(CHAPTER 3)

INTRODUCTION

  Ethylene reacts by addition to many inexpensive reagents such

as water (H2O), chlorine (Cl2), hydrogen chloride (HCl), and
oxygen (O2) 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. For example, when ethylene
is polymerized with propylene, a thermoplastic elastomer is
obtained.
  The figure below illustrates the 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.
  Also known as Oxirane
  A colorless gas or liquid and has a sweet, etheric odor.
  Very reactive chemical due to its single bond
  A versatile chemical intermediates
  A hazardous compound because it has been severaly involved
in a number of seriouse accident.
  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.
 PROPERTIES

  Ethylene oxide is a colorless, odorless gas at room temperature

and normal pressure,
  Liquid at 10.4o C or at higher pressure. The liquid has a
characteristic ether-like odor.
  Ethylene oxide is completely miscible with water, alcohol,
acetone, benzene, ether, and most organic solvents.
  Its vapors are inflammable and explosive.
  It is relatively stable in aqueous solutions or when diluted with
carbon dioxide or halocarbons, but it may undergo slow
polymerization during storage.
  Ethylene oxide is highly reactive and potentially explosive
when heated or in the presence of alkali metal hydroxides
and highly active catalytic surfaces.
  Incomplete combustion releases carbon monoxide.
  Ethylene oxide is available commercially in the United
States as a high-purity chemical that contains a maximum
of 0.03% water, 0.003% aldehydes as acetaldehyde, 0.002%
acidity as acetic acid, and 0.005 g residue/100 ml.
  It is also available as a 10%-80% pressurized or liquified gas
formulated with carbon dioxide, trichlorofluoromethane, or
dichlorofluoromethane to reduce fire hazards.
 THE USES

  The primary use of ethylene oxide is as an intermediate in the

production of several industrial chemicals, most notably,
ethylene glycol.
  Ethylene glycol is used primarily in automotive antifreeze and
polyester is used in fibers, films, and bottles.
  Ethylene oxide was also used to produce nonionic surfactants
(14%), ethanolamines (8%), glycol ethers (6%), diethylene glycol
(6%), and triethylene glycol (2%)
  Approximately 8% of the total U.S. demand for ethylene oxide is
as a sterilant and fumigant in the health product and medical
fields
  Ethylene oxide has also been used in flame retardants and to
accelerate the maturing of tobacco leaves.
  It has been investigated for use as an agent to improve wood
durability
 Production  Ethylene  oxide  

Manufacture  of  
Ethylene  Oxide   From  
Ethylene  
chlohydrin  
Direct  
Oxidation  
Process  
Not  
economically  
competitive  due  
to    Cl  and  
unwanted  Cl  by-­‐  
Air-­‐based   Oxygen-­‐ product  
Process   based   generated  
process  
Reaction  Mechanism  of  Ethylene  
Oxide  
Ag
C2H4 + 0.5O2 → C2H4O Original process discover by
Lefort in 1931
C2H4 + 3O2 →2CO2 + 2H2O Combustion reaction of ethylene oxide.

C2H4O + O2 →2CO2 + 2H2O Further oxidation of Ethylene Oxide

Production process

  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:
  This reaction is highly exothermic; the excessive
temperature increase reduces ethylene oxide yield and
causes catalyst deterioration.
  Over oxidation can be minimized by using modifiers such
as organic chlorides.
  It seems that silver is a unique epoxidation catalyst for
ethylene. All other catalysts are relatively ineffective, and
the reaction to ethylene is limited among lower olefins.
Propylene and butylenes do not form epoxides through this
route.
  Using oxygen as the oxidant versus air is currently favored
because it is more economical.
  Epoxidation reaction occurs at approximately 200–300°C
with a short residence time of one second. A selectivity of
70–75% can be reached for the oxygen based process.

  Selectivity is the ratio of moles of ethylene oxide produced

per mole of ethylene reacted.

  Ethylene oxide selectivity can be improved when the

reaction temperature is lowered and the conversion of
ethylene is decreased (higher recycle of unreacted gases).
 PFD
 of
 Ethylene
 Oxide
 
  Reactor- multi tubular reactor
  Ethylene Oxide Scrubber-water
  CO2 scrubber-potassium carbonate to contained the CO2
  CO2 desober-separate potassium carbonate with CO2
  Ehtylene Oxide stripping- separate Ethylene Oxide with water
  Distillation column-water and heavy end are removed to produce
pure Ethylene Oxide.
Compressed oxygen, ethylene, and
recycled gas are fed to a multi tubular
reactor. The temperature of oxidation
is controlled by boiling water in the
shell side of the reactor.
Effluent gases are cooled and passed
to the scrubber where ethylene oxide
is absorbed as a dilute aqueous
solution. Unreacted gases are
recycled.

Stripper
- To recover the ethylene oxide from
the solution

Purification
2 series of Fractionator column
Licensor: Scientific Design Company, Inc
Derivatives of Ethylene Oxide

  Ethylene oxide is a highly active intermediate. It reacts with all

compounds that have a labile hydrogen such as water, alcohols, organic
acids, and amines. The epoxide ring opens, and a new compound with a
hydroxyethyl group is produced. The addition of a hydroxyethyl group
increases the water solubility of the resulting compound.
  Further reaction of ethylene oxide produces polyethylene oxide
derivatives with increased water solubility.
  Many commercial products are derived from ethylene oxide by reacting
with different reagents. The following reviews the production and the
utility of these chemicals.
 The  active   Silver is commonly used in the
metal   commercial.
catalyst  
(Carrier) - Alumina, silicon
carbide, MgO, SiO2 and
ZrO2

Bulk  
support   Catalyst   Inhibitors  
Organic halide are very
effective for supressing
the undesireable
oxidation of EO to CO2
To enhances the activity and and H2O, although not
the selectivity of the catalyst significantly altering the
and improves its long-term Promoters   main reaction to EO.
stability. However, excess
addition will lower the
performance.-Alkaline earth
metal- cesium, rubidum or
potassium.
 HAZARD OF EO

  Ethylene oxide is toxic and a human carcinogen and EO gas

is flammable, even without being mixed with air, and can auto
decompose explosively. The chemical properties of EO require
various techniques to prevent any type of losses.
  In particular EO/EG storage and loading design must
guarantee that there is no ingress of air or impurities likely to
react dangerously with EO, prevention of leaks and a vapor
return system on EO loading to minimize the gaseous
streams to be handled.

video
Handling  And  storage  
precautions  
  Make sure that the sterilizer is properly grounded.
  Protect the container from physical damage and inspect for any
cracks and leaks
  Do not store in direct sunlight
  Do not drop it, move gently.

Engineering control
  EO is a major fire hazard, can burn in the absence of oxygen. All
electrical devices used must be engineered and designed to
applicable to local / fire codes.
Environmental impact of EO plant

The main air emissions from ethylene oxide (EO)/ethylene

glycol (EG) plants are the following:
  Carbon dioxide, as a by-product during the manufacture of
EO, removed by absorption in a hot carbonate solution, and
then stripped and vented to air with minor quantities of
ethylene and methane;
  Purge gas from recycle gas to reduce the build-up of inert
gases and vented to air after treatment. In the oxygen based
process the purge gas consists mainly of hydrocarbons
(e.g., ethylene, methane, etc.) and inert gases (mainly
nitrogen and argon impurities present in the ethylene and
oxygen feedstock). After treatment, the remaining gases
(mainly nitrogen and carbon dioxide) are vented to
atmosphere;
  VOC and some compounds with lower volatility (due to
mechanical entrainment) from open cooling towers where
EO-solution is stripped, cooled and re-routed to the
absorber;
  EO containing non condensable gases like argon, ethane,
ethylene, methane, carbon dioxide, oxygen and/or nitrogen
vent gases from various sources in the process (i.e.,
flashing steps in the EO recovery section, EO purification
section, process analyzers, safety valves, EO storage or
buffer vessels and EO loading / unloading operations);
  Fugitive emissions with VOC releases of EO, ethylene, and
methane (where methane is applied as diluents in the
recycle gas loop).
Recommended emission prevention and control
measures include the following:

  Direct oxidation of ethylene by pure oxygen due to the lower

ethylene consumption and lower off-gas production;
  Optimization of the hydrolysis reaction of EO to glycols in
order to maximize the production of glycols, and to reduce
the energy (steam) consumption;
  Recovery of absorbed ethylene and methane from the
carbonate solution, prior to carbon dioxide removal, and
recycling back to the process. Alternatively, they should be
removed from the carbon dioxide vent either by thermal or
catalytic oxidizers;
  Inert gas vent should be used as a fuel gas, where possible.
If their heating value is low, they should be routed to a
common flare system to treat EO emissions;
  Adoption of high integrity sealing systems for pumps,
compressors and valves and proper types of O-ring and
gasket materials;
  Adoption of a vapor return system for EO loading to
minimize the gaseous streams requiring further treatment.
Displaced vapors from the filling of tankers and storage
tanks should be recycled either to the process or scrubbed
prior to incineration or flaring. When the vapors are
scrubbed (e.g., vapors with low content in methane and
ethylene), the liquid effluent from the scrubber should be
routed to the desorber for EO recovery;
  Minimization of the number of flanged connections and
installation of metal strips around flanges with vent pipes
sticking out of the insulation to allow monitoring of EO
release;
  Installation of EO and ethylene detection systems for
continuous monitoring of ambient air quality.
Alcohol 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. The reaction with alcohols could
be represented as:
  The solubility of the product ethoxylates can be varied according
to the number of ethylene oxide units in the molecule.
  The solubility is also a function of the chain-length of the alkyl
group in the alcohol or in the phenol.
  Longer-chain alkyl groups reduce water solubility. In practice, the
number of ethylene oxide units and the chain-length of the alkyl
group are varied to either produce water-soluble or oil-soluble
surface active agents.
  Linear alcohols used for the production of ethoxylates are
produced by the oligomerization of ethylene using Ziegler
catalysts or by the Oxo reaction using alpha olefins.
  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.
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 production process

  The hydrolysis reaction occurs at a temperature range of 50–

100°C.
  Contact time is approximately 30 minutes. Di- and triethylene
glycols are co products with the monoglycol. Increasing the
water/ethylene oxide ratio and decreasing the contact time
decreases the formation of higher glycols.
  A water/ethylene oxide ratio of 10 is normally used to get
approximately 90% yield of the monoglycol.
  However, the di- and the triglycols are not an economic burden,
because of their commercial uses.
  A new route to ethylene glycol from ethylene oxide via the
intermediate formation of ethylene carbonate has recently been
developed by Texaco.
  Ethylene carbonate may be formed by the reaction of carbon
monoxide, ethylene oxide, and oxygen.
  Alternatively, it could be obtained by the reaction of phosgene and
methanol.
  Texaco process : Ethylene carbonate is a reactive chemical. It
reacts smoothly with methanol and produces ethylene glycol in
addition to dimethyl carbonate:
  The reaction occurs at approximately 80-130°C with the proper
catalyst
  Oxirane process: Ethylene glycol could also be obtained directly
from ethylene by the Oxirane 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 hydrolysis reaction occurs at approximately 107–130°C and
1.2 atmospheres.
  Acetic acid is then recovered for further use:
  A higher glycol yield (94%) than from the ethylene oxide process is anticipated.
Drawbacks of the process:
a) Corrosion caused by acetic acid
b) Incomplete hydrolysis of the acetates
c) The separation of the glycol from unhydrolyzed monoacetate is hard to
accomplish.
Uses of ethylene glycol

Coolant
  The major use of ethylene glycol is as a medium for
convective heat transfer in, for example, automobiles and
personal computers.
  Due to its low freezing point, it is also used as a de-icing
fluid for windshields and aircraft.
  Ethylene glycol is also commonly used in chilled water air
conditioning systems that place either the chiller or air
handlers outside, or systems that must cool below the
freezing temperature of water.
Hydrate inhibition
  Ethylene glycol is being widely used to inhibit the formation
of natural gas clathrates (NG trapped within a crystal
structure of water, forming a solid similar to ice) in
long multiphase pipelines that convey natural gas from
remote gas fields back to an onshore processing facility.
  Ethylene glycol can be recovered from the natural gas and
reused as an inhibitor after a purification treatment that
removes water and inorganic salts.
Manufacturing
  Ethylene glycol has become increasingly important in the plastics
industry for the manufacture of polyester fibers and resins,
including polyethylene terephthalate (PET), which is used to
make plastic bottles for soft drinks.
  The antifreeze capabilities of ethylene glycol have made it an
important component of vitrification mixtures for low-temperature
preservation of biological tissues and organs.
  Minor uses of ethylene glycol include the manufacture of
capacitors (ethylene  glycol  mixture  exhibits  a  high  dielectric  
strength  (up  to  66  V),  a  low  water  content  and  self-­‐
extinguishing  properties  for  employment  as  electrolyte  in  an  
aluminum  electrolytic  capacitor), as a chemical intermediate in
the manufacture of 1,4-dioxane and as an additive to prevent
corrosion in liquid cooling systems for personal computers.
Conclusion  

  EO are widely used in the Industry.

  Use appropriate PPE for handling EO.
  Avoid direct contact with EO.
  Ethylene glycol is the derivative of EO.
  Important to read the MSDS before dealing with
EO!