ASSIGNMENT-2

PETROLEUM REFINERY AND PETROCHEMICAL( CH-416)

GROUP MEMBERS
1. DUA YOUSUF (CH-17018)
2. TAIMOOR AHMED KHAN LODHI (CH-17040)
3. BAZIL AHMED KHAN (CH-17309)
4. IFFAT FAROOQI (CH-17310)

Submitted to: MISS TUBA SIRAJ

DEPARTMENT OF CHEMICAL ENGINEERING

NED UNIVERSITY OF ENGINEERING AND TECHNOLOGY

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Section TABLE OF CONTENTS Page no. PAGE NO.
SECTION
1.1 Ethy Introduction of ethylene oxide production 04
1.2 Selection of process for ethylene oxide production 04
1.3 Description of the process 04
1.4 PROD Production of ethylene oxide by the oxidation of ethylene with air 05
1.4.1 Air purification 06
1.4.2 Primary reactor ( oxidation of ethylene) 06

1.4.3 Packed column absorber (primary absorber) for recovery of ethylene 07

oxide

1.4.4 PURGE Purge reactor for recovery of ethylene oxide 08

1.4.5 Purge absorber to recover ethylene oxide 08
1.4.6 Desorber to remove CO2 and other gases 09
1.4.7 Stripping of ethylene oxide to separate gases 09
1.4.8 Refining of ethylene oxide to remove impurities 09
1.5 Safety and handling of ethylene oxide 09
1.6 Safety 09
1.7 10
Explosion and fire control
1.8 Environmental protection 10
1.9 Handling, storage, and transportation 10
1.10 Ethylene oxide as a primary product 10
2.1 Introduction of ethylene-di-chloride 11
2.2 Process selection for the formation of ethylene-di-chloride 12
2.3 Process description of ethylene dioxide 13
2.4 Uses of Ethylene-di-chloride 14
2.5 Safety concerns 14
2.5.1 Storage of ethylene-di-chloride 14
2.5.2 Safety concerns regard to Handling 14
2.5.3Exp Exposure control and personal protection 15
2.6 Environmental precautions 15
3.1 Introduction of vinyl acetate monomer 16
3.2 Properties of vinyl acetate monomers 17
3.3 Process selection for the production of vinyl acetate monomers 17
3.4 Description of process for the production of vinyl acetate monomers 18
3.5 Uses Uses of vinyl acetate monomers 19
3.6 Safety while using vinyl acetate monomers 19
3.7 Storage 20
3.8 Handling 20
3.9 Environmental protection 20

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 PAGE NO

FIGURES :

Fig 1-1 Production of ethylene oxide by direct oxidation of air with ethylene-----------------------------05

Fig 1-2 Oxidation of ethylene in primary reactor -------------------------------------------------------------06

Fig 1-3 Primary absorber -----------------------------------------------------------------------------------------07

Fig 1-4 Purge reactor to recover ethylene oxide---------------------------------------------------------------08

Fig 1-5 Purge absorber to recover ethylene oxide ------------------------------------------------------------08

Fig 2-1 Density vs temperature-----------------------------------------------------------------------------------12

Fig 2-2: Production of Ethylene-di-Chloride----------------------------------------------------------------------13

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 SECTION #01

ETHYLENE OXIDE
1.1 INTRODUCTION

Ethylene oxide (C2H4O) is an organic compound with functional group ether attached to it. It can be
produced by the direct oxidation of ethylene oxide in the presence of air or oxygen. About 60 to 77% of
ethylene is consumed to form ethylene oxide in the oxidation process. In oxidation process side reaction
also occur, CO2, H20, small amount of acetaldehyde and formaldehyde is produced as a side product.
Ethylene oxide is a very reactive, versatile compound. Its reaction takes place mainly via ring-opening and
is highly exothermic. It can also produce by the photochemical decomposition of alkyl peroxide.

1.2 PROCESS SELECTION

Ethylene oxide can be produced by continuous direct oxidation of ethylene in the presence of a
catalyst (silver). The oxidizing agent may be air or pure oxygen.

I. Oxidation of ethylene oxide in presence of air

II. Oxidation of ethylene in presence of oxygen

1.3 PROCESS DESCRIPTION

Before 1973 ethylene oxide was produced from ethylene and ethylene chlorohydrin intermediate. But it could
not compete economically with the direct oxidation process. In the direct ethylene oxidation process, the
reaction takes place in the vapor phase. The two main reactions are

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1.4 PRODUCTION OF ETHYLENE OXIDE BY THE OXIDATION OF ETHYLENE WITH AIR:

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 FIG 1-1 PRODUCTION OF ETHYLENE OXIDE BY DIRECT OXIDATION OF AIR
WITH ETHYLENE

1.4.1 AIR PURIFICATION

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 The air used in the oxidation of ethylene oxide is purified in a chamber to remove impurities so
that it cannot deactivate catalysts and to avoid any side reaction.

1.4.2 PRIMARY REACTOR ( OXIDATION OF ETHYLENE)

Ethylene and compressed air after mixing with recycle stream coming from the primary absorber enter to
the primary reactor. Ethylene to air feed ratio is 10:1 by weight.
. The reaction takes place in the vapor phase. The reaction is exothermic so heat must be removed for best
conversion and yield of product(ethylene oxide).In the primary reactor, the reaction takes place in the
presence of a catalyst (packed in a tube). The reaction takes place between a temperature range of 220 C to
280 C and at a pressure of 1 to 3 MPa

ACTIVITY OF CATALYST:

The activity of the catalyst is enhanced by adding promoters such as alkali metal or alkaline earth metal.
Catalyst inhibitors such as halide are added to avoid any side reaction like conversion of ethylene to CO2.
Addition of Halide not altering the primary reaction.
A small amount of Formaldehyde and Acetaldehyde is also formed as a bi-product.
OUTLET OF PRIMARY REACTOR
Ethylene oxide and CO2 is produced in the primary rector while the remaining ethylene (2-3 mol%)
remains unreacted. The CO2, Ethylene oxide, and ethylene are cooled compressed and entered into the
primary absorber. The gases which were not absorbed in the water are exit from the top of the absorber,
cools down and recycle to the primary reactor, and processed.

FIG 1-2 OXIDATION OF ETHYLENE IN PRIMARY REACTOR

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1.4.3 PACKED COLUMN ABSORBER (PRIMARY ABSORBER)

The gases from the primary reactor are entered from the bottom of the absorber while H2O is coming from
the top. Both H20 and gases counter currently come in contact and ethylene oxide, some CO2, aldehyde, and
hydrocarbon absorb in water.

In the packed column absorber the stream is countercurrent with cold water, ethylene oxide, some CO2,
aldehyde, and hydrocarbon dissolves in water.

While the unabsorbed gases are recycled back to the primary reactor after cooled in the HE with the outlet
of the primary reactor. A smaller amount of unabsorbed gas stream is purged to prevent the accumulation
of inert gases such as N2 and CO2 in the system.

FIG 1-3 PRIMARY ABSORBER

1.4.4: SECONDARY ( PURGE REACTOR)

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 The purge stream may contain a small amount of ethylene oxide which is recovered in the purge reactor.
The effluent stream from the secondary purge reactor is then sent to the purge absorber.

FIG 1-4 PURGE REACTOR TO RECOVER ETHYLENE OXIDE

1.4.5: PURGE ABSORBER:

In the purge, absorber gases enter from the bottom and water enters from the top of the purge absorber is
counter currently come in contact. Water absorbs ethylene oxide while the overhead gases from the purge
absorber are recycled to the purge reactor and some stream is vented.

FIG 1-5 PURGE ABSORBER TO RECOVER ETHYLENE OXIDE

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1.4.6: DESORBER ( to remove dissolved gases in the ethylene oxide)

The dilute aqueous solution of ethylene oxide, Carbon dioxide, and other volatile compounds from the
primary absorber and purge absorber is mixed and entered into the desorbed.

In the desorber, ethylene oxide and inert gases are distilled under reduced pressure. Now the water
becomes free from ethylene oxide and inert gases, this water is then reused in the primary and purge reactor
to make the process economical. The crude ethylene oxide is then sent to the stripper.

1.4.7: STRIPPING OF ETHYLENE OXIDE TO SEPARATE GASES

In the stripper, the CO2 and inert gases present in the crude ethylene oxide is removed. Light gases are
stepped out and vented from the top. The ethylene oxide is then sent to the final refining column.

1.4.8: REFINING COLUMN TO PURIFY ETHYLENE OXIDE

The final product is 99.5mole % ethylene oxide which is stored in a pressurized tank under nitrogen
pressure.

FUGITIVE EMISSION (Emission of gases and vapors from pressurized equipment due to leak or other):

The fugitive emission of ethylene oxide is from the pump seal. Pressure relief devices, valves, flanges, etc.
The fugitive emission can be controlled by inspection and maintenance.

1.5 SAFETY AND HANDLING OF ETHYLENE OXIDE:

To avoid flammability, explosion, and health hazards ethylene oxide handling units have always been
designed. The emergency holding tank can also cause some emission of ethylene oxide to the
environment

1.6 SAFETY :

The following safety should be made to reduce ethylene oxide emission from ethylene oxide production
plant to the environment

 Install ethylene oxide and flammable gas emission detector and analyze the sample
 The ethylene oxide pump should be sealed properly
 Use pressurized nitrogen in labyrinth shaft seal of centrifugal ethylene oxide compressors.
 Welding should be done to reduce the flange joint. Because joint may cause leakage of ethylene
oxide to the environment under high pressure.
 EPA reference method 21 Determination of volatile organic compound leaks is used to detect,
locate the leakage. Method 21 is used to produce no leak.
 Install leak detector where the possibility of leakage is present in the pipes and fittings
 The rotating equipment should be analyzed properly and Vibration should be minimized.

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  If there is an emission due to leakage then the emitted Ethylene oxide should be absorbed in water
and then discharge to the drainage.
1.7 EXPLOSION AND FIRE CONTROL
Pure ethylene oxide vapor or ethylene oxide vapor mixed with air or inert gases can decompose
explosively. Explosiveness depends on temperature pressure and concentration, the type, form, and
energy of the ignition source, and the type of the container. High pressure can be generated on the
explosion of ethylene oxide, therefore for safe handling, the exact explosive limit must be known.
Pure ethylene oxide vapors at 101.3 Kappa decomposes when passed through a heated platinum coil
at 571 C.
1.8 ENVIRONMENTAL PROTECTION

The occupational safety and health administration (OSHA) has enacted a 1ppm,8 hours - weighted average
occupational exposure standard that may result in some control of ethylene oxide emission.

1.9 HANDLING, STORAGE, AND TRANSPORTATION:

 Ethylene oxide has repeatedly caused serious explosions, fires, and accidents. It is an extremely
hazardous substance because it can explode and is highly flammable and extremely reactive
(exothermic reaction).
 Ethylene oxide is toxic and possess a danger to health AND TO THE ENVIRONMENT
Ethylene oxide can be released to the atmosphere during its production, consumption in the raw
material in other manufacturing processes, and during its use as a fumigant and sterilant. Ethylene
oxide gas is produced at ambient temperature so this gas is stored under nitrogen at 10 C approx.
Loses from the storage tank are only because of displacement during filling. This loss can be
prevented by proper control.

1.10 ETHYLENE OXIDE AS PRIMARY PRODUCT

About 99% of ethylene oxide is used as a chemical intermediate for the production of

1. Ethylene glycol
2. Mono, di, tri, and polyethylene glycol
3. Glycol ethers and surface-active agents
4. Ethoxylates

ETHYLENE DI-CHLORIDE
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SECTION 2

2.1 INTRODUCTION

The chemical compound 1,2-dichloroethane, also known as ethylene dichloride (EDC). It is a

chlorinated hydrocarbon that is widely used in the production of vinyl chloride monomer (VCM,
chloroethene), the major precursor for PVC production. The elemental composition of EDC is
Carbon 24.27%, Hydrogen 4.07%, and Chlorine 71.66%.

Structure

PROPERTIES
Chemical formula C2H4Cl2
Molar mass 98.95 g·mol−1
Appearance Colorless liquid
Odor characteristic, pleasant chloroform-like odor
Density 1.253 g/cm3, liquid
Melting point −35 °C (−31 °F; 238 K)
Boiling point 84 °C (183 °F; 357 K)
Viscosity 0.84 mPa·s at 20 °C
Solubility in water 0.87 g/100 mL (20 °C)

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 Fig 2-1: Density vs Temperature

2.2 PROCESS SELECTION

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Ethylene dichloride is produced by the direct chlorination or oxychlorination of ethylene. Most
EDC plants are combined with vinyl chloride monomer (VCM) plants. The VCM process produces
considerable quantities of hydrogen chloride (HCl), which is moved to oxychlorination for
recycling to generate more EDC. When operating both the oxychlorination and the direct
chlorination pathway at the same time, the problem of disposal of hydrogen chloride is eliminated
in the overall process. This technology (often known as the balanced process) is being used in the
majority of the developed regions (figure 2 for this process).

Fig 2-2: Production of Ethylene-di-Chloride

2.3 PROCESS DESCRIPTION

In the first step, Direct chlorination is performed in the liquid phase where the reaction of liquid
chlorine and pure ethylene takes place in the presence of ferric chloride. The reaction can be carried
out at either low (20-70°C) or high (100-150°C) temperatures.

H2C=CH2 + Cl2 → Cl-CH2-CH2-Cl

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The advantage of the low-temperature process is low by-product formation but requires more
energy to recover the EDC. While at high-temperature process utilizes the heat of reaction of the
EDC in the distillation, and helps in considerable energy savings.

In the second step the oxychlorination process, the reaction of pure ethylene and hydrogen chloride,
mixed with oxygen takes place at 200-300°C and 4-6 bar in the presence of a catalyst, usually
cupric chloride. Either a fixed bed or fluid bed reactor is used for reaction, the latter being preferred
as it is easier to control the temperature.

H2C=CH2 + 2 HCl + ½ O2 → Cl-CH2-CH2-Cl + H2O

2.4 USES

Ethylene dichloride is mainly used as a raw material in the manufacture of vinyl chloride monomer
(VCM). The vinyl chloride, in turn, is used to manufacture polyvinyl chloride (PVC) resin. It is also
used as an intermediate in the manufacture of chlorinated and fluorinated compounds. Ethylene
dichloride has been used as a solvent in the textile, metal cleaning, and adhesive industries.

2.5 SAFETY CONCERNS

2.5.1 Storage

Ethylene dichloride should be kept in containers tightly closed in a dry, cool, and well-ventilated
place. Keep away from heat and sources of ignition.

2.5.2 Handling

Wear personal protective equipment. Do not get in eyes, on the skin, or clothing. Do not
ingest. Use only under a chemical fume hood. Do not breathe vapors or spray mist. Keep away from
open flames, hot surfaces, and sources of ignition. Use only non-sparking tools. To avoid ignition
of vapors by static electricity discharge, all metal parts of the equipment must be grounded. Take
precautionary measures against static discharges.

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 2.5.3 Exposure controls / personal protection

Component ACGIH TLV OSHA PEL NIOSH IDLH Mexico OEL

(TWA)

Ethylene TWA: 10 ppm (Vacated) TWA: 1 ppm IDLH: 50 ppm TWA: 10 ppm
dichloride (Vacated) TWA: 4 mg/m3 TWA: 1 ppm TWA: 40 mg/m3
Ceiling: 100 ppm TWA: 4 mg/m3
(Vacated) STEL: 2 ppm STEL: 2 ppm
(Vacated) STEL: 8 mg/m3 STEL: 8 mg/m3
TWA: 50 ppm

Legend
ACGIH - American Conference of Governmental Industrial Hygienists
OSHA - Occupational Safety and Health Administration
NIOSH IDLH: The National Institute for Occupational Safety and Health Immediately Dangerous
to Life or Health

2.6 Environmental Precautions

Should not be released into the environment. Do not empty into drains because of their toxicity

Component Freshwater Algae Freshwater Fish Microtox Water Flea

Ethylene EC50: = 166 mg/L, 96h LC50: 110 - 123 mg/L, 96h Not listed EC50: 140 - 190
dichloride static (Desmodesmus flow-through (Pimephales mg/L, 48h
subspicatus) promelas) Static (Daphnia
EC50: > 433 mg/L, 96h LC50: 230 - 710 mg/L, 96h Magna)
(Pseudokirchneriella flow-through (Lepomis
subcapitata) macrochirus)
LC50: = 225 mg/L, 96h static
(Oncorhynchus mykiss)

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 VINYL ACETATE MONOMER
SECTION 3

3.1 INTRODUCTION:

Vinyl acetate is an organic compound with the formula CH3CO2CH=CH2. This colorless liquid is

the precursor to polyvinyl acetate, an important industrial polymer. Its IUPAC name is ETHENYL
ACETATE. The worldwide production capacity of vinyl acetate was estimated at 6,969,000
tonnes/year in 2007, with the most capacity concentrated in the United States (1,585,000 all in
Texas), China (1,261,000), Japan (725,000), and Taiwan (650,000). It has the formula
CH3COOCH=CH2 and is a key raw material in the production of chemicals which are then used to
manufacture a wide variety of consumer and industrial products.

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3.2 PROPERTIES OF VINYL ACETATE :

Properties for industrial vinyl acetate are given below in the table

3.3 PROCESS SELECTION:

The vinyl acetate monomer (VAM) has the following process;

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 Design of the reactor for vinyl-acetate manufacturing in a recycle stream

Following are the main components used in the process;

3.4 PROCESS DESCRIPTION:

Vinyl acetate monomer can be produced by the catalyzed gas-phase process in which ethylene
reacts with acetic acid and oxygen over a fixed bed catalyst at a pressure of 1 to 30 bar and a
temperature of 130⁰C to 200 ⁰C in a fixed bed tubular reactor.

Main Reaction
C2H4 + CH3COOH + 1/2O2  CH2=CHOCOCH3 + H2O

Side Reaction:
In the side reaction, ethylene is oxidized to CO₂

C2H4 + 3O2 2CO2 + 2H2O

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 • The main reaction generates VAM (CH2=CHOCOCH3) product and by-product water
(H2O) from C2H4, AcOH (CH3COOH), and O2. The side reaction generates. Both
reactions are exothermic, thus reaction heat is removed by boiler feed water (BFW)
circulation and steam is generated at the shell side of the reactor.
• The reactor outlet gas containing about 5mol% VAM product is cooled down to 37 C with
two coolers. Unreacted AcOH, H2O, and VAM are condensed as liquid VAM crude at the
separator. On the other hand, separated gas leaving from the separator includes unreacted
C2H4, O2, byproduct CO2, inert ethane (C2H6), and a small amount of uncondensed VAM.
• This separated gas is compressed by the compressor to circulate recycle gas flow, then
introduced to the absorber.
• The uncondensed VAM is absorbed by the cold AcOH which is fed from the top of the
absorber.
• The mixture of VAM and AcOH is discharged from the bottom of the absorber and mixed
with the VAM crude at the intermediate buffer tank.
• Part of VAM removed from the top of the absorber is recycled to the inlet of the process.
The remaining part of the gas is introduced to the CO2 remover and the gas purge system,
which keeps the concentration of CO2 around 5~10mol% and C2H6 around 5mol% in the
gas recycle line.
• The VAM crude at the intermediate buffer tank is fed to the azeotropic distillation column.
VAMH2O mixture discharged from the top of the column is condensed at the condenser and
separated at the decanter.
• VAM product is discharged as an organic product from the decanter. Unreacted AcOH is
discharged from the bottom and recycled to both the vaporizer and the absorber.

3.5 USES:
 The major uses of VAM are in coatings for the Textile and Paper industries.
 VAM is also used in laminated safety glass, packaging, automotive fuel tanks, and acrylic
fibers.
 The second-largest consumer of VAM is polyvinyl alcohol (PVOH) which is manufactured
from PVA. Main uses for PVOH include textiles, adhesives, packaging films, thickeners,
and photosensitive coatings.
 The fast-growing use of VAM in the manufacture of ethylene vinyl alcohol (EVOH) is used
as a barrier resin in food packaging, plastic bottles, and gasoline tanks, and engineering
polymers.

3.6 SAFETY:

 VAM is an eye, skin, and respiratory tract irritant. Workers should be warned to avoid skin
and/or eye contact with VAM and to avoid breathing its vapors

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  Safety showers and eyewash facilities should be provided in areas where VAM is being
handled.
 Workers should be trained to promptly wash any area of the skin exposed to VAM with
large amounts of water.
 Store in tightly closed containers in a cool, well-ventilated area away from HEAT and
DIRECT SUNLIGHT.
 Use non-sparking tools and equipment, especially when opening and closing containers of
vinyl acetate
 The complete protective suit includes SCBA with a full facepiece operated in pressure-
demand or other positive-pressure mode and impervious gloves.

3.7 STORAGE:

Vinyl acetate monomer (VAM) can be stored, transported, and handled safely if its hazards are
understood. Two guiding principles for the proper storage, transport, and handling of VAM are to
avoid,

 Situations such as inhibitor depletion, excess heat, or cross-contamination could result in

spontaneous or uncontrolled polymerization.
 Situations that could result in uncontrolled releases (spills, overfills, runaway
polymerization) create potential fire risks.
A recommended storage temperature below 30oC (86⁰F). The temperature should not exceed 100
°F (38 °C). Tank heating is due to ambient temperature changes only. It is not recommended to heat
the tank with other heating media. It should therefore be stored in a cool, dry, well-ventilated area
that is free from the risk of ignition. For transportation purposes, it is classified as packing group II
and hazard class 3 and it is an irritant. Turnover of the tank contents every 60 days or less for VAM
at 3 ppm HQ min.; 90 days for VAM at 6 ppm min.; and 120 days for VAM at 12 ppm min. In the
end, we should have a rust-free storage environment.

3.8 HANDLING:

When bulk shipments are loaded or unloaded, the storage tank vent gas may be returned to the
shipping vessel through a dedicated vapor return line or may be sent to the vapor
collection/abatement systems such as a flare, thermal oxidizer, or incinerator. Before use, hoses
should be checked for cleanliness and integrity. If hoses are used for multiple services, they should
be thoroughly cleaned after each use to avoid cross-contamination. Blanketing with dry gas is
important because the presence of water initiates a hydrolysis reaction of the VAM to acetic acid

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and acetaldehyde. Nitrogen is preferred as the blanket gas. Equipment should be grounded to
prevent a build-up of static electricity.

3.9 ENVIRONMENTAL:

Released into the environment the vinyl acetate evaporates easily, being degraded rapidly by
photochemical reactions, as well as biodegraded by either anaerobic or aerobic mechanisms. Vinyl
acetate is dangerous when exposed to heat, flame, or oxidizers, and as a consequence, it requires
adhering to safety measures when stored or manipulated by operators. The same precaution is valid
for the raw materials. Ethylene is highly explosive in a mixture with oxygen, the explosion limit
being at 10% vol. Acetic acid is a highly toxic and corrosive substance. Stainless steel of Cr/Ni/Co
type is employed for operations involving acetic - acid solutions in boiling conditions, but normal
stainless steel may be used for vapor - phase operations. Vinyl acetate is slightly or moderately
toxic to humans and animals. The vapor irritates the eyes starting with 20 ppm, while the detection
threshold is reported to be about 0.5 ppm.

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guage=en

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