CHEMICALS

BASED ON
ETHYLENE
José Martín Rosas Castor
INTRODUCTION
Ethylene is sometimes known as the “king of
petrochemicals” because more commercial
chemicals are produced from ethylene than from
any other intermediate.

This unique position of ethylene among other

hydrocarbon intermediates is due to some
favorable properties inherent in the ethylene
molecule as well as to technical and economical
factors.
These could be summarized in the
following:
• Simple structure with high reactivity.
• Relatively inexpensive compound.
• Easily produced from any hydrocarbon
source through steam cracking and in high
yields.
• Less by-products generated from ethylene
reactions with other compounds than from
other olefins.
Ethylene reacts by addition to many
inexpensive reagents such as water,
chlorine, hydrogen chloride, and oxygen to
produce valuable chemicals.
It can be initiated by free radicals or by
coordination catalysts to produce
polyethylene, the largest-volume
thermoplastic polymer. It can also be
copolymerized with other olefins producing
polymers with improved properties.
Most important chemicals based on ethylene
OXIDATION OF ETHYLENE
Ethylene can be oxidized to a variety of useful chemicals.
The oxidation products depend primarily on the catalyst
used and the reaction conditions. Ethylene oxide is the
most important oxidation product of ethylene.
Acetaldehyde and vinyl acetate are also oxidation
products obtained from ethylene under special catalytic
conditions.
 ETHYLENE
OXIDE
Ethylene oxide (EO) is a colorless gas that liquefies
when cooled below 12°C. It is highly soluble in water
and in organic solvents.
Ethylene oxide is a precursor for many chemicals of
great commercial importance, including ethylene
glycols, ethanolamines, and alcohol ethoxylates.
Ethylene glycol is one of the monomers for polyesters,
the most widely-used synthetic fiber polymers. The
current US production of EO is approximately 8.1
billion pounds.
 PRODUCTION (ETHYLENE
OXIDE)
The main route to ethylene oxide is oxygen or air oxidation of ethylene over a silver catalyst.
The reaction is exothermic; heat control is important:

A concomitant reaction is the complete oxidation of ethylene to carbon dioxide and water:
 DERIVADES OF
ETHYLENE OXIDE:
ETHYLENE GLYCOL
Ethylene glycol (EG) is colorless syrupy liquid, and
is very soluble in water. The boiling and the
freezing points of ethylene glycol are 197.2° and –
13.2°C, respectively.
Current world production of ethylene glycol is
approximately 15 billion pounds. Most of that is
used for producing polyethylene terephthalate
(PET) resins (for fiber, film, bottles), antifreeze, and
other products. Approximately 50% of the world
EG was consumed in the manufacture of polyester
fibers and another 25% went into the antifreeze.
The main route for producing ethylene glycol is the hydration of ethylene oxide in presence of
dilute sulfuric acid.

The hydrolysis reaction occurs at a temperature range of 50–100°C. Contact time is

approximately 30 minutes. Di- and triethylene glycols are coproducts with the monoglycol.
Increasing the water/ethylene oxide ratio and decreasing the contact time decreases the
formation of higher glycols.
 ALTERNATIVE ROUTES TO PRODUCING ETHYLENE
GLYCOL
Ethylene glycol could also be obtained directly from ethylene by two methods, the Oxirane
acetoxylation and the Teijin oxychlorination processes.
In the Oxirane process, ethylene is reacted in the liquid phase with acetic acid in the presence of
a TeO2 catalyst at approximately 160° and 28 atmospheres. The product is a mixture of mono-
and diacetates of ethylene glycol: 

The acetates are then hydrolyzed to ethylene glycol and acetic acid.
 ETHOXYLATES
The reaction between ethylene oxide and long-chain fatty alcohols or fatty acids is called
ethoxylation. Ethoxylation of C10-C14 linear alcohols and linear alkylphenols produces
nonionic detergents.

Similarly, esters of fatty acids and polyethylene glycols are produced by the reaction of long-
chain fatty acids and ethylene oxide

The Cl2-Cl8 fatty acids such as oleic, palmitic, and stearic are usually ethoxylated with EO for
the production of nonionic detergents and emulsifiers.
 ETHANOLAMINES
A mixture of mono-, di-, and triethanolamines is
obtained by the reaction between ethylene oxide
(EO) and aqueous ammonia. The reaction conditions
are approximately 30–40°C and atmospheric
pressure.
Ethanolamines are important absorbents of acid
gases in natural gas treatment processes. Another
major use of ethanolamines is the production of
surfactants.
The reaction between ethanolamines and fatty acids
produces ethanolamides.
 1,3-PROPANEDIOL
1,3-Propanediol is a colorless liquid that boils at 210–
211°C. It is soluble in water, alcohol, and ether. It is an
intermediate for polyester production. It could be
produced via the hydroformylation of ethylene oxide
which yields 3-hydroxypropionaldehyde. Hydrogenation
of the product produces 1,3-propanediol:
ACETALDEHYDE  
Acetaldehyde is a colorless liquid with a pungent odor. It is a
reactive compound with no direct use except for the synthesis
of other compounds. It is oxidized to acetic acid and acetic
anhydride. It is a reactant in the production of 2-ethylhexanol
for the synthesis of plasticizers and also in the production of
pentaerythritol.
Acetaldehyde is an intermediate for many chemicals such as
acetic acid, n-butanol, pentaerithritol, and polyacetaldehyde.
PRODUCTION: WACKER
CATALYST
Acetaldehyde is obtained from ethylene by
using a homogeneous catalyst (Wacker
catalyst): the oxidation
of ethylene to acetaldehyde in the presence
of palladium(II) chloride as the catalyst
The Wacker reaction can also be carried out
for other olefins with terminal double bonds.
IMPORTANT CHEMICALS
FROM ACETALDEHYDE
 Acetic acid
Acetic acid is obtained from different
sources. Carbonylation of methanol is
currently the major route. Oxidation of
butanes and butenes is an important source
of acetic acid.
It is also produced by the catalyzed
oxidation of acetaldehyde:
 N-BUTANOL
n-Butanol is normally produced from propylene by the Oxo reaction. It may also be obtained from the aldol
condensation of acetaldehyde in presence of a base.

The formed 3-hydroxybutanal eliminates one mole of water in the presence of an acid producing
crotonaldehyde. Hydrogenation of crotonaldehyde produces n-butanol:
VINYL ACETATE
Vinyl acetate is a reactive colorless liquid that polymerizes
easily if not stabilized. It is an important monomer for the
production of polyvinyl acetate, polyvinyl alcohol, and vinyl
acetate copolymers.
it is produced by the catalytic oxidation of ethylene with
oxygen, with acetic acid as a reactant and palladium as the
catalyst
OXIDATIVE CARBONYLATION
OF ETHYLENE
Acrylic acid
The liquid phase reaction of ethylene with
carbon monoxide and oxygen over a
Pd2+/Cu2+ catalyst system produces acrylic
acid. The yield based on ethylene is about
85%. Reaction conditions are approximately
140°C and 75 atmospheres
CHLORINATION
OF ETHYLENE
The direct addition of chlorine to ethylene produces
ethylene dichloride (1,2-dichloroethane). Ethylene
dichloride is the main precursor for vinyl chloride,
which is an important monomer for polyvinyl
chloride plastics and resins.
Other uses of ethylene dichloride include its
formulation with tetraethyl and tetramethyl lead
solutions as a lead scavenger, as a degreasing agent,
and as an intermediate in the synthesis of many
ethylene derivatives.
VINYL CHLORIDE
Vinyl chloride is a reactive gas soluble in alcohol but slightly
soluble in water. It is the most important vinyl monomer in
the polymer industry.
The production of vinyl chloride via ethylene is a three-step
process. The first step is the direct chlorination of ethylene to
produce ethylene dichloride. Either a liquid- or a vapor-phase
process is used:

The exothermic reaction occurs at approximately 4

atmospheres and 40–50°C in the presence of FeCl3, CuCl2
or SbCl3 catalysts.
The second step is the dehydrochlorination of ethylene dichloride (EDC) to vinyl chloride and
HCl. The pyrolysis reaction occurs at approximately 500°C and 25 atmospheres in the presence
of pumice on charcoal:

The third step, the oxychlorination of ethylene, uses by-product HCl from the previous step to
produce more ethylene dichloride:

Ethylene dichloride from this step is combined with that produced from the chlorination of
ethylene and introduced to the pyrolysis furnace.
PERCHLORO AND
TRICHLOROETHYLENE
Perchloro- and trichloroethylenes could be produced from ethylene
dichloride by an oxychlorination/oxyhydrochlorination process without
by-product hydrogen chloride.

A fluid-bed reactor is used at moderate pressures at approximately

450°C. The reactor effluent, containing chlorinated organics, water, a
small amount of HCl, carbon dioxide, and other impurities, is condensed
in a water-cooled graphite exchanger, cooled in a refrigerated condenser,
and then scrubbed. Separation of perchlor from the trichlor occurs by
successive distillation
HYDRATION OF
ETHYLENE (ETHANOL
PRODUCTION)
Ethyl alcohol (CH3CH2OH) production is
considered by many to be the world’s oldest
profession. Fermenting carbohydrates is still the
main route to ethyl alcohol in many countries
with abundant sugar and grain sources.
The direct hydration of ethylene with water is the
process currently used:
USES OF
ETHANOL
Ethanol’s many uses can be
conveniently divided into solvent
and chemical uses. As a solvent,
ethanol dissolves many organic-
based materials such as fats, oils,
and hydrocarbons. As a chemical
intermediate, ethanol is a precursor
for acetaldehyde, acetic acid, and
diethyl ether, and it is used in the
manufacture of glycol ethyl ethers,
ethylamines, and many ethyl esters.
 OLIGOMERIZATION OF ETHYLENE
 The addition of one olefin molecule to a second and to a third, etc. to form a dimer, a trimer,
etc. is termed oligomerization. The reaction is normally acid-catalyzed. When propene or
butenes are used, the formed compounds are branched because an intermediate carbocation is
formed. These compounds were used as alkylating agents for producing benzene alkylates, but
the products were nonbiodegradable.
Oligomerization of ethylene using a Ziegler catalyst produces unbranched alpha olefins in the
C12-C16 range by an insertion mechanism.

Dimerization of ethylene to butene-l has been developed recently by using a selective titanium-
based catalyst. Butene-l is finding new markets as a comonomer with ethylene in the
manufacture of linear lowdensity polyethylene (LLDPE).
ALPHA OLEFINS
PRODUCTION
The C12-C16 alpha olefins are produced by
dehydrogenation of n-paraffins,
dehydrochlorination of monochloroparaffins, or
by oligomerization of ethylene using trialkyl
aluminum (Ziegler catalyst)
The oligomerization of ethylene using
triethylaluminum:
The triethylaluminum and l-butene are recovered by the reaction
between tributylaluminum and ethylene:

Alpha olefins are important compounds for producing biodegradable

detergents. They are sulfonated and neutralized to alpha olefin
sulfonates (AOS):
LINEAR ALCOHOLS
Linear alcohols (Cl2-C26) are important chemicals for producing various compounds such as
plasticizers, detergents, and solvents. They are also produced by the oligomerization of ethylene
using aluminum alkyls (Ziegler catalysts).
The Alfol process for producing linear primary alcohols is a four-step process:
1. Reaction of ethylene with hydrogen and aluminum metal.
2. Ethylene is polymerized
3. The oxidation of triethylaluminum
4. Hydrolysis of the trialkoxides with water to the corresponding even-numbered primary
alcohols
ALFOL PROCESS
BUTENE-1
A new process developed by Institut
Francais du Petrole produces butene-l (l-
butene) by dimerizing ethylene. A
homogeneous catalyst system based on a
titanium complex is used. The reaction is a
concerted coupling of two molecules on a
titanium atom, affording a titanium (IV)
cyclic compound, which then decomposes
to butene-l by an intramolecular β-hydrogen
transfer reaction.
ALKYLATION USING
ETHYLENE
Ethylene is an active alkylating agent. It can be used to alkylate
aromatic compounds using Friedel-Crafts type catalysts. Comercially,
ethylene is used to alkylate benzene for the production of ethyl
benzene, a precursor for styrene