Department of Chemical Engineering

NED University of Engineering and Technology

Environmental safety and sustainability in

petrochemical industry
Assignment #1

Group Members: Roll Numbers:

Bilal Nadeem CH-19034
Ibraheem Shaikh CH-19029
Muhammad Mubeen CH-19040
Abdul Rafay Sarfraz CH-19045

Course: Petroleum Refinery & Petrochemicals

Course Code: CH-416
Batch: 2019-2023
Course Instructor: Ms. Tuba Siraj Ansari

1
 Table of Contents

Table of Contents ........................................................................................................... 2

Chapter 1 ........................................................................................................................ 5
ETHYLENE OXIDE ..................................................................................................... 5
1.1 INTRODUCTION ................................................................................................ 5

1.2 PRODUCTION PROCESS .................................................................................. 6

1.2.1 The Basic Chemistry ..................................................................................... 6

1.2.2 Process Description ....................................................................................... 6

1.3 SUSTAINABILITY IN PROCESS ..................................................................... 9

1.4 SAFETY CONCERNS AND HAZARDS ......................................................... 10

1.4.1 Environmental Concerns ............................................................................. 10

1.4.2 Storage Concerns ........................................................................................ 10

1.4.3 Handling Concerns...................................................................................... 10

1.4.4 USES OF ETHYLENE OXIDE ................................................................. 11

1.5 REFERENCES ................................................................................................... 11

Chapter 2 ...................................................................................................................... 12
METHYL TERTIARY BUTYL ETHER (MTBE) ..................................................... 13
2.1 Process Selection ................................................................................................ 13

2.1.1 Standard Process ......................................................................................... 13

2.1.2 Reactive Distillation Process ...................................................................... 14

2.2 Process Description ............................................................................................ 14

2.2.1 Pump ........................................................................................................... 15

2.2.2 First Heat Exchanger................................................................................... 15

2.2.3 Reactor ........................................................................................................ 15

2.2.4 First Distillation Column ............................................................................ 16

2.2.5 Second Heat Exchanger .............................................................................. 16

2.2.6 Third Heat Exchanger ................................................................................. 16

2.2.7 Absorber ...................................................................................................... 16

 2.2.8 Second Distillation Column ........................................................................ 17

2.2.9 Fourth Heat Exchanger ............................................................................... 17

2.2.10 Fifth Heat Exchanger ................................................................................ 17

2.3 Uses & Safety Concerns ..................................................................................... 18

2.3.1 Storage ........................................................................................................ 18

2.3.2 Handling ...................................................................................................... 18

2.3.3 Environmental Concern .............................................................................. 18

Chapter 3 ...................................................................................................................... 20
VINYL CHORIDE MONOMER ................................................................................ 20
3.1 INTRODUCTION .............................................................................................. 20

3.2 PRODUCTION PROCESS ................................................................................ 20

3.3 Process Description ............................................................................................ 21

3.4 SUSTAINABILITY IN PROCESS ................................................................... 22

3.5 SAFETY CONCERNS AND HAZARDS ......................................................... 22

3.5.1 Environmental Concerns ............................................................................. 22

3.5.2 Storage Concerns ........................................................................................ 23

3.5.3 Handling Concerns...................................................................................... 23

3.6 USES OF VINYL CHLORIDE MONOMER ................................................... 24

Chapter 4 ...................................................................................................................... 25
ACETALDEHYDE ..................................................................................................... 25
4.1 INTRODUCTION .............................................................................................. 25

4.2 OCCURRENCE ................................................................................................. 25

4.3 USES .................................................................................................................. 25

4.4 Different Manufacturing Processes .................................................................... 26

4.4.1 Oxidation of Ethylene: ................................................................................ 26

4.4.2 By Oxidation of ethyl alcohol: .................................................................... 27

4.4.3 By ethyl alcohol Dehydrogenation: ............................................................ 28

4.4.4 Selection of Process with Justification ....................................................... 29

4.5 Safety in Process Industries................................................................................ 29

4.5.1 Initial aid: .................................................................................................... 29

4.5.2 Skin Contact:............................................................................................... 30

4.5.3 Warning: ..................................................................................................... 30

4.6 Handling: ............................................................................................................ 30

4.7 Shipping and storage: ......................................................................................... 31

4.8 Environmental Effects ........................................................................................ 31

4.8.1 Air emissions: ............................................................................................. 31

4.8.2 Water discharge: ......................................................................................... 31

4.8.3 Solid waste: ................................................................................................. 31

4.8.4 Spills and Leaks Prevention: ....................................................................... 32

4.8.5 Risk assessment: ......................................................................................... 32

4.8.6 Environmental regulations: ......................................................................... 32

4.9 Sustainability in acetaldehyde production.......................................................... 32

4.9.1 Utilize alternative feedstock: ...................................................................... 33

4.9.2 Invest in renewable energy: ........................................................................ 33

4.9.3 Implement carbon capture and storage: ...................................................... 33

4.9.4 Enhance process effectiveness: ................................................................... 33

4.9.5 Implement recycling and recovery strategies: ............................................ 33

4.9.6 Conduct a Life Cycle Assessment (LCA):.................................................. 33

 Chapter 1

ETHYLENE OXIDE

1.1 INTRODUCTION

Ethylene oxide is an organic compound with the formula C2H4O. It is a cy-

clic ether and the simplest epoxide: a three-membered ring consisting of
one oxygen atom and two carbon atoms. Ethylene Oxide is colorless, odorless, flam-
mable, toxic gaseous cyclic ether with a sweet ether-like smell with a flash point be-
low 0 °F. Liquid less dense than water. Vapors heavier than air. May polymerize exo-
thermically if heated or contaminated.
1.2 PRODUCTION PROCESS

1.2.1 The Basic Chemistry

The ethylene oxide process involves the direct vapor phase oxidation of ethylene over
a silver containing catalyst at elevated temperatures to give ethylene oxide according
to

The required oxygen is normally supplied from an air separation plant. The main by-
products formed are carbon dioxide and water. A very small amount of the ethylene
oxide formed may isomerize to acetaldehyde, which in turn is in general rapidly oxi-
dized to carbon dioxide and water. Therefore, only traces of acetaldehyde are found in
the reactor product.

1.2.2 Process Description

The direct oxidation process for the manufacture of ethylene oxide from ethylene can
be divided into two sections, an oxidation section and a purification section. This ap-
plies to both the air case and the oxygen case process. In view of the commercial
dominance of the oxygen case process, we will in general describe mainly the oxygen
case technology with limited excursions into the air case technology to emphasize the
major differences. The typical basic process flow schemes for the oxygen-type and
air-type ethylene oxide process are shown in Figs. 1 and 2, respectively,
As only partial conversion of the ethylene and oxygen will be applied, a large eth-
ylene recycle stream is forced around into which make-up ethylene is fed and oxygen
is injected by means of a specially designed mixing nozzle. Diluents in the form of
nitrogen, methane, and ethane can be added to the system, carbon dioxide can be left
in the recycle gas after the removal of part of the carbon dioxide to achieve an optimal
concentration.
This ethylene and oxygen-enriched gas will-after exchanging heat with reactor exit
gas- water a multitubular reactor where over a silver-containing catalyst the reaction
to ethylene oxide and by-products takes place at temperatures varying between 200-
300°C. Ethylene concentrations are normally between 20-30%vol (in the air case
around 5%) and oxygen concentrations as high as a margin from the flammability
limit will allow. A space velocity of between 2500 and 5000 Nm 3/h per m3 catalyst is
normally chosen. Reaction pressures vary between 15 and 25 atm.
In the reactor shell a liquid coolant is pumped around to remove the heat of reaction.
The coolant liquid is then returned to the reactor. To obtain optimum yields of eth-
ylene oxide, it is necessary to use a moderator which suppresses the complete oxida-
tion reaction. Chlorinated hydrocarbons like 1,2-dichloroethane or vinyl chloride are
normally used.
The ethylene oxide produced in the reactor is recovered from the reactor effluent gas-
es by absorption in water in the ethylene oxide absorber. The ethylene oxide is then
stripped from the fat absorbent in the ethylene oxide stripper and subsequently sent to
the ethylene oxide purification section for the removal of light ends, water, and alde-
hydes. The ethylene oxide absorber overhead stream is for the larger part sent to a re-
cycle compressor (a small process vent, 0.1 to 0.2%, is necessary to remove inerts)
and then to a carbon dioxide absorber. The carbon dioxide is partly removed from the
recycle gas by absorption in a hot potassium carbonate solution. The carbon dioxide
absorber overhead gas is returned to the ethylene oxide reactor as reactor feed.
The fat absorbent from the carbon dioxide absorber is sent to the carbon dioxide strip-
per, where carbon dioxide is rejected to the atmosphere or recovered for further pro-
cessing. The stripped carbonate is returned to the absorber by the carbonate pump.
The ethylene oxide (EO) and water vapors from the top of the EO stripper are sent to
a light ends column after condensation in a series of heat exchangers. Light ends (e.
g., C02) are removed from the EO product down to a level to meet final product speci-
fications. Depending on final product specifications, the ethylene oxide is then dehy-
drated and aldehydes are removed in the final purification column.
1.3 SUSTAINABILITY IN PROCESS

Technology improvements during recent years have been concentrated on improve-

ments related to a more efficient utilization of ethylene and energy (steam and elec-
tricity) in view of their greatly increased prices, which in Europe and Japan are still
above those in the USA. A
more detailed inspection of the breakdown of cost elements in the manufacturing
costs per unit of ethylene oxide shows that around 70% of those costs are attributable
to ethylene, assuming a 15% depreciation per annum on investment costs for a large-
scale size plant (say 100,000 t/a or higher). The remaining 30% is divided over oxy-
gen (10%), utilities plus catalyst and chemicals (8%), and depreciation and mainte-
nance (12%). It is therefore clear that savings of ethylene using higher selectivity
catalyst are of major importance.

A lower consumption of ethylene demands a catalyst with higher selectivity. Over the
last decade catalysts with improved selectivities have been developed and are being
used in commercial plants. Selectivities have been improved from 67-70% in the early
1970s. to between 75-81% for initial operation at practical production conversions. In
addition, the use of high-purity feedstocks will-in particular in the oxygen-type pro-
cess-allow for very small vent streams to purge the inert components (e.g., argon)
from the recycle gas loop, thereby minimizing ethylene losses. Further improvements
in the degree of recovery of the unintentionally formed amount of glycol in the eth-
ylene oxide unit will add to the total recovered amount of ethylene oxide equivalent.

Savings in energy as far as they are already not consequential on the selectivity im-
provements of the catalyst (and here it should be noted that a catalyst with a higher
selectivity will generate less carbon dioxide which will require correspondingly less
energy to remove it) can be found in a more efficient use of heat in the process
streams.

In connection with energy saving, it is also worthwhile to mention the use of water-
cooled reactors, generating steam directly from the reactor and not via an intermediate
coolant, thereby contributing to improved energy economics.
1.4 SAFETY CONCERNS AND HAZARDS

1.4.1 Environmental Concerns

Sources of ethylene oxide emissions to the air include uncontrolled emissions or vent-
ing with other gases in industrial settings. Other sources of ethylene oxide emissions
to air include use as medical device sterilizers and emissions from fumigated materi-
als. The general public can be exposed to ethylene oxide by breathing polluted air,
smoking cigarettes, or being near smokers. workers, sterilizers and fumigators) may
be exposed in the workplace.
The immediate effects of exposure to high concentrations of ethylene oxide can mean
death of animals, birds or fish and death or low growth rate in plants. Long-term ef-
fects on animal life may include shortened lifespan, reproductive problems, lower fer-
tility, and changes in appearance or behavior. Ethylene oxide has moderate long-term
toxicity to aquatic life.

1.4.2 Storage Concerns

Severe explosion hazard when exposed to heat or flame. When heated, an irritating
gas is generated. Vapors are heavier than air and can travel considerable distances to
the source of ignition and flash back. Vapors form explosive mixtures with air over a
wide area. Liquids cannot be exploded, but vapors can easily decompose explosively.
Metal fittings containing magnesium, copper, or silver should be avoided, as trace
amounts of acetylene in ethylene oxide can form metal acetylides that can explode
vapors. Violent polymerization occurs on contact with strong bases (alkaline hydrox-
ides, ammonia) or acids.
Due to the potential for violent decomposition, ethylene oxide containers should be
adequately blanketed with inert gas and extensively protected from the effects of fire.

1.4.3 Handling Concerns

Ethylene Oxide is a CARCINOGEN and TERATOGEN in humans. There may be no
safe level of exposure to a carcinogen, so all contact should be reduced to the lowest
possible level. The above exposure limits are for air levels only. When skin contact
also occurs, you may be overexposed, even though air levels are less than the limits
listed above.
Ethylene oxide is irritating to the eyes, respiratory tract, and skin. Exposure to high
concentrations of ethylene oxide vapor or eye splashes of concentrated solutions can
cause eye irritation, inflammation of the eye membrane and corneal injury. Exposure
to ethylene oxide has also been linked to the development of cataracts.

Aqueous solutions of ethylene oxide or solutions formed when the anhydrous calcium
comes in contact with moist skin are irritating and may lead to a severe dermatitis
with blisters, blebs and burns. It is also absorbed by leather and rubber and may pro-
duce burns or irritation. Allergic eczematous dermatitis has also been reported.
Exposure to the vapor in high concentration leads to irritation of the eyes. Severe eye
damage may result if the liquid is splashed in the eyes. Large amounts of ethylene ox-
ide evaporating from the skin may cause frostbite.

1.4.4 USES OF ETHYLENE OXIDE

 Ethylene oxide is primarily utilized as a chemical intermediary in the produc-
tion of ethylene glycol (antifreeze), as well as other goods such textiles, deter-
gents, polyurethane foam, solvents, medications, and adhesives.
 Additionally, ethylene oxide is used as a fumigant, a sterilant for food (spices)
and cosmetics, as well as in hospitals to sterilize plastic gadgets and surgical
instruments that cannot be sterilized by steam.
 ETO is used to minimize microbiological activity of organisms that might
contaminate components while processing various gums and dyes in the pro-
duction of cosmetics.
 Library and museum artifacts are treated with ETO to control various pests,
such as fungi and insects.

1.5 REFERENCES

 https://en.wikipedia.org/wiki/Ethylene_oxide#Molecular_structure_and_prope
rties
 https://pubchem.ncbi.nlm.nih.gov/compound/Ethylene-oxide#section=Fire-
Hazards
 https://www.dcceew.gov.au/environment/protection/npi/substances/fact-
sheets/ethylene-
ox-
ide#:~:text=The%20immediate%20effects%20of%20exposure,changes%20in
%20appearance%20or%20behaviour.
 https://cameochemicals.noaa.gov/chemical/694
 https://www.epa.gov/sites/default/files/2016-09/documents/ethylene-oxide.pdf
 https://webwiser.nlm.nih.gov/substance?substanceId=52&identifier=Ethylene
%20Oxide&identifierType=name&menuItemId=67&catId=69
 J. C. Zomerdijk & M. W. Hall (1981) Technology for the Manufacture
of Ethylene Oxide, Catalysis Reviews—Science and Engineering, 23:1-2, 163-
185, DOI:
10.1080/03602458108068074
 Daniela R.G. de Faria, Lara de Oliveira Arinelli, Jose Luiz de Medeiros, Ofe-
lia de Q. F. Araújo Novel ethylene oxide production with improved sustaina-
bility: Loss prevention via supersonic separator and carbon capture, Journal of
Environmental Management 269 (2020) 110782
https://doi.org/10.1016/j.jenvman.2020.110782
 FULLMAN’S ENCYCLOPEDIA OF INDUSTRIAL CHEMISTRY
SIEGFRIED REBSDAT, Winh€oring, Federal Republic of Germany

Chapter 2
 METHYL TERTIARY BUTYL ETHER (MTBE)

Methyl-Tertiary-Butyl Ether (MTBE) is an organic compound having a structural

formula (CH3)3COCH3 and its molecular weight is 88.15 g/mol. Methyl Tertiary-
Butyl Ether is flammable at room temperature. It is a volatile and highly soluble col-
orless liquid. Its odor and taste is very different just like turpentine. It is also used as a
fuel additive and it is blended into gasoline at volume concentrations ranging from
3% to 5% in order to reduce any kind of unwanted emissions and increasing the
knock resistance. To increases the oxygen content of gasoline it also used as an oxy-
genate which is an additive. The chemical reaction of methanol, natural gas, and iso-
butylene produces Methyl Tertiary Butyl Ether.

Structure

2.1 Process Selection

By applying the catalyst of sulphonated ion exchange resin, methanol and isobu-
tylene are directly reacted to produce methyl tertiary butyl ether. Methyl Tertiary
Butyl Ether can be produced in two different ways.
2.1.1 Standard Process
 It primarily consists of a reactor along with a separate distillation column having
conversion rates between 87 and 92%.
2.1.2 Reactive Distillation Process

2.2 Methyl Tertiary Butyl Ether can now be produced using a new process that was
developed in 1980 by scientist Smith, who also recorded the first patent for MTBE
synthesis using this approach. Reactive distillation is the procedure used to produce
this MTBE, and it has a number of intriguing characteristics that make it both desira-
ble and feasible, with a conversion rate of about 99.2%.

2.3 Process Description

The majority of procedures that are readily available on the market are equivalent and
comprise a reaction and a refining stage. The mixed butylene and methanol feed is
first pumped to reaction conditions.
2.3.1 Pump
The pump raises the mixed methanol and butylene feed pressure to the reaction
condition pressure. By utilizing a linear average of the pure component densities,
weighted by their mass fractions in the mixture, one can approximate the liquid densi-
ty.
2.3.2 First Heat Exchanger

This heat exchanger raises the feed's temperature to that of the reactor's feed. At the
specified pressure, each component must stay in the liquid phase.

2.3.3 Reactor
The equipment where the reaction takes place is this. The reaction is exothermic, and
the reactor is adiabatically operating. To ensure that the reaction takes place in the
liquid phase, the reactor runs in the 20 bar range. The reaction is reversible, and to
achieve a desirable equilibrium behaviour, the feed temperature to the reactor is typi-
cally kept below 90 °C. As a result, the heat produced by the reaction elevates the exit
stream's temperature. The conversion affects the exit temperature. To guarantee that
all of the components stay in the liquid phase in the reactor, the reaction must be op-
erated at a pressure and temperature. In order to prevent unwanted side reactions that
lead to undesirable byproducts, methanol must be present in the reactor feed at a min-
imum of 200% excess. The feed and exit temperatures, as well as the reactor's operat-
ing pressure, should be optimized. A working pressure must be selected. It is neces-
sary to establish an ideal conversion and temperature. In order to reduce the heat pro-
duced by exothermic reactions, cooling coils are also attached.
2.3.4 First Distillation Column

This distillation column is operating at a pressure of 19 atm. In this column, methanol

and Methyl tertiary butyl ether are separated, and the feed is then deliv-
ered into another heat exchanger.

2.3.5 Second Heat Exchanger

Some part of the contents of the stream leaving the base of the distillation column and
heat exchanger 1 are vaporized in this heat exchanger and then returned to the col-
umn. These streams' temperature corresponds to the boiling point of MTBE at column
pressure. The quantity of steam required to evaporate the stream has a cost associated
with it. The temperature of the steam must always be higher than the stream being va-
porized.

2.3.6 Third Heat Exchanger

The overhead distillation column's contents are partially condensed in this heat ex-
changer from saturated vapor to saturated fluid at column pressure. 99% of the water
and MTBE condense, while 99% of the remaining substances are still in the vapor
phase. The MTBE condenses with the remaining 1% of the other components. This
stream is likely to condense at the methanol boiling point at the column pressure. The
temperature of the stream being condensed must always be lower than that of the
cooling water leaving the third heat exchanger.

2.3.7 Absorber
 At a pressure of 5 atm and a temperature of 90 °C, the absorber is operational. 99%
of the methanol in the absorber is absorbed into the water. Scrubber pro-
cessed water is managed to consume 5.0 kmol of water for every kmol of metha-
nol.
2.3.8 Second Distillation Column

At a pressure of 5 atm, this column is operational. A valve in the product stream from
column three regulates the pressure. In this column, methanol and water are separated.
99% of the methanol in one stream is transferred to another. In a similar vein, 99 per-
cent of water enters streams where it has to be treated.
2.3.9 Fourth Heat Exchanger

A part of the contents of the stream exiting column two's bottom and heading to the
fourth heat exchanger are vaporized in this heat exchanger and then returned to the
column. The boiling point of water at column pressure is the temperature of these
streams. The temperature of the steam must always be higher than the stream being
vaporized.
2.3.10 Fifth Heat Exchanger
The second distillation column's top contents are completely converted from saturated
vapor to saturated liquid at the column pressure in this heat exchanger. This stream is
likely to condense at the methanol boiling point at the column pressure. The stream's
flow rate from the absorber to the fifth heat exchanger is three times that of stream
15's. The temperature of the stream being condensed must always be lower than that
of the cooling water exiting the fifth exchanger.
2.4 Uses & Safety Concerns

Ninety percent of the methyl tertiary butyl ether (MTBE) produced is used to aerate
gasoline and increase octane. It is suitable for use where higher octane gasoline types
are offered because to its high octane level. It was chosen over ethanol due to its supe-
rior ability to reduce benzene and formaldehyde from gasoline as well as its lower
percentage of volatile organic compounds. High purity isobutylene, which can then be
processed to create butyl rubber, strongly reactive poly isobutylene, methyl methacry-
late , and a few other significant organic wastes, may also be produced using MTBE.

MTBE is listed as a hazardous substance since it is flammable and on the special list
of substances that pose a special health risk. It has a variety of adverse effects on the
environment, workplaces, and skin.
2.4.1 Storage

• • Whenever possible, use an automated pump to transfer liquid methyl-tert-butyl

ether from drums or other storage containers to processing containers.
• Make sure there isn't an explosive concentration present before entering a space that
is off-limits and contains methyl-tert-butyl ether.
• Avoid eating, drinking, or smoking in areas where the chemical is handled, pro-
cessed, or stored.
• Eye wash fountains should be available in the vicinity of the work area for emergen-
cy use prior to eating, drinking, smoking, or using the toilet facilities.
2.4.2 Handling

• MTBE could be dangerous if inhaled or absorbed through the skin, and contact with
it can irritate the skin and eyes.
• Methyl-tert-butyl ether may irritate the nose and throat when inhaled.
• Contact with methyl-tert-butyl ether may cause headaches, nausea, drowsiness, and
lethargy.

2.4.3 Environmental Concern

Numerous researchers have discovered methyl tertiary butyl ether in groundwater
sources, in certain instances; these contaminated streams serve as supplies of drinking
water. Small amounts of MTBE could make fresh water sources unhealthy for drink-
ing due to their unpleasant taste and smell.

References

 https://www.wiley.com/en-
pk/Ullmann's+Encyclopedia+of+Industrial+Chemistry,+40+Volume+Set,+
7th+Edition-p-9783527329434

 https://www.academia.edu/25570258/Production_of_MTBE_Using_Reacti
ve_Distillation_Technology
 Chapter 3

VINYL CHORIDE MONOMER

3.1 INTRODUCTION

Vinyl Chloride Monomer (VCM) is an organic compound having formula C2H3Cl. It

is an organochloride, also called chloroethene. VCM is a colorless, flammable gas
having sweet odor at room temperature. It is highly flammable (when exposed to fire),
toxic, and carcinogenic. It is mostly used to produce polyvinyl chloride derivative
(PVC), a plastic that extremely stable, non-flammable, light, and durable.

3.2 PRODUCTION PROCESS

VCM is mostly produced by two chemical processes direct chlorination and oxychlo-
rination. In direct chlorination, two main feed stock chlorine and ethylene react with
catalyst form ethylene dichloride (EDC) which after cracking to form VCM and HCL
as a byproduct. In oxychlorination HCL is reacted with ethylene to produce again
EDC, which is then thermally cracked to form VCM. These two processes are usually
combined to achieve higher conversion.
In another 1 step process HCL can also be reacted with Acetylene in a Vinylation
process to form Vinyl Chloride

3.3 Process Description

Ethylene is initially allowed to react with gaseous chlorine to produce ethylene di-
chloride (EDC), which is then used to create vinyl chloride. Ethylene dichloride is
produced when ethylene reacts with chlorine gas at a temperature of 65C while Fe Cl2
is present (Equation - 1). The reaction is highly exothermic. The selectivity for this
step is more than 99% for this reaction, and the conversion is 100%. Thermal pyroly-
sis is used to create vinyl chloride from EDC at a temperature between 480 and 550 C
and 4 atmospheres of pressure (Equation -2). Thermal cracking of EDC is occurring
in the tubular pyrolysis (cracking) furnace.

Furthermore, Oxychlorination or Vinylation is performed to use the product HCl pro-

duced in the thermal cracking reaction or as a Standin in the process for the synthesis
of VCM. Acetylene and HCl (generated in a thermal pyrolysis process) are allowed to
react at 200o C and 1 atmosphere pressure in a vinylation reaction. Acetylene and hy-
drogen chloride react in the vapor phase at 150-250o Cover a mercuric chloride cata-
lyst. A catalyst is used in the process of oxychlorination.
3.4 SUSTAINABILITY IN PROCESS

By employing both direct chlorination and oxychlorination for EDC generation, bal-
anced units provide a high degree of chlorine usage without releasing HCl as a by-
product. Assuming 100% absorption of chlorine input into EDC inside a balanced
unit, each of the applied processes, direct chlorination and oxychlorination, produces
half of the generated EDC. Furthermore, the heat gain from both highly exothermic
chlorination processes might be utilized in the linked VCM production, reducing the
total energy requirement of the EDC/VCM/PVC synthesis.

3.5 SAFETY CONCERNS AND HAZARDS

3.5.1 Environmental Concerns

Vinyl chloride monomer endangers human health and pollutes the environment.
VCM is projected to have high mobility in soil. When VCM is discharged into water,
it is not likely to adsorb to suspended particles and silt and will be degraded with half-
life of 28 and 110 days in aerobic and anaerobic waters, respectively.
VCM, on the other hand, is almost non-toxic to fish in the short term, however higher
accumulation can result in severe effect.
If VCM is discharged into the atmosphere, it will only exist as a gas. It will decom-
pose in the air through reaction with photochemically produced hydroxyl radicals, the
half life for the reaction in atmosphere is predicted to around 50 hours; nonetheless, it
can cause damage to people living near the industries.

3.5.2 Storage Concerns

There is a substantial risk of explosion when exposed to high temperatures or flame.
When heated, an irritant gas is released. Because vapours are heavier than the air, they
can travel considerable distances to the origin of the fire before flashing back. Vapors
mix explosively with air and can dissolve explosively across a vast region.

VCM-enabled workplaces should be resistant to fire. VCM must be kept in a National

Fire Prevention Association (NFPA) Class I site.To prevent static charge buildup dur-
ing VCM transfers from one container to another, equipment should be properly
grounded and bonded. If discharged, this buildup might ignite a spark.When storing in
a container, keep it well closed and properly labeled, in cool dry place with good ven-
tilation

3.5.3 Handling Concerns

Vinyl chloride is a recognized carcinogen in humans. Exposed tissue may become

frostbitten if it comes into contact with fluids. Through extended or repeated expo-
sure, it is suspected of creating genetic flaws and causing symptoms of central nerv-
ous system depression, eye irritation, and respiratory irritation.
Workplaces where VCM is utilised should be adequately ventilated to keep solvent
vapours and possibly flammable vapour concentrations below exposure limits. VCM
has an odor threshold of around 3,000 ppm. The concentration of VCM vapor in the
workplace must be monitored with extra controls installed if vapors exceed exposure
restrictions.
Protective clothing, such as gloves and safety glasses, when dealing with VCM should
be worn.
The proper material must be used in the processing and storage of VCM. Additional-
ly, the personnel responsible for the VCM handling and production processes must be
properly trained.

3.6 USES OF VINYL CHLORIDE MONOMER

 VCM is almost exclusively used to produce PVC and its derivative products

 In the past VCM was used in aerosol spray propellant and was briefly used as
an inhalational anesthetic, however today its use is limited to its hazardous na-
ture.

REFERENCES

 https://www.oxy.com/globalassets/documents/chemicals/stewardship/vinyl-
chloride-monomer.pdf
 https://www.ijser.org/researchpaper/Cleaner-Production-of-Vinyl-Chloride-
Monomer-VCM.pdf
 https://www.ou.edu/class/che-design/a-design/projects-
2003/VINYL%20CHLORIDE%20PRODUCTION-original.pdf
 Computers & chemical engineering, 23/4–5, A. Lakshmanan, W.C. Rooney,
L.T. Biegler,
 https://pvc4pipes.com/wp-content/uploads/2018/02/PlasticsEurope_Eco-
profile_VCM_PVC_2015-05.pdf
 Dreher E-L et al; Chloroethanes and Chloroethylenes. Ullmann's Encyclopedia of Indus-
trial Chemistry 7th ed. (1999-2018). NY, NY: John Wiley & Sons. Online Posting Date:
November 19, 2014
 Chapter 4

ACETALDEHYDE

4.1 INTRODUCTION

With the IUPAC name ethanol, acetaldehyde, CH3CHO, is a crucial step in the com-
mercial synthesis of organic compounds. It is one of the most significant aldehydes,
present in enormous amounts in both natural and industrial production. In acetalde-
hyde, the carbon atom forms double bonds with oxygen and hydrogen as well as sin-
gle bonds with two other carbon atoms. All aldehydes have a carbonyl group, which is
a double bond between carbon and oxygen.

4.2 OCCURRENCE

Acetaldehyde is a potential carcinogen, an irritant, and hazardous when applied exter-

nally over extended periods of time. It is a combustion-related air pollution, similar to
cigarette smoke and vehicle exhaust. In the synthesis of acetic acid, ethyl acetate,
peracetic acid, acetic anhydride, and pyridines and more acetaldehyde is a crucial
step. During World War I, acetaldehyde was first widely utilised as a step in the pro-
duction of acetone from acetic acid.

4.3 USES

 About 95% of the acetaldehyde produced internally by the manufacturers is used

as an intermediary in the synthesis of other organic compounds.
 2-ethyl hexanol and N-butanol are the next most common derivatives of acetalde-
hyde, followed by acetic acid and acetic anhydride.
 A range of additional compounds, the most important of which are pyridines,
peracetic acid, crotonaldehyde, chloral, and lactic acid, consume 20% of the acet-
aldehyde. Acetaldehyde is a chemical compound that is used to make basic col-
ours, polyester resins, and fragrances.
 Acetaldehyde is also used in the rubber and paper industries as a solvent and as a
flavoring agent, in fuel formulations, for gelatin hardening and additionally as a
fish and fruit preserver.
 To make acetic acid, which is used to make vinegar, cellulose acetate, which is
used to make films and fibres, as well as other products like acetic anhydride and
esters, acetaldehyde is utilized as a feedstock. It also serves as an intermediary in
the synthesis of other compounds like pyridine, 1, 3-butadiene, and n-
butyraldehyde.

4.4 Different Manufacturing Processes

The economics of the various processes for the manufacture of acetaldehyde is strong-
ly dependent on the price of the feedstock used.

4.4.1 Oxidation of Ethylene:

Reactions:

A solution of PdCl2 and CuCl2 in water serves as the catalyst. In 1894, F.C. Phillips
noticed that acetaldehyde is produced when ethylene and an aqueous solution of pal-
ladium chloride is mixed. Thus ethylene is progressively oxidized through a series of
oxidation and reduction reactions.

In the entire process,

Overall reaction

The oxidation of ethylene results in one of two mechanisms that produces acetalde-
hyde.
4.4.1.1 Wacker Chemie(Two Stage):
Ethylene and oxygen (air) undergo a two-stage liquid phase reaction in the two-stage
process. Ethylene is almost entirely transformed into acetaldehyde in one pass during
the first stage in a titanium-made tubular plug-flow reactor. The reaction is carried out
at 125–1300 °C with palladium and cupric chloride catalysts at 1.13 MPa (150 PSIG).
Through adiabatic flashing in a tower, the acetaldehyde produced in the first reactor is
eliminated from the reaction loop. The heat of the reaction is also removed during the
flash stage. In the second stage (or oxidation) reactor, where the cuprous salt is oxi-
dised to the cupric state with air, the catalyst solution is recycled from the flash tower
base. The liquid catalyst solution is separated from the high-pressure off-gas from the
oxidation reactor, which is primarily nitrogen. The off-gas is then cleaned to remove
acetaldehyde before being vented. The flasher overhead is fed into a distillation sys-
tem, where organic contaminants, such as chlorinated aldehydes, are separated from
the refined acetaldehyde product and water is removed for recycling to the reactor
system.

4.4.1.2 Farbwerke Hoechst (One stage):

In the one-stage process, ethylene, oxygen, and recycled gas are routed to a vertical
reactor for interaction with the catalyst solution while under mild pressure. Water that
evaporates during the reaction absorbs the heat that is released, and additional water is
added as needed to maintain the concentration of the catalytic solution. The gases are
water-scrubbed, and the acetaldehyde solution that is produced is supplied to a distil-
lation column to produce acetaldehyde.

4.4.2 By Oxidation of ethyl alcohol:

Reaction:
, ΔH = 242 kJ/mol (57.84 kcal / mol)

Temperature: 4800C
Catalyst: silver

The oxidation is accomplished by passing heated air and alcohol vapours over a silver
catalyst at a temperature of 4800C. Conversions of 74–82% per pass may be achieved
using a multi-tubular reactor while producing steam that can be utilised in other parts
of the process.
4.4.3 By ethyl alcohol Dehydrogenation:

Reaction:

Catalyst:
Temperature: 280oC – 350 oC.

4.4.3.1 Process description:

Ethanol, the primary component, is evaporated, and the resultant vapors are heated in
a heat exchanger by a hot product stream to the reaction temperature. All of the un-
treated ethanol and acetaldehyde condenses when the product stream is refrigerated to
-100C. Dilute alcohol (alcohol + water) is used to scrub the exiting gaseous stream,
which primarily contains hydrogen, to get rid of any uncondensed products and undis-
solved gas. The remaining 98 per cent of pure hydrogen is burned in a stack. In the
vaporizer and heat exchanger, ethanol is heated to the reactor's temperature. The con-
verter is used to process the heated vapours. The product stream is cooled using water
and liquid ammonia first in heat exchangers and subsequently in condensers. Most of
the unreacted ethanol and acetaldehyde condense as a result.
Ethanol scrubs the departing gas, which is virtually entirely hydrogen, to get rid of
any remaining product residue. Acetaldehyde is produced by distilling a liquid stream
that mostly contains ethanol and acetaldehyde in a distillation column.
4.4.4 Selection of Process with Justification

Here, the dehydrogenation of ethyl alcohol is chosen to produce acetaldehyde. Be-

cause hydrogen is extracted as a byproduct in this process, it can be used in other pro-
cesses or to produce heat. Compared to other processes, the dehydrogenation process
gives higher conversion. Although the dehydrogenation catalyst shows a long
lifespan, it needs to be periodically reactivated. Since there are fewer compounds pro-
duced during the dehydrogenation process, it is not difficult to separate acetaldehyde
from other products.

4.5 Safety in Process Industries

4.5.1 Initial aid:

In case of contact lenses remove them and rinse your eyes with cold water for at least
15 minutes. Get medical help right away.
4.5.2 Skin Contact:
In the event of contact, remove contaminated clothing and shoes and promptly wash
the skin with lots of water for at least 15 minutes. Apply an ointment to the skin that
is inflamed. Before reusing clothing or shoes, wash it thoroughly. Get medical help
right away in this instance as well.

4.5.3 Warning:
When an inhaled substance is toxic, contagious, or caustic, doing mouth-to-mouth re-
suscitation may be dangerous to the person administering help. Get medical help right
away. Acetaldehyde’s primary harmful effect is skin and mucous membrane irritation.
Acetaldehyde's main impact is anaesthesia. For instance, although paraldehyde (acet-
aldehyde trimer) is a very safe hypnotic, its use has been constrained due to its un-
pleasant taste and odour.

4.6 Handling:

Acetaldehyde must be handled carefully since it is a highly reactive chemical that is

readily oxidised, polymerized, or reduced. Acetaldehyde is also considered very reac-
tive to oxygen. It needs to be handled as a poisonous, flammable, and volatile com-
pound (flashpoint 100°F).
Safety measure as listed below must me followed.

 Must always be used in closed environment, Incase exposure to air a blanket made
of nitrogen or another inert gas should be utilized.
 Safety glasses must be worn.
 Transfers should if possible be performed in open air spaces or while wearing a
gas mask or other self contained breathing apparatus.
 Drums should be stored outdoors to prevent direct solar exposure.
 Use a nitrogen blanket and cool the acetaldehyde before transferring it.
 When transporting liquids, acetaldehyde (Class 1 Flammable Liquids) must be
grounded and bonded.
4.7 Shipping and storage:

Acetaldehyde is transported in insulated tank trucks, insulated tank carriages, and 55-
gallon drums. Most metals do not corrode when acetaldehyde is liquid, but they are
quickly converted to acetic acid when it enters in the vapour phase. Both aluminium
and stainless steel are excellent construction materials. There have also been phenolic
resin-coated drums employed. Carbon steel can be utilised if a deeper colour and
some iron contamination are acceptable. Acetaldehyde must be transported with a red
DOT (Department of Transportation) shipping label since it is a flammable liquid.
Instead of storing bulk materials in pressure vessels, it is advised to do so at low pres-
sure and temperature.

4.8 Environmental Effects

To reduce the environmental effects of acetaldehyde synthesis, appropriate environ-

mental controls are required.
Among the environmental safety factors to take into account are:

4.8.1 Air emissions:

The synthesis of acetaldehyde can cause the discharge of air pollutants such as carbon
dioxide (CO2) and volatile organic compounds (VOCs). To reduce emissions, appro-
priate air pollution control tools like scrubbers and catalytic converters should be em-
ployed.

4.8.2 Water discharge:

Wastewater containing acetaldehyde and other pollutants may be produced during the
production process. Before releasing this effluent into the environment, it must be
thoroughly treated.

4.8.3 Solid waste:

To prevent negative effects on the environment, solid waste from the production pro-
cess, such as used catalysts, must be appropriately disposed of.
4.8.4 Spills and Leaks Prevention:
Preventing spills and leaks of acetaldehyde and other production-related chemicals
requires using appropriate handling and storage techniques.

4.8.5 Risk assessment:

To identify and assess the potential environmental effects of the acetaldehyde produc-
tion process and to define the appropriate controls and procedures to prevent these
impacts, a risk assessment must be carried out.

4.8.6 Environmental regulations:

The facility must abide by all applicable laws, rules, and guidelines on waste man-
agement, air and water emissions, and other environmental issues.

4.9 Sustainability in acetaldehyde production

 Although producing acetaldehyde is a crucial step in the chemical industry, there

is a chance that it will harm the environment.
 The release of carbon dioxide (CO2) during production, which contributes to cli-
mate change, is one of the key worries.
 In addition, using fossil fuels as a feedstock for the synthesis of acetaldehyde in-
creases greenhouse gas emissions.
 Companies have been looking into alternative feedstock including biomass and
renewable energy sources to lower the carbon footprint of acetaldehyde manufac-
turing to address these sustainability challenges.
 To capture and store CO2 emissions and lessen their environmental impact, some
businesses are also investing in carbon capture and storage technologies.
 In general, efforts are being made to increase the sustainability of acetaldehyde
production, but more has to be done to fully address the environmental impacts of
this process.
Here are a few steps that can be taken to make the production of acetaldehyde more
sustainable:
4.9.1 Utilize alternative feedstock:
Businesses can look into using biomass, such as agricultural waste or wood chips, as a
carbon source for the production of acetaldehyde in place of fossil fuels as feedstock.
This can greatly lessen the process' carbon footprint.

4.9.2 Invest in renewable energy:

Running the acetaldehyde production process on renewable energy, such as solar or
wind power, can significantly cut greenhouse gas emissions.
4.9.3 Implement carbon capture and storage:
Acetaldehyde manufacturing may trap CO2 emissions and store them underground,
decreasing the environmental impact. This is known as carbon capture and storage
(CCS).

4.9.4 Enhance process effectiveness:

By making the acetaldehyde production process more effective, less energy and mate-
rial input is needed to generate the same quantity of product, which lowers emissions
and lowers costs.

4.9.5 Implement recycling and recovery strategies:

Recycling and recovery strategies can be used to cut down on waste and emissions
produced during production.

4.9.6 Conduct a Life Cycle Assessment (LCA):

An LCA of the process can help identify environmental problem areas and help pri-
oritise actions to increase sustainability.

REFERENCES
 https://www.encyclopedia.com/reference/encyclopedias-almanacs-transcripts-
and-maps/wacker-process
 https://core.ac.uk/download/pdf/235707229.pdf
 https://onlinelibrary.wiley.com/doi/full/10.1002/bbb.1360?casa_token=TeS81
uz-
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