘digest’ bauxite and remove impurities
Textiles Wet chemical processes of desizing, scouring, mercerisation

and dying cotton
Sodium Silicates Hydrothermal process. Detergent zeolites found in laundry &

dishwashing detergents
Caustic Soda
Propylene Oxide Considered a more environmentally friendly alternative to lime
in chlorohydrin process. PO goes into foams, elastomers,
coatings, adhesives and some molded polymers
Epichlorohydrin Dehydrochlorination. Protective coatings, laminates & glycerin
TDI/MDI Used for flexible & rigid foams in insulation/refrigeration
Polycarbonates Polycondensation process. Automotive, glazing, electronics
Ethylene Amines Neutralisation of amine hydrochlorides
Titanium Dioxide Caustic soda is used to clean exhaust gases
Other Neutralisation, scrubbing, pH control, refining, gas processing,

bleach, monosodium glutamate (MSG)
160 ~
World
2007 Caustic Soda Demand By Region
Northeast Asia
36% Southeast Asia
6%
Indian
Subcontinent
4%
North America
22%
Middle East
2%
Africa
2%
States 6%
West Europe
3% 17%
Central Europe
2%
Total Demand = 58.7 Million Dry Metric Tons
World
2007 Caustic Soda Capacity By Region
Northeast Asia
42%
Southeast Asia
3%
Indian
Subcontinent
4%
Middle East
3%
Africa North America
1% 21%
CIS & Baltic
States
3% South America
3%
3% 17%
Total Capacity = 67.8 Million Dry Metric Tons
161 ~
World
2007 Caustic Soda Demand By Sector
Pulp & Paper
Others 14%
24%
Alumina
11%
Propylene Oxide
Water Treatment 5%
5%
Epichlorohydrin
1%
Organic
Inorganic
Chemicals
Chemicals
12%
14%
Textile Soaps &
8% Detergents
6%
Total Demand = 58.7 Million Dry Metric Tons
Caustic Soda
2007
Share
Owner
% of World Capacity
Dow 9.83%
Occidental 5.24%
Formosa Group 3.50%
Solvay 2.88%
PPG 2.86%
Olin 2.19%
Bayer 1.94%
Akzo Nobel 1.71%
TOSOH 1.64%
Asahi Glass 1.61%
Total 33.41%
162 ~
CHLORINE & CAUSTIC SODA
• Membrane cell process
• Diaphragm cell process
• Mercury cell process
• Chlorine can also be produced from hydrogen chloride and co-produced with a metal
KEY PROCESS – MEMBRANE CELL PROCESS
Water Salt
Brine
Saturation
Evaporation Purification
Purified Brine
Water
Electrolysis
Chlorine
Caustic Soda
Cooling Cooling (Sodium Hydroxide)
Compression Evaporation
Liquefaction Cooling
Evaporation Storage
Caustic Soda
Hydrogen Chlorine (Sodium Hydroxide)
163 ~
Basis of Chlor-Alkali Production
The basis of caustic soda production involves a salt crystal (sodium chloride, NaCl) dissolved in
water, with an electric current passed through the solution (brine) between immersed conductors.
Positive sodium ions (Na+) move toward the negative electrodes (cathodes), and negative chlorine
ions (Cl-) move toward the positive electrodes (anodes). At the electrodes, the ions lose their
molecular charges and neutral molecular products are released. The decomposition process
continues as long as the current flows.
NaCl + H2O NaOH + ½ Cl2 + ½ H2
Sodium Water Caustic Chlorine Hydrogen

Chloride Soda
(Salt) (Sodium Hydroxide)
Due to the various physical properties and the chemical nature of the reaction, there is a definite
ratio of products from the reaction. Chemically equivalent amounts of the products will always be
produced. In other words, to make 1.0 unit of chlorine, 1.1 dry units of sodium hydroxide (caustic
soda) will be produced. The combined volume of 1.0 unit of chlorine and 1.1 dry units of sodium
hydroxide is called an Electro Chemical Unit, or ECU.
Process Description
In the membrane process, the anolyte and catholyte are separated by a cation-exchange
membrane that selectively transmits sodium ions but suppresses the migration of hydroxyl ions
from the catholyte into the anolyte. A brine solution of sodium chloride is fed into the anode
compartment, where chlorine gas is produced, and sodium ions migrate into the catholyte
through the membrane. Depleted brine is discharged from the cell. In the cathode compartment,
hydrogen is produced at the cathode, leaving hydroxyl ions, which, together with the sodium ions
that have crossed the membrane, form caustic soda. Pure water is added to the catholyte to
control the concentration of the caustic soda solution.
Chloride ions in the anolyte are excluded by the cation-exchange membrane so the rate of
diffusion of chloride from the anolyte to the catholyte is extremely low. As a result, a high purity
caustic solution is produced as the catholyte effluent. Since the catholyte is strongly caustic,
there is some back migration of hydroxyl ions from the catholyte into the anolyte.
The membrane is the key component of the membrane cell. Its primary requirements are durability
during electrolysis, high selectivity for sodium ion transport, low electrical resistance, and sufficient
mechanical strength for practical use. The energy requirements and the quality of the solution
depend upon the membrane. Only ion-exchange membranes made of perfluoro-polymer can
withstand severe conditions of exposure to chlorine and caustic soda at high temperatures.
This process produces a higher purity caustic soda solution (32-34 percent), with very low
sodium chloride content. Advantages of the membrane process include its energy efficiency,
which allows for less costly cell operations, and its ability to produce with no asbestos or mercury
environmental contaminants. Disadvantages include the high purity brine requirement and the
high cost of the membrane itself.
164 ~
SODA ASH
- +
O Na
O C
- +
O Na
Soda ash is a basic chemical product with a primary application in the glass industry. It is also
known as di-sodium carbonate, soda, or simply ash. It takes its name from the historical method
of production, which was to combine water with the ashes from specific salt marsh plants (known
as soda in Latin).
It was first brought into commercial production by Nicolas Leblanc in 1791 who patented the
‘Leblanc’ process. This process was, however, rather inefficient and a significant pollutant, which
led to the drive for a more economical procedure. In 1861, Ernest Solvay developed the Solvay
Ammonia process, which is still to this day the dominant process used in the manufacture of soda
ash, accounting for over 50 percent of the world’s total soda ash production.
It is a strong alkali and will easily dissolve in water to form a solution; however, it is generally sold
as a white crystalline powder. As well as being processed from ammonia, salt, and limestone in
the Solvay process, it is also found in large natural deposits around the globe. The majority of
this naturally occurring soda ash is found in the United States at Green River, Wyoming. There
are further commercial natural soda ash mining operations at Searles Lake, California and in
Botswana and Kenya as well as several other locations worldwide.
Soda Ash is a highly versatile chemical and one of the most widely used due to its key end use
applications. As mentioned previously, the largest end use for soda ash is glass. Other important
uses are soaps and detergents as well as being used to manufacture certain chemicals, including
sodium chromates and sodium silicates.
1. Chemicals
2. Glass
3. Soaps & detergents, STPP (sodium tripolyphosphate)
4. Metals & mining
5. Pulp & paper
6. Others: Caustic swing
165 ~
End-Use Products
1. Glass: construction, automotive, containers, consumer products, medical products
2. Chemicals: sodium silicates, sodium dichromates, sodium bicarbonate, caustic soda
3. Soaps & Detergents: used as a surface-active agent, also used indirectly in the production of
other chemicals used as builders in detergent formulations such as sodium tripolyphosphate
(STPP)
4. Metals & Mining: removal of impurities from end products
5. Pulp & Paper: used as a source of alkalinity
6. Caustic Swing: for markets where soda ash is used as a source of sodium or alkalinity it
is often in competition with caustic soda; the choice between soda ash and caustic soda
depending on the relative price of the two materials.
7. Others: effluent treatment and other environmental applications where it is mostly used to
neutralize waste acid streams.
166 ~
World
2007 Soda Ash Demand By Region
Southeast Asia
4%
North America
17%
South America
5%
Northeast Asia
36%
West Europe
15%
Central Europe
3%
Indian CIS & Baltic
Subcontinent States
6% 8%
Middle East Africa
4% 2%
World
2007 Soda Ash Capacity By Region
Southeast Asia
1%
Northeast Asia
38%
North America
23%
South America
Indian <1%
Subcontinent
6% West Europe
12%
Middle East
3%
Africa CIS & Baltic Central Europe
2% States 6%
9%
167 ~
World
2007 Soda Ash Demand By Sector
Chemicals
Others 10%
18%
Pulp & Paper

1% Flat Glass
20%
Metals & Mining
5%
Soaps &
Detergents
16%
Other Glass Container Glass

6% 24%
Soda Ash
2007
Share
Owner
% of World Capacity
Solvay 13.23%
FMC Corp. 5.38%
Tata Chemicals 5.14%
Sterlitamsk Combine 3.83%
Shandong Ocean 3.29%
Ciech 3.11%
Tangshan SanYou Group 2.92%
Sisecam 2.80%
General Chemical (Soda Ash) Partners 2.32%
Sun Capital Partners 2.02%
Total 44.05%
168 ~
• Natural Soda Ash Mining
• Solvay Ammonia Process (the most common synthetic process)
• HOU Process (common synthetic process in China)
KEY PROCESS – SOLVAY AMMONIA PROCESS
CO2 Gas
Compression
Brine
Ammonia
Purification
Carbonation
Brine
Ammonia
Absorption Filtration Calcination Light Soda Ash

Limestone
Hydrator
Coke Lime Kiln Crystallizer
Distillation
Lime milk
Dryer
Water Lime slaker
Steam Dense Soda Ash
Distillation Liquid
Process Description
The Solvay Ammonia process is the most commonly used process to make synthetic soda ash.
This process was developed in 1861 by Ernest Solvay. The Solvay process, also called the
Ammonia Soda process, uses salt (NaCl) and limestone (CaCO3) as raw materials. Ammonia,
which is also used in the process, is almost totally regenerated and recycled.
169 ~
The main advantage of this process is the availability of the raw materials, which can be found
almost anywhere in the world and therefore allows operating production units to be relatively
close to the market. The main production process steps are:
i. Brine purification
ii. Lime kilns and slaker (dissolver); Limestone calcination and milk of lime production
iii. Absorption of ammonia
iv. Carbonation: Precipitation of NaHCO3
v. Filtration: Separation of NaHCO3 crystals from mother liquor
vi. Calcination: Decomposition of NaHCO3 to Na2CO3
vii. Distillation: Recovery of ammonia
viii. Densification: Production of dense soda ash
170 ~
METHANOL
C O H
Methanol was first isolated by Robert Boyle in 1661 by distillation of the vegetation boxwood. It is
the simplest of the class of compounds known as alcohols with a chemical formula of CH3OH. It
is a liquid that is colorless, flammable and poisonous with a smell similar to ethanol, the alcohol
that is consumed in beverages.
Methanol’s flammable nature allows it to be used as a fuel source, primarily in racing. The
production and use of methyl tertiary-butyl ether (MTBE) from methanol and its use as a major
component in the automotive fuel pool was wide spread until recently. Concerns of ground
water contamination from leaking gasoline storage tanks forced the removal of it from gasoline
blending. Methanol can be used as a solvent and in conjunction with other chemicals to produce
a wide variety of end products.
Methanol is produced almost entirely from reacting methane, a component of natural gas, with
steam and/or oxygen over a catalyst bed and has three basic steps: synthesis gas production,
methanol synthesis and distillation. Of the production methods employed, it is the manner
in which these stages are performed that differs. The methods available are: low pressure,
combined reforming, two stage reforming and auto-thermal reforming.
1. Organics: formaldehyde, MTBE, acetic acid, dimethyl ether, and methyl methacrylate
2. Others: fuels and solvents
End-Use Products
Methanol is used to make fuel and is a precursor to acrylic sheeting, coatings, resins and
biodiesel
171 ~
World
2007 Methanol Demand By Region
Southeast Asia
6% North America
19%
South America
3%
Northeast Asia
36%
West Europe
18%
Indian
Subcontinent Central Europe
3% 3%
Middle East CIS & Baltic
Africa States
6% 1% 5%
World
2007 Methanol Capacity By Region
North America
Southeast Asia
3%
5%
South America
Northeast Asia 26%
24%
Indian
Subcontinent West Europe
1% 7%
Central Europe
1%
Middle East
CIS & Baltic
20% Africa States
4% 9%
172 ~
World
2007 Methanol Demand By Sector
Others
20%
Formaldehyde
35%
Solvents
4%
Dimethyl Ether
3%
Gasoline/Fuel
6%
Methyl
Methacrylate
3% DMT
3%
MTBE/TAME Acetic Acid
15% 11%
Methanol
2007
Share
Owner
% of World Capacity
Methanex 12.87%
SABIC 4.47%
NPC-Iran 4.25%
Japanese Methanol Consortium 3.87%
MHTL - M5 3.87%
Metafrax 2.04%
Azot Tolyatti 2.04%
Norwegian Government 1.85%
Tomsk Methanol 1.53%
Petronas 1.49%
Total 38.27%
173 ~
• Natural gas/light gases process
• Heavy liquid feedstock process
• Coal feedstock process
KEY PROCESS – METHANOL VIA NATURAL GAS (STEAM REFORMING)

Low Pressure
Steam
Water Removal
Synthesis
Natural Sulfur Gas
Gas Removal Reforming and
Saturator
Heat Recovery
Makeup Water CH4 + H2O CO + 3H2
Purge Gas
To Fuel
Purification
Methanol
Separation
Methanol Synthesis
Synthesis Gas
Crude Methanol Reaction
CO + 3H2 CH3OH
This process employs catalytic steam reforming of a hydrocarbon feedstock to yield synthesis
gas. This is then compressed and reacted over a catalyst bed to produce methanol which is
then purified by distillation. Due to the stoichiometry of the reactions, there is excess hydrogen
produced. The yields can be increased through the addition of carbon dioxide if available.
Combined Reforming
With this technology, a portion of the natural gas is reformed at high pressure and relatively low
temperature and then re-mixed with the remainder of the natural gas feed. This makes it possible
to adjust the composition of the synthesis gas to compensate for longer carbon chain components
as well as reducing the size or cost of the reformer. This combined stream is totally reformed
at high pressure using oxygen as a reforming agent. As only about half of the stream is fed to
the steam intensive reformer, overall energy requirements are reduced. Methanol synthesis and
purification are essentially the same as the low pressure process.
174 ~
Two Stage Reforming
This process is conceptually similar to the combined reforming process described above in that it
involves reducing the load to a conventional steam reformer. Instead of an autothermal reformer
downstream of the conventional steam reformer however, a pre-reformer is utilized to adjust
the feed gas stoichiometry, resulting in a lower steam to carbon ratio of the generated synthesis
gas.
Autothermal Reforming
In this process, oxygen, natural gas and steam are all introduced into the reactor (over a catalyst)
to form the synthesis gas. This simplifies the process, and reduces the plot area and construction
costs. Methanol synthesis and distillation are essentially the same as the other processes. The
higher pressure and low steam requirements of this process are more favorable for larger scale
plants where the higher capital costs can be defrayed over more tons. The plant size achievable
is restricted by the air distillation columns in the oxygen plant.
175 ~
176 ~
Conversion Factors
177 ~
ETHYLENE DERIVATIVES
Feed Derivative Feed Per Metric Ton of

Derivative
Ethylene Acetaldehyde 0.68
Acetaldehyde Acetic Acid 0.77
Acetic Acid Ethyl Acetate 0.69

Acetic Acid Ethylene Glycol Monoethyl Ether Acetate 0.48
Acetic Acid Chloroacetic Acid 0.68
Acetic Acid n-Butyl Acetate 0.54
Acetic Acid Isobutyl Acetate 0.52
Acetic Acid Acetic Anhydride (via ketene) 1.20
Acetic Acid Vinyl Acetate 0.72
Ethylene Alpha Olefins 1.10
Ethylene Ethanol 0.64
Ethanol Ethyl Acetate 0.59

Ethanol Ethyl Acrylate 0.48
Ethanol Monoethyl Ether 0.57
Ethanol Ethyl Ether 1.30
Ethylene Ethyl Chloride 0.48

Ethylene Ethylbenzene 0.275
Ethylbenzene See under Benzene-Ethylbenzene
Ethylene Ethylene Dichloride 0.30
EDC Vinyl Chloride Monomer 1.60
VCM See under Ethylene-VCM
EDC 1,1,1 - Trichloroethane 0.80

EDC Trichloroethylene 0.85
178 ~
Conversion Factors

Derivative
EDC Perchloroethylene 0.70

EDC Vinylidene Chloride 1.26
EDC Ethyleneamine 2.30
Ethylene Monoethylene Glycol 0.60
MEG Antifreeze 0.95

MEG Polyester Fiber 0.35 - 0.355
MEG Polyester Film 0.34 - 0.36
MEG Polyester Bottle Resin 0.36
MEG Polyester Polymer 0.35 average
Ethylene Ethylene Oxide 0.84
Ethylene Oxide Monoethylene Glycol 0.72
MEG See under Ethylene-MEG
Ethylene Oxide Diethylene Glycol 0.84

Ethylene Oxide Triethylene Glycol 0.92
Ethylene Oxide Monoethanolamine 0.74
Ethylene Oxide Diethanolamine 0.86
Ethylene Oxide Triethanolamine 0.92
Ethylene Oxide Ethanolamine 0.84 average
Ethylene Oxide Ethoxylate 0.84 average
Ethylene Oxide Glycol Ether 0.55 average
Ethylene Oxide Polyethylene Glycol 0.90
Ethylene Ethylene Propylene Rubber 0.55

Ethylene High Density Polyethylene 1.02
Ethylene Linear Low Density Polyethylene 0.93
Ethylene Low Density Polyethylene 1.015
Ethylene Propionaldehyde 0.54
Ethylene Styrene 0.30
Ethylene Vinyl Acetate 0.38
179 ~
Conversion Factors

Derivative
Vinyl Acetate Ethylene/Vinyl Acetate copolymer 0.20 typical

Vinyl Acetate Polyvinyl Acetate 1.05
Vinyl Acetate Vinyl Acetate/VCM copolymer 0.14
Ethylene Vinyl Chloride Monomer 0.49
VCM Polyvinyl Chloride homopolymer 1.00

VCM 1,1,1 - Trichloroethane 0.50
VCM Vinylidene Chloride 0.75
VCM VCM/Vinyl Acetate copolymer 0.90
VCM VCM/Vinylidene Chloride copolymer 0.15 typical
180 ~
Conversion Factors
PROPYLENE DERIVATIVES

Derivative
Propylene Acrylic Acid 0.73
Acrylic Acid n-Butyl Acrylate 0.59

Acrylic Acid Ethyl Acrylate 0.77
Acrylic Acid 2-Ethylhexyl Acrylate 0.41
Acrylic Acid Methyl Acrylate 0.88
Propylene Acrylonitrile 1.10
Acrylonitrile Acrylonitrile Butadiene Styrene 0.24

Resin
Acrylonitrile Acrylamide 0.77
Acrylonitrile Acrylic Fiber 0.96
Acrylonitrile Adiponitrile 1.09
Acrylonitrile Nitrile Rubber 0.35
Acrylonitrile Styrene Acrylonitrile Resin 0.30
Propylene Butyraldehyde 0.72

Propylene Cumene 0.39
Propylene Dodecene 1.30
Propylene Epichlorohydrin 0.72
Epichlorohydrin Epoxy Resin - modified 0.43

Epichlorohydrin Epoxy Resin - unmodified 0.47 - 0.68
Epichlorohydrin Glycerin 1.12
Epichlorohydrin Phenoxy Resin 0.40
Propylene Ethylene Propylene Rubber 0.40

Propylene 2-Ethylhexanol 0.90
2-Ethylhexanol Dioctyl Phthalate 0.70
Propylene Glycerine 0.78

Propylene Heptene 0.58
Propylene Isobutanol 0.75
Propylene Isopropanol 0.78
181 ~
Conversion Factors

Derivative
Isopropanol Acetone 1.08
Acetone Bisphenol A 0.28

Bisphenol A See under Benzene-Cumene-
Phenol-Bisphenol A
Acetone Methyl Isobutyl Ketone 1.25
Acetone Methylmethacrylate 0.68
Propylene n-Butanol 0.75

Propylene Nonene 1.10
Propylene Polypropylene 1.03
Propylene Propylene Oxide (via Chlorohydrin 0.85
process)
Propylene Propylene Oxide (via PO/SM 0.79
process)
Propylene Oxide Propylene Glycol 0.77

Propylene Oxide Dipropylene Glycol 0.94
Propylene Oxide Urethane Polyol - flexible 0.90 average
Propylene Oxide Urethane Polyol - rigid 0.70
Propylene Oxide Nonurethane Polypropylene Glycol 1.00
182 ~
Conversion Factors
Butadiene DERIVATIVES

Derivative
Butadiene Acrylonitrile Butadiene Styrene Resin 0.21

Butadiene Adiponitrile 0.62
Butadiene C4 Hydrogenation (as contained 0.50
butadiene)
Butadiene Nitrile Rubber 0.65
Butadiene Polybutadiene Rubber 0.93
Butadiene Polychloroprene Rubber 0.75
Butadiene Styrene Butadiene Latex 0.41
Butadiene Styrene Butadiene Rubber (emulsion) 0.615
Butadiene Styrene Butadiene Rubber (solution) 0.76
Butadiene Cyclododecatriene 1.15

Butadiene Ethylidene Norbornine 1.10
Butadiene Hexadiene 1.05
Butadiene Hydroxy Polybutadiene 1.15
Butadiene K-Resin 0.25
Butadiene Polymethacrylate Butadiene Styrene 0.30
Butadiene Thermoplastic Elastomer (SBS & SIBS) 0.69
Butadiene 2,6-Naphthalene Dicarboxylic Acid 0.33
Isobutylene Methyl Tertiary Butyl Ether 0.65

Isobutylene Butyl Rubber 0.98
Isobutylene Polyisobutylene 1.20
Isobutylene Methylmethacrylate 0.68
Isobutylene Methacrylonitrile 1.58
Normal Butylene Methylethylketone 1.79

Normal Butylene Linear Low Density Polyethylene 0.08
183 ~
Conversion Factors
BENZENE DERIVATIVES

Derivative
Benzene Alkylbenzene 0.40

Benzene Aniline 0.88
Benzene Chlorobenzene 0.76
Benzene Cumene 0.67
Cumene Alphamethylstyrene 1.13

Cumene Phenol 1.35
Phenol Adipic Acid 0.72

Phenol Aniline 1.02
Phenol Alkylphenol 0.46
Phenol Bisphenol A 0.88
Bisphenol A Epoxy Resin 0.75

Bisphenol A Tetrabromobisphenol 0.50
Bisphenol A Polycarbonate 0.92
Phenol Caprolactam 0.90

Phenol Cyclohexanone 0.98
Phenol Phenolic Resin 0.45
Benzene Cyclohexane 0.93
Cyclohexane Adipic Acid 0.73
Adipic Acid Adiponitrile 1.67

Adipic Acid Hexamethylenediamine 1.50
Adipic Acid Nylon Melt 0.61
Cyclohexane Caprolactam 1.02
Caprolactam Nylon Melt 1.045
Benzene Dichlorobenzene 0.62

Benzene Ethylbenzene 0.75
184 ~
Conversion Factors

Derivative
Ethylbenzene Styrene 1.12
Styrene Polystyrene - EPS Bead 1.00

Styrene Polystyrene - GP Crystal 1.00
Styrene Polystyrene - High Impact 0.93
Styrene Acrylonitrile Butadiene Styrene Resin 0.52
Styrene Styrene Acrylonitrile Resin 0.71
Styrene Styrene Butadiene Latex 0.55
Styrene Styrene Butadiene Rubber 0.23
Styrene Unsaturated Polyester Resin 0.36
Styrene K Resin® Styrene Butadiene 0.70
copolymer
Styrene Methacrylate Butadiene Styrene 0.30
Styrene Styrene Maleic Anhydride 0.88
Styrene Terpine Resin 0.40
Styrene XT Polymer 0.24
Styrene Floor Coating 0.40
Styrene PS Latex 0.67
Styrene Thermoplastic Elastomer (SIS & SBS) 0.25
Styrene High SM copolymer 0.91
Styrene Acrylic/SM Emulsion 0.20
Styrene Opaque Polymer 0.79
Styrene Plastics Additive 0.30
Styrene Ion Exchange Resin 0.90
Styrene Toner Resin 0.40
Styrene Ethylene Styrene Inter 0.50
Styrene Syndiotactic Polystyrene 0.90
Benzene Maleic Anhydride 1.25

Benzene Nitrobenzene 0.65
185 ~
Conversion Factors
TOLUENE & XYLENE DERIVATIVES

Derivative
Toluene Benzene (via disproportionation) 2.50

Toluene Benzene (via hydroalkylation) 1.23
Toluene Benzl Chloride 0.80
Toluene Benzoic Acid 0.84
Toluene Caprolactam 1.05
Toluene Toluene Diisocyanate 0.59
Toluene Diisocyanate Urethane Foam - flexible 0.32 average

Toluene Diisocyanate Urethane Foam - rigid 0.40 average
Toluene Diisocyanate Urethane Elastomer 0.30 average
Orthoxylene Phthalic Anhydride 0.96
Phthalic Anhydride Alkyd Resin 0.35 average

Phthalates:
Phthalic Anhydride Butyloctyl 0.47
Phthalic Anhydride Diethyl 0.78
Phthalic Anhydride Diisodecyl 0.34
Phthalic Anhydride Dimethyl 0.81
Phthalic Anhydride Di-n-butyl 0.55
Phthalic Anhydride Dioctyl 0.39
Phthalic Anhydride Unsaturated Polyester Resin 0.25 average
Metaxylene Isophthalic Acid 0.70
Paraxylene Dimethyl Terephthalate 0.59
DMT PET Resin 1.02

DMT Polyester Fiber 1.06
DMT Polyester Melt 1.045
DMT Polybutylene Terephthalate 0.89
DMT Other DMT(Cyclohexane Dimethanol) 0.94
Paraxylene Purified Terephthalic Acid 0.67
186 ~
Conversion Factors

Derivative
PTA DMT 0.87

PTA PET Resin 0.87
PTA Polyester Fiber 0.90
PTA Polyester Melt 0.88
PTA Polytrimethylene Terepthalate 0.78
187 ~
Conversion Factors
CHLOR-ALKALI DERIVATIVES
Feed Derivative Feed per Metric Ton of

Derivative
Chlorine Ethylene Dichloride 0.73

Chlorine Vinyl Chloride Monomer 0.60
Chlorine Propylene Oxide 1.40
Chlorine Epichlorohydrin (allyl chloride process) 2.12
Chlorine Toluene Diisocyanate (via phosgene) 0.96
Chlorine Methylene Diphenyl Diisocyanate 0.66
(via phosgene)
Chlorine Chloroform 0.90
Chlorine Methylene Chloride 0.84
Chlorine Perchloroethylene 0.86
Chlorine Trichloroethylene 0.81
Chlorine 1,1,1 - Trichloroethane 0.80
Chlorine Carbon Tetrachloride 0.93
Chlorine Titanium Dioxide 0.15
Chlorine Bromine 0.65
Chlorine Methyl Chloride 0.80
Chlorine Polycarbonates (via phosgene) 0.31
Chlorine Chemical Pulp (non-ECF Mills) 0.02 - 0.04
Caustic Soda Propylene Oxide 1.20

Caustic Soda Epichlorohydrin 0.80
Caustic Soda Toluene Diisocyanate (via phosgene) 0.05
Caustic Soda Methylene Diphenyl Diisocyanate 0.15
(via phosgene)
Caustic Soda Titanium Dioxide 0.12
Caustic Soda Vinylidine Chloride 0.46
Caustic Soda Polycarbonate (via phosgene) 0.50
Caustic Soda Chemical Pulp 0.047
Caustic Soda Alumina 0.03 - 0.10
Sodium Chlorate Softwood Pulp 0.045

Sodium Chlorate Hardwood Pulp 0.030
Sodium Chlorate Eucalyptus Hardwood Pulp 0.028
188 ~
Conversion Factors
SODA ASH DERIVATIVES

Derivative
Soda Ash Glass 0.14 - 0.23

Soda Ash Sodium Silicates 0.41
Soda Ash Sodium Dichromate 0.90
Soda Ash STPP 0.893
189 ~
Conversion Factors
METHANOL DERIVATIVES

Derivative
Methanol Acetic Acid 0.55

Methanol Biodiesel 0.13
Methanol Carbon Tetrachloride 0.22
Methanol Chloroform 0.29
Methanol Chloromethane 0.68
Methanol DMT - retained methanol 0.06
Methanol DMT - non retained methanol 0.38
Methanol Diethylene Glycol Monomethyl Ether 0.30
Methanol Dimethyl Ether 1.50
Methanol Ethylene Glycol Monomethyl Ether 0.47
Methanol Formaldehyde (37%) 0.45
Methanol Methyl Tertiary Butyl Ether 0.36
Methanol Methanol-To-Olefins 6.601
(per metric ton propylene)
Methanol Methanol-To-Propylene 3.189
Methanol Methyl Acetate 0.43
Methanol Methylamine 1.45
Methanol Methyl Methacrylate 0.39
Methanol Methylene Chloride 0.41
Methanol Polyacetyl (via formaldehyde) 1.50
Methanol Synthetic Gasoline 2.80
Methanol Tert Amyl Methyl Ether 0.31
Methanol Triethylene Glycol Monomethyl Ether 0.22
190 ~
Densities
191 ~
DENSITIES
Density @ Temperature
Compound Form
3 o
g/cm C
Benzene Liquid 0.879 20
1,3-Butadiene Gas 0.621 20
Caustic Soda Deliquescent 2.130 15-20
Chlorine Liquid 1.560 -33.6
Cumene Liquid 0.862 20
Ethylene Gas 0.570 -102
Ethylene Dichloride Liquid 1.256 20
Ethylene Glycol Liquid 1.116 15-20
Ethylene Oxide Liquid 0.887 7
Methanol Liquid 0.792 20
Phenol Needles 1.071 25
Polystyrene Powder 1.050 15-20
Polyvinyl Chloride Liquid 1.400 15-20
Propylene Gas 0.609 -47
Soda Ash Powder 2.533 15-20
Styrene Liquid 0.903 20
Toluene Liquid 0.866 20
Vinyl Chloride Gas 0.908 25
Metaxylene Liquid 0.881 20
Orthoxylene Liquid 0.867 17
Paraxylene Liquid 0.861 20
192 ~
Heat Values
193 ~
HEAT VALUES
Molecular Standard Net Enthalpy of Combustion Heat Value *
Compound Formula
Weight J/kmol X 1E-09 kJ/kg Btu/lbm
Acetylene C2H2 26.037 -1.257 48,277 20,756
Ammonia H3N 17.031 -0.31683 18,603 7,998
Benzene C6H6 78.112 -3.136 40,147 17,260
1,3-Butadiene C4H6 54.090 -2.409 44,537 19,147
Butane C6H10 58.122 -2.65732 45,720 19,656
1-Butanol C4H10O 74.122 -2.454 33,108 14,234
Carbon Monoxide CO 28.010 -0.283 10,104 4,344
Cumene C9H12 120.192 -4.951 41,192 17,710
Ethane C2H6 30.069 -1.42864 47,512 20,427
Ethanol C2H6O 46.068 -1.235 26,808 11,525
Ethylene C2H4 28.053 -1.323 47,161 20,275
Ethylene Glycol C2H6O2 62.068 -1.0527 16,960 7,292
Ethylene Oxide C2H4O 44.053 -1.218 27,649 11,887
Hydrogen H2 2.016 -0.24182 119,950 51,569
Methane CH4 16.042 -0.80262 50,032 21,510
Methanol CH4O 32.042 -0.6382 19,918 8,563
Phenol C6H6O 94.111 -2.921 31,038 13,344
Propane C3H8 44.096 -2.04311 46,333 19,920
1-Propanol C3H8O 60.095 -1.844 30,685 13,192
Propylene C3H6 42.080 -1.9262 45,775 19,680
Styrene C8H8 104.149 -4.219 40,509 17,416
Toluene C7H8 92.138 -3.734 40,526 17,423
Vinyl Chloride C2H3Cl 62.498 -1.178 18,849 8,103
Metaxylene C8H10 106.165 -4.3318 40,803 17,542
Orthoxylene C8H10 106.165 -4.33 40,786 17,535
Paraxylene C8H10 106.165 -4.33 40,786 17,535
* The compounds are considered to be formed from the elements in their standard states at 298.15 K and 101,325 Pa.
Enthaply of combustion is the net value for the compound in its standard state at 298.15 K and 101,325 Pa.
194 ~
Glossary
195 ~
Glossary OF Chemistry Terms
A dipic Acid – Combines with Hexamethylene Diamine to form Nylon 6,6.
Alcohol – The family name of a group of organic chemical compounds composed of carbon,
hydrogen and oxygen. The series of molecules vary in chain length, and are composed of a
hydrocarbon plus a hydroxyl group; CH3–(CH2)n–OH (e.g. methanol, ethanol and tertiary butyl
alcohol).
Alkylate – Gasoline blend stock component manufactured by chemically joining several short
chain molecules such as propylene and butylene. The product of an alkylation reaction. It usually
refers to the high octane product from alkylation units. This alkylate is used in the blending of
high octane gasoline.
Alkylation – A refining process for chemically combining isobutane with olefin hydrocarbons
(e.g. propylene and butylene) through the control of temperature and pressure in the presence of
an acid catalyst, usually sulfuric acid or hydrofluoric acid. The product, alkylate, an isoparaffin,
has high octane value, and is blended with motor and aviation gasoline to improve the antiknock
value of the fuel.
Alloy – A macroscopically homogenous mixture or solid solution, usually of two or more metals.
Ambient – Atmospheric conditions, generally refers to temperature or pressure.
Associated Gas – Gas that is found in conjunction with oil.
B arrel – A unit of volume equal to 42 U.S. gallons.
Beam – A large spool, typically of aluminum, used to wrap multiple filaments for future processing.
A typical use is where multiple yarns of the same length and tension are needed at the same time.
An example is weaving where the longitudinal fibers are fed as the shuttle makes the weave.
Beaming/Warping – The process of winding fiber onto a beam.
Bitumen – Any of a various mixture of hydrocarbons found in asphalt or tar used for surfacing
roads and waterproofing products.
Blow Molding – Type of processing for plastic resins that uses air to conform hot plastics to the
shape of the mold. Product examples include plastic milk bottles, shampoo bottles and children’s
toys.
Bobbin – A cylindrical support on which yarn or filament fiber is wound.
C apacity – The quantity of standard product that can be produced at an operation. Standard
product refers to either a typical commercial product or mixture of products that is typical of
the industry.
196 ~
Glossary
Caprolactam – Often referred to as “Capro”, it is the feedstock to Nylon 6.
Catalyst – Substance that modifies, particularly the rate, of a chemical reaction without being
consumed in the process.
Catalytic Cracking – A process of breaking down the larger, heavier, and more complex
hydrocarbon molecules into simpler and lighter molecules. Catalytic cracking is accomplished
by the use of a catalytic agent, and is an effective process for increasing the yield of gasoline
from crude oil. Catalytic cracking processes fresh feeds and recycled feeds.
Catalytic Hydrocracking – A refining process that uses hydrogen and catalysts with relatively
low temperatures and high pressures for converting middle boiling or residual material to high-
octane gasoline, reformer charge stock, jet fuel and/or high grade fuel oil. The process uses one
or more catalysts, depending upon product output, and can handle high sulfur feedstocks without
prior desulfurization.
Catalytic Hydrotreating – A process used in refineries for treating petroleum fractions from
atmospheric or vacuum distillation units (e.g. naphthas, middle distillates, reformer feeds, residual
fuel oil and heavy gas oil) and other petroleum (e.g. cat cracked naphtha, coker naphtha, gas oil
etc.) in the presence of catalysts and substantial quantities of hydrogen. Hydrotreating includes
desulfurization, removal of substances (e.g. nitrogen compounds) that deactivate catalysts,
conversion of olefins to paraffins to reduce gum formation in gasoline and other processes to
upgrade the quality of the fractions.
Catalytic Reforming – A refining process using controlled heat and pressure with catalysts
to rearrange certain hydrocarbon molecules, thereby converting paraffinic and naphthenic type
hydrocarbons (e.g. low-octane gasoline boiling range fractions) into petrochemical feedstocks
and higher octane stocks suitable for blending into finished gasoline.
Commodity – An article of trade or commerce that can be processed and resold. Typically used
to refer to the standard industry product without any addition or upgrade.
Compounding – The process of mixing two materials together to obtain physical properties that
are different than the original components. For example, glass fibers are sometimes added to
plastics resins in order to obtain greater strength, rigidity and creep properties.
Condensate – A mixture consisting primarily of pentanes and heavier hydrocarbons which is

recovered as a liquid from natural gas in separation facilities. This category excludes natural gas
liquids, such as butane and propane, which are recovered at downstream natural gas processing
plants or facilities.
Cone – A conical support on which yarn or filament fiber is wound.
Conversion – Transforming a feedstock into another product.
Cracking – A process which separates the bonds between carbon atoms. It generally occurs under
high pressure or high temperature. A familiar example is cracking ethane to form ethylene.
Cryogenic Separation – Separation of materials based on differences in freezing points.
Cube Out – Fulfilling the maximum amount of volume that can be shipped aboard the transport
before it has reached the maximum weight.
197 ~
Glossary
D emand – The amount of product being requested by potential customers. Total demand in
a country is the sum of domestic demand and exports. High demand with low supply will
equate to very high prices, while low demand with ample supply will help to push prices down as
suppliers try to move inventory.
Derivative – Chemical compound derived or made from other chemicals. For example,
polyethylene is an ethylene derivative.
Denier – The weight, in grams, of 9,000 meters of fiber. Denier is a direct fiber numbering
system for expressing weight per unit length of a fiber. It can be thought of as an approximation
of diameter when considering the same type of polymer(s) of similar specific gravity (density).
Downstream – The process(es) being fed by the process under consideration.
Downstream Activities – Refers to the processing of hydrocarbons such as crude oil and natural
gas into compounds that form petrochemical feedstocks or other useable products.
DMT – Dimethyl Terephthalate. Used to produce PET via the DMT route, although most PET is
now produced via the PTA route.
Dyeing – The application of applying color to textiles in fiber, yarn or fabric form.
E ffluent – A discharge of liquid waste that flows out of a treatment plant, sewer, or industrial
outfall.
Electrochemical Unit (ECU) – The chlor-alkali process produces chlorine and caustic soda in
set ratios of 1.0 unit of chlorine and 1.1 dry units of caustic soda. The combination of 1.0 unit of
chlorine and 1.1 dry units of caustic soda is an ECU.
Electron – Negatively charged material orbiting the nucleus of an atom. The sharing of electrons
between atoms results in chemical bonds.
Electronegativity – Having a negative electric charge.
Endothermic – A chemical reaction in which heat is absorbed.
Engineering Thermoplastics (ETP) – Thermoplastics are organic materials that melt when
heated. ETP are plastics that have higher physical performance attributes than commodity
polymers such as polyethylene, polypropylene, polystyrene and polyvinyl chloride. Engineering
materials generally include nylons, polyesters, polycarbonates, etc.
Exothermic – A chemical reaction in which heat is released.
Extrusion – The process of forcing molten polymer through holes in a die plate. In fiber, the
die plate is called a spinneret and the process is referred to as spinning. Once the polymer is
extruded through the spinneret, it is quenched to a solid in order to maintain the shape of the
spinneret holes.
F eedstocks – The physical components that are combined to produce a product.
198 ~
Glossary
Fiber – Textile raw material, generally characterized by length, diameter and flexibility. Fibers
are either natural or manmade, and are generally characterized by having a length of at least 100
times their diameter.
Filament – Extruded fiber that is used and processed in a continuous form without being cut into
discrete increments of length.
Finished Good – The final product of a manufacturing operation produced for commerce.
Floor Price – Generally the lowest price for which a product will trade. The floor price is often
equal to the cost of producing the product. Prices lower than the floor price will not cover the
cash cost of production and the producer is losing money on each unit sold.
Fluid Catalytic Cracking (FCC) – The refinery process in which crude oil fractions are converted
to gasoline. The process requires high temperatures and the presence of a specialized catalyst.
Propylene is a petrochemical by-product of FCC units.
Fractionation Column – A column in which fractionation or chemical separation by boiling point

takes place.
G as Oil – A liquid petroleum distillate having a viscosity intermediate between that of kerosene
and lubricating oil. It derives its name from having originally been used in the manufacturing
of illuminating gas, and is now used to produce distillate fuel oils and gasoline.
Gasoline – A complex mixture of relatively volatile hydrocarbons with or without small quantities
of additives, blended to form a fuel suitable for use in spark-ignition engines. Motor gasoline
is characterized as having a boiling range of 122-158oF at the 10 percent recovery point to
365-374oF at the 90 percent recovery point. “Motor Gasoline” includes conventional gasoline;
all types of oxygenated gasoline, including gasohol; and reformulated gasoline, but excludes
aviation gasoline.
Gasoline Blending Components – Naphthas (e.g. straight-run gasoline, alkylate, reformate,

benzene, toluene, xylenes etc.) used for blending or compounding into finished motor gasoline.
These components include reformulated gasoline blendstock for oxygenate blending but exclude
oxygenates (e.g. alcohols and ethers), butane and pentanes plus.
Greenfield Plant – Capacity added to a site where none existed. Generally includes items
such as roads, sewers, communication equipment etc. that do not have to be added at existing
plants.
H alides – A binary chemical compound of a halogen with a more electro-positive element or

group.
High Density Polyethylene (HDPE) – A thermoplastic resin made from ethylene. Commonly
used for grocery bags, tupperware, and milk jugs.
HMDA – Hexamethylene Diamine. Combines with Adipic Acid to form Nylon 6,6.
Hopper Rail Car – A rail car designed for loading and unloading of powder or pellet material.
199 ~
Glossary
Hydrocarbon – Compounds containing only carbon and hydrogen atoms. Hydrocarbons are the
basic materials in the oil, gas and chemical industries.
Idle Capacity – That part of operable capacity that is not in operation and not under active
repair, but capable of being placed in operation in short order. Also refers to capacity not in
operation but under active repair that can be completed in a reasonable period of time.
Industrial Gases – Gases used in industrial and manufacturing processes such as steel
production, semi-conductor manufacture and oil drilling. The most common industrial gases are
oxygen, nitrogen and argon.
Injection Molding – Plastic processing application in which molten plastic fills a mold. The
plastic then cools and solidifies. Common uses include plastic milk crates, plastic cups and
children’s toys.
Inorganic chemistry – Non-carbon based chemistry.
Integrated – All components of conversion are owned by the same entity. This is significant in
economic models as individual components are often modeled at cash cost plus cost of capital
to cover reinvestment. Integrated producers may not be exposed to the market swings in their
integrated raw materials.
Intermodal Container – A large metal, stackable container specifically designed to facilitate

economic loading and unloading as well as transport via cargo ships. “Containers” can be affixed
with wheels such that they can be transported by road to their final designation without being
individually loaded and unloaded.
Isomer – A compound having the same molecular weight, but differing in chemical or physical
properties. For example, iso-butane is an isomer of butane.
Isomerization – A refining process which alters the fundamental arrangement of atoms in the
molecule without adding or removing anything from the original material. Used to convert normal
butane into isobutane (C4), an alkylation process feedstock, normal pentane and hexane into
isopentane (C5) and isohexane (C6), high-octane gasoline components.
L inear Low Density Polyethylene (LLDPE) – A thermoplastic resin made from ethylene,
commonly used for shrink wrap, trash-can liners and packaging.
Liquefied Petroleum Gases (LPG) – A group of hydrocarbon-based gases derived from crude
oil refining or nautral gas fractionation, which includes ethane, ethylene, propane, propylene,
normal butane, butylene, isobutane and isobutylene. For convenience of transportation, these
gases are liquefied through pressurization.
Low Density Polyethylene (LDPE) – A thermoplastic resin made from ethylene, commonly
used for food packaging and plastic coatings for paper products.
M argins – The difference between the particular cost and selling prices being considered.
200 ~
Glossary
Middle Distillates – A general classification of refined petroleum products that includes distillate
fuel oil and kerosene.
Monoethylene Glycol (MEG) – A feedstock used to produce PET as well as automotive engine
coolants, antifreeze etc.
Monomer – The repeated unit in a polymer. For example, ethylene is a monomer.
N atural Gas – A gaseous mixture of hydrocarbon compounds, the primary one being
methane.
Natural Gas Liquids – Those hydrocarbons in natural gas that are separated from the gas as
liquids through the process of absorption, condensation, adsorption or other methods in gas
processing or cycling plants. Generally, such liquids consist of propane and heavier hydrocarbons
and are commonly referred to as condensate, natural gasoline and liquefied petroleum gases.
Natural gas liquids include natural gas plant liquids (primarily ethane, propane, butane and
isobutane) and condensate (primarily pentanes).
Neutron – Material found in the nucleus of an atom, with neither a positive or negative electric
charge.
Nylon – A generic name for a family of long-chain polyamides having recurring amide groups
[–CO–NH–] as an integral part of the main polymer chain. The second number, if used, denotes
the number of carbon atoms derived from a diacid.
Nylon 6 – Also known as polycaprolactam. Made by the polycondensation of caprolactam.
Nylon 6,6 – Made by condensing hexamethylene diamine H2N(CH2)6NH2 with adipic acid
COOH(CH2)4COOH.
O ff–take Agreement – Within the petrochemical industry, this refers to a contractual

agreement for one party to supply another with a product within certain conditions such as
purity, timing, volume etc. Off-take agreements are sometimes necessary to obtain financing in
the development of capital intensive petrochemical projects.
Opportunity Cost – The value given to the amount of product or service that might otherwise
have been produced if the current option was not pursued.
Organic Chemistry – Chemistry based on carbon atoms.
Oxidation – The combination of a substance with oxygen. When a metal develops “rust”,
oxidation has occurred.
Oxygenates – Substances which, when added to gasoline, increase the amount of oxygen in that
gasoline blend. Ethanol, Methyl Tertiary Butyl Ether (MTBE), Ethyl Tertiary Butyl Ether (ETBE),
and methanol are common oxygenates.
P ackage – A spool, bobbin, cone, or tube wrapped with fiber for future processing.
201 ~
Glossary
Parrafin – Another term for alkane or a single-bonded hydrocarbon. From Latin, meaning “small
affinity”.
Pasteurize – To destroy disease-causing microorganisms and limit fermentation in liquids by

partial or complete sterilization.
Polycondensation – Polymerization in which a condensation bi-product is formed, typically

water.
Polyethylene Terephthalate (PET) – Also known as polyester bottle resin.
Polymer – A molecule produced by linking together numerous smaller molecules, or monomers,

in a chain-like structure. All synthetic fibers are polymers.
Polymerization – Process by which monomers are joined together in long chains to form
polymers, generally requiring high heat or pressure or the presence of a catalyst.
Propane dehydrogenation – On-purpose process to produce propylene from propane.
Proton – Positively charged material found in the nucleus of an atom.
PTA – Purified Terephthalic Acid, also known as Terephthalic Acid. A feedstock used in the
primary route to produce PET.
Q uenched – The process of cooling a molten, liquid polymer into a solid. How a polymer is
quenched affects its finished properties.
R esin – General label for polymerized synthetics or chemically modified natural resins used
in making plastics.
Reformulated Gasoline – Finished motor gasoline formulated for use in motor vehicles,
the composition and properties of which meet the requirements of the reformulated gasoline
regulations promulgated by the U.S. Environmental Protection Agency.
S alt Domes – Naturally occurring underground salt deposits, which are solution mined for
salt. The holes left in underground salt domes form caverns that are used for petrochemical
storage.
Share Shift – The process of competing products exchanging market share without changing the
overall size or scale of the market.
Slurry – A suspension formed when a quantity of powder is mixed into a liquid in which the
solid(s) is only slightly or not soluble.
Solid State Polymerization (SSP) – The process of lengthening a polymer’s molecular chain
length by subjecting the solidified polymer to heat and vacuum. This process is used to increase
the physical properties of a polymer, without the polymer moving into the liquid phase.
Solvent – A substance that dissolves another substance.
202 ~
Glossary
Staple – Fiber of discrete sizes. Staple fibers can be joined together to form a yarn.
Stranded Gas – Remotely located natural gas with few or no commercially-viable local
consumption options.
Supply – The amount of product coming into a market to meet demand.
Synthetic Fibers – Fibers that are not of natural origin, either prepared or made artificially.
T ransalkylation – A process that converts low value toluene and heavy aromatics into value-
added mixed xylenes.
Tube – A hollow cylindrical or slightly tapered support on which yarn or filament fiber is wound.
U pstream – The process(es) that feed(s) the process under consideration. For example,
crude oil, benzene and caprolactam are all upstream of nylon.
Upstream Activities – Refers to the exploration and production of hydrocarbons such as crude
oil and natural gas.
Utilization Rate – Production volume relative to capacity, typically in percent terms. Utilization
Rate = Production/Capacity.
W eigh Out – Fulfilling the maximum amount of weight that can be shipped aboard the
transport before it is completely full on a volume basis.
World-scale Plant Size – The plant size necessary to achieve economies of scale and be
competitive in the global markets. Plant size differs by product, but new investments are generally
at, or close to, world-scale plant sizes.
203 ~
Glossary
GLOSSARY OF Contractual Terms
Applicable Law – A very simple concept that avoids many future problems if the parties go to
dispute resolution or court. Whose law is used? Domestically, it is common for the law of the
state within which either of the parties resides (or is incorporated within) in to be the applicable
law. Internationally, the parties typically negotiate this to be a neutral, third party country’s law.
Assignability – A contract provision that allows for a successor of either the buyer or the seller
to be “assigned” the contract in all aspects, subject to all existing terms and conditions.
Audit Clauses – General category of language to provide for either party to justify actions to the
other. For example, a buyer that is obligated to purchase a percentage of his requirements from
the seller may be audited to prove that he has done so. Conversely, said buyer may have rights
to audit the seller’s raw material costs if product pricing is formula tied to such.
Boiler Plate – The common name given to the general terms and conditions of sale. Many of the
components are defined further in this section.
Contract Sale – A buyer/seller transaction subject to previously negotiated terms. Typical

contracts specify terms, volumes, pricing methods and other criteria that apply to each purchase.
A contract can be considered seller’s obligation to provide the required volumes and buyer’s
obligation to purchase such from seller, both at previously agreed upon terms.
Dead–end versus Evergreen – Contract terminology referring to the disposition of the contract
at the end of the stated term of agreement. A dead-end contract simply ends on a certain date
and time, while an evergreen contract contains provisions to automatically extend the contract for
some additional period if not cancelled by either party at some point before an anniversary date.
Dispute Resolution – A commonly used clause to agree upon a mutually acceptable mechanism
to settle any future disagreement that may arise. Typically these involve using expert, independent
third parties whose decisions are binding upon both parties.
Force Majeure – Legal terminology for excusing either party for failure to comply with the contract
for reasons that are out of their immediate control. Examples include unexpected production
outages, acts of God (like weather), war or an inability to procure feedstocks.
Formula versus Market Pricing – Market pricing, as the name implies, is a freely negotiated
price between buyer and seller with each having other options. Formula pricing is more commonly
agreed upon for products with a very limited number of either buyers or sellers, or simply in cases
where both parties are willing to agree to fix a component such as costs or margin.
Meet or Release Clauses – Common contract language to allow the seller to meet any
competitive situation that buyer may bring to the table. If buyer “meets” the situation (e.g. price,
quality, discount, quantity, time frame etc.), then seller is assured that buyer will purchase from
him. If seller chooses to “release”, then buyer is free to purchase the material elsewhere and
reduce his purchase volume commitment from seller commensurately.
Most Favored Nation – A buyer-negotiated clause that ensures the seller treats no other
customer any better than the buyer. While typically associated with price, a lower price offer to
another must also be offered to the buyer, other points such as payment terms, length of contract
or product quality may also be included.
204 ~
Glossary
Product Exchanges – A common practice, especially among commodity products, is to exchange

product with a competitor for one of a few reasons. Whether to minimize freight costs to a
customer, to cover for production outages or merely to enhance logistics, exchanges provide for a
cost efficient means of delivering specification-based material to customers. Typical agreements
include volumes, timing of returns, any freight differentials to be paid, product specifications and
any other specific information germane to the exchange.
Rights of First Refusal/Offer – Similar in nature to the Meet or Release Clauses, this concept is
more aligned with the buyer. Additional sales volumes (sometimes at different pricing levels) are
first made available to buyer to accept or decline. This also applies to joint venture ownership
structures where existing partners would be allowed to buy out an exiting partner before any third
party were so offered.
Spot Sale – A buyer/seller transaction categorized by singular purchases at a point in time, from
potentially any supplier, typically at a negotiated price. No pre-negotiated volume commitment
by either buyer or seller.
Take or Pay – Refers to buyer’s obligation to actually take the volume committed to. Buyer is
responsible for paying seller the actual sales price for all volumes whether or not he physically
takes possession of the product. If buyer fails to lift product, seller can inventory, resell or re-
process said product with no recourse to buyer.
Title and Risk of Loss – Title is typically passed from one owner to another for a chemical
product at a flange of a meter station (in case of pipeline movements), upon exit of a seller’s
facility or upon delivery of product to the buyer’s location. Risk of loss most often follows the point
at which title is transferred.
Tolling – Commercial arrangement in which buyer provides feedstocks to seller, who in turn
converts them to finished products for buyer. Buyer is typically responsible for conversion
costs and some agreed-upon fee for such services. At times, the conversion costs plus toll fee
themselves will be "paid" by feedstock.
Volume Minimums and Maximums – A primary component of any contract, the definition of
the minimum and maximum quantity to be sold by seller and bought by buyer subject to the
pricing terms (which may be fixed or freely negotiated). Equally important is the ratability of the
sales/purchases, with contracts commonly stating volumes to be in roughly equal (+/– some
percentage) quantities per month or quarter. Any volumes “released” by seller upon request
by buyer (see Meet or Release Clauses) are deducted from the periodic volume and cannot be
called on at a later date unless agreed to by seller.
Warranty of Merchantability – Most warranties of merchantability go hand in hand with limits

on liability, that together limit the seller's liability to replacement of material that may not conform
to specification. Basically, the seller warrants that his product meets the stated specification, but
does not warrant that it is suitable for the intended purpose of the buyer.
205 ~
Glossary
GLOSSARY OF Freight TERMS
The International Chamber of Commerce, based in Paris, publishes a book that defines terms
generally used in both domestic and international commercial transactions. These definitions
pinpoint the responsibilities and liabilities of both buyer and seller, and are accepted almost
universally. By understanding and using these terms in contracts, it may be possible to eliminate
misunderstandings and disputes. In case a dispute completely deteriorates, the Chamber
also has a court of arbitration available to all concerned parties. In addition, it publishes books
covering commercial practices, banking (e.g. letters of credit, guarantees, documentation etc.),
transportation and arbitration.
Anyone that is, or intends to be, involved in international trade should familiarize themselves with
Incoterms, especially the ones most frequently used. Three major difficulties that people face in
international business are uncertainty as to what country's law will govern, difficulties arising from
inadequate information, and diversity of interpretation. Incoterms tend to reduce this confusion.
Incoterms were revised in 1990 in an effort to adapt to the increasing use of electronic data.
At the same time, some of the terms were standardized in order to provide easier reading and
understanding. The terms have been grouped in four different categories centered with the term
whereby the seller makes the goods available to the buyer. They are as follow:
"E" (ex works) term – Basically refers to the seller delivering goods to a carrier appointed by the
buyer at the manufacturing facility.
"F" (FAS/FOB) term – Generally refers to the seller delivering goods to a carrier appointed by the
buyer but away from the seller’s premises, such as a loading dock.
"C" (C & F/CFR/CIF) term – Under these terms, the seller contracts for the freight but it is extremely
important and worth repeating continuously that all risks of loss or damage to the goods or any
additional cost because of these events are for the account of the buyer.
"D" (DAF/DES) term – Generally applies to the product being delivered in the country of destination.
Again, all risks exchange between the seller and the buyer at the point of first loading. "D" terms
do not generally apply to the shipment of bulk petrochemicals.
206 ~
Glossary
Here is a general outline of the new 1990 Incoterms:
Group "E" (departure)

EXW EX works
Group "F" (main carriage/transportation/unpaid)

FCA Free carrier
FAS Free alongside ship
FOB Free onboard
Group "C" (main carriage/transportation/paid)

CFR Cost and freight (this is a new designation that replaces the old C and F or C&F)
CIF Cost insurance and freight
CPT Carriage paid to
CIP Carriage and insurance paid to
Group "D" (arrival)
DAF Delivered at frontier

DES Delivered ex ship
DEQ Delivered ex quay
DDU Delivered duty unpaid
DDP Delivered duty paid
Generally speaking, the primary designations listed above that will apply to the bulk petrochemical
international trade are FOB, CFR and CIF, although occasionally we see shipments made DDU
or DDP. In the packaged petrochemical trade (drums/bags), the term FAS is used much more
frequently.
It is impossible to include here the complete details of Incoterms. Therefore, we highlight and
define in our interpretation the important items in the terms most used in the international (and
sometimes domestic) bulk petrochemical trade.
207 ~
Glossary
CFR/C+F (Cost and Freight)
Under this term (and the following one), the seller is responsible for chartering the space on the
ship, at his own expense, and he is responsible for all costs (except ocean insurance) until the
vessel arrives at the port of destination. However (and this is important), the seller's risk ends
and title transfers as the cargo is loaded on board at the port of shipment.
The buyer must accept the cargo at the discharge port, even if it has become contaminated
during the voyage or did not meet specifications. The ship must be allowed to discharge and sail.
He is also responsible for any charges relating to the discharge, for obtaining any required import
documents, and for the ocean insurance.
CIF (Cost, Insurance, Freight)
This term is basically the same as C+F, except the seller arranges for the ocean insurance.
However, the insurance is obtained on behalf of the buyer, who is responsible for processing
any claims, but the seller should assist where he can. In the liquid bulk petrochemical industry,
a deductible or franchise, usually 0.5-1.0%, generally applies. This means that the insurance
company will not be responsible for that deductible or franchise which must then be absorbed by
the shipper.
CIF Landed
It is very seldom that international transactions take place under this term, and it is not included
in Incoterms. In essence, the seller is responsible for all risks, including quality and quantity, until
the product is received in tanks at the discharge port. However, most of this risk will be covered
by marine insurance provided shore tank to short tank coverage is acquired. For liquid bulk
shipments the seller should increase his sales price by at least 0.5 (one half) percent to hedge
against the deductible (franchise) of a similar amount not covered by insurance companies.
Insurance companies will not cover loss by evaporation, which is an inherent risk. Before agreeing
to this sales and shipping term, the seller should investigate the availability of incremental storage
space at the discharge port, in case the parcel arrives off-spec. In such a case, it must be
discharged and may have to be segregated. However, the insurance company will be involved.
FAS (Free Alongside Ship)
This term applies to packaged cargo, such as drums or bags, but is included in case some of our
clients become involved in this type of sale or purchase.
Under FAS terms of sale, the seller is responsible to deliver the cargo, at his cost, alongside the
ship (usually to mean within reach of the ship’s tackle), whether on a dock or a lighter (barge).
The delivery is made to the port, berth, and ship, named by the buyer, during the agreed time
frame. All costs up to this point, such as packing and inland transportation, are borne by the
seller. He should also receive a dock receipt from the shipping company or agent which certifies
that the cargo was received.
The buyer makes all arrangements for booking the ocean freight and insurance, and informs the
pertinent details to the seller. He is also responsible and liable for all costs from this point onward,
208 ~
Glossary
such as freight, insurance, heavy lift and export documentation. However, it is common for the
seller to arrange export documentation and charge the buyer for these out-of-pocket costs.
FOB (Free on Board)
Under this term, the seller is responsible for loading the cargo on board the buyer’s vessel.
The seller must obtain any necessary export license and pay any taxes or dues on the cargo
up to this point. Any harbor tax or dues will be for the account of the buyer. The seller will also
arrange for any export documentation required, as requested by the buyer. The actual transfer
of responsibility for liquid bulk cargoes is usually at the flange connecting the shore line to the
ship’s, or as the cargo passes the ship’s rail.
The buyer books the ship, nominates it to the seller, and is responsible for the cargo from this
point onward.
FOR/FOT (Free on Rail/Truck)
This term is not used in the U.S., but is widely known in European countries. It is basically the
same as FOB, but pertains to rail cars and trucks.
We took some liberties in writing the above, since Incoterms do not specifically apply to shipments
in bulk. For example, Incoterms stipulate the buyer must receive the cargo under CFR/C+F or CIF,
not going into detail should the cargo be off-spec or contaminated. In general practice, chemical
tanker operators insist the cargo be discharged regardless of any extenuating circumstances,
to enable the ship to go about its business and meet other commitments. Also, under CIF, it is
generally accepted in this trade that, although the seller procures the marine insurance, it is for
and on behalf of the buyer. Should any insurable problems develop, it is up to the buyer to file
the claim but of course, the seller should assist where he can.
Another important detail is worth mentioning again. Regardless of whether a transaction is

FOB, CFR/C+F, or CIF, the risk transfers to the buyer at loading. In our experience, we have
witnessed some heated disputes over this, that were eventually settled by referring to Incoterms,
usually to someone's dismay.
Although the seller has many costs (especially under CIF), they should be calculated and included
in the sales price. There is one item governing bulk chemical shipments that should be shared
on a 50/50 basis, and that is the cost of inspection at the load port. Incoterms does not mention
this, but it is customary in this trade. An independent, reputable and recognized inspector
almost always is appointed to survey the loading, and whose findings for quality and quantity
are accepted by all parties, including the ship. In order to prove the inspector's independence,
insurance companies prefer to see this fee shared by both buyer and seller.
209 ~

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Handbook of the World Petrochemical Industry

Handbook of the World

Copyright 2008 by Chemical Market Associates, Inc.

All rights reserved. Reproduction of any part of this work

Published in Houston, Texas, USA

Section Page No.

Conversion Factors 177

Heat Values 193

CMAI is pleased to present the Handbook of the World Petrochemical Industry, a

This handbook was completed by a team of Research Associates in CMAI:

CMAI – New York CMAI – Europe CMAI – Europe Gmbh

CMAI – Middle East CMAI – Asia CMAI – China

NORTH AMERICA SOUTH AMERICA WEST EUROPE

POLYESTER CYCLOHEXANE& PHENOL POLYPROPYLENE

TEXTILE/APPAREL CYCLOHEXANE PHENOL NONWOVENS BUTYLENE GLASS

NYLON FIBERS ACETONE

INORGANIC & ORGANIC CHEMISTRY DIFFERENCES

Hydrogen & Carbon Elements

SINGLE CARBON BONDED HYDROCARBON

ORGANIC CHEMISTRY BASICS

Petrochemicals (natural gas (C1), olefins, aromatics)

Polymers (derivatives of petrochemicals)

Fine Chemicals (soaps, pesticides, pharmaceuticals, dyes)

INORGANIC CHEMISTRY BASICS

The Alkali Industry

The Acid Industry

Nitrogen Based Chemicals

COMMERCIAL CHEMICAL PROCESSES

Heating and Cracking

Naphtha Furnace Quench Primary Distillation

Fractional Distillation FRACTIONAL DISTILLATION

OVERVIEW of ORGANIC CHEMISTRY NOMENCLATURE & PRODUCT CHAINS

12% 16% Cumene Toluene

Solvents 13% 76%

Selected Global Polymer Capacity

Pulp and Paper

1. Polyethylenes – LLDPE, LDPE and HDPE

2. Ethylene oxide and glycol

Total Capacity = 125.2 Million Metric Tons

Total Demand = 114.0 Million Metric Tons

• Methanol to Oleﬁns (MTO)

KEY PROCESS – STEAM CRACKING

are generated commercially by pyrolysis (cracking) of parafﬁnic hydrocarbon feedstocks including

LOW DENSITY POLYETHYLENE

1. Film and sheet

1. Shrink ﬁlm, agricultural ﬁlm, rubbish bags and packaging

2. Coating of ﬁnished packages (i.e. milk cartons)

3. Medical bottles, closures, housewares, toys and industrial items

Total Demand = 18.7 Million Metric Tons

Northeast Asia North America

Total Capacity = 20.6 Million Metric Tons

Pipe & Extrusion

Total Demand = 18.7 Million Metric Tons

Low Density Polyethylene

• Tubular process (e.g. Basell Lupotech T technology)

• Autoclave process (e.g. ExxonMobil technology)

KEY PROCESS – CONVENTIONAL HIGH PRESSURE TUBULAR PROCESS

HIGH DENSITY POLYETHYLENE

1. Film and sheet

1. Grocery and merchandise bags