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PROJECT REPORT
“Manufacture of Ethylene Glycol”
Submitted in partial fulfillment of the requirements of the degree of
Bachelor of Engineering (Chemical Engineering)
Name SAP ID
Palak Kothari 60011200013
Rutuj Tatu 60011200009
Department of Chemical Engineering
Dwarkadas J. Sanghvi College of Engineering
2023-24
2
Project Report Approval
This project report entitled “Manufacture of MEG” by Palak Kothari,
Aryan Bhatia, Rutuj Tatu is approved for the term work.
Professor-in-charge:
Prof. Vishal Shah
Department of Chemical Engineering
DJSCE
Date:
Place: Vile Parle(W), Mumbai.
3
Declaration
I declare that this written submission represents my ideas in my own words and where
others' ideas or words have been included, I have adequately cited and referenced the
original sources. I also declare that I have adhered to all principles of academic honesty and
integrity and have not misrepresented or fabricated or falsified any idea/data/fact/source in
my submission. I understand that any violation of the above will be cause for disciplinary
action by the Institute
andcanalsoevokepenalactionfromthesourceswhichhavethusnotbeenproperlycitedorfrom
whom proper permission has not been taken whenneeded.
Date:
4
Acknowledgements
We, Palak Kothari, Aryan Bhatia, Rutuj Tatu present before you the project report entitled
“Manufacture of MEG”. This report is the result of constant inspiration, encouragement
and valuable guidance provided by Prof. Vishal Shah.
We also thank her for her continuous guidance whenever we needed in course of our
complete project. Overall, it was a learning experience and we are sure it’ll help us in our
future life as Chemical Engineers when we pass out of the college.
5
CERTIFICATE
DWARKADAS J. SANGHVI COLLEGE OF ENGINEERING
VILE PARLE WEST, MUMBAI-400 056
This is to certify that the project report entitled “Manufacture of MEG” is submitted to
the University of Mumbai in the partial fulfillment of the requirement for the degree of
‘’BACHELOR OF ENGINEERING IN CHEMICAL ENGINEERING” for the academic
year 2023-2024.
By,
Name SAP ID
Palak Kothari 60011200013
Aryan Bhatia 60011210001
Rutuj Tatu 60011200009
Prof. Vishal Shah Dr. Rupali D Karande Dr. Hari Vasudevan
(InternalGuide) (Head ofDept,Chemical) (Principal)
6
INDEX
Sr.No Particulars Page No.
1. History 8
2. Chemistry 9
3. Physical Properties 10
4. Chemical Properties 12
5. Economics 19
6. Demand Supply 25
7. Manufacturing Processes 31
8. Comparison of
Manufacturing Processes
36
9. Process description 38
10. Material Balance 40
11. MSDS Data Sheet for
Ethylene Oxide
55
7
HISTORY
Ethylene Glycol / Mono-Ethylene Glycol (MEG), HOCH2CH2OH is a Diol. Di-etylene
glycol and Tri-ethylene glycol are homologues of Ethylene glycol.
Wurtz was the first to prepare MEG in 1859. MEG was synthesized only after World War I
from ethylene dichloride. It was used as an alternative antifreeze to glycerol. It was also
used as an intermediate to explosives. It was patented as an antifreeze in the US in 1917, but
its commercial use as an antifreeze began after 1925. by National Carbon Co. (Now Union
Carbide Corp.) introduced MEG in the antifreeze retail by the name ‘Prestone’. . In 1937
Carbide started up the first plant-based on Lefort’s process for vapour phase oxidation of
ethylene oxide.
In 1940 DuPont set up an MEG plant in West Virginia based on the formaldehyde methanol
process.
Today the worldwide capacity for production of MEG via hydrolysis of ethylene oxide is
projected to be 7×106 ton/annum.
8
ABOUT MEG
Compounds containing more than one –OH group are called Polyhydric Alcohol (Dihydric alcohol) or
polyols. Diols are called as Glycols because they have a sweet taste (Greek, glycys= Sweet).
Compounds contain two –OH groups on one carbon are rarely encountered. This happens because they are
unstable and undergo spontaneous decomposition to give corresponding carbonyl compound and water.
For IUPAC system of nomenclature, IUPAC name of glycol is obtained by adding suffix Diol to the name
of parent alkanes.
Formula Common name IUPAC name
CH2OHCH2OH Ethylene Glycol Ethane-1, 2-Diol
9
PHYSICAL PROPERTIES
 Monoethylene glycol and lower poly-glycols associated with MEG are clear, odourless, colourless,
syrupy liquid with a sweet taste.
 It is completely miscible with polar solvents, such as water, alcohols, glycol ethers, and acetone.
 However in non-polar solvents, such as benzene, toluene, dichloromethane, and chloroform its
solubility is very low.
 It is miscible in ethanol in all proportion, completely miscible with many polar solvents such as water,
alcohols, glycol ethers and acetone. It is insoluble in ether and it has low solubility in nonpolar solvents,
such as benzene, toluene, dichloromethane and chloroform.
 When taken orally it is as toxic as methyl alcohol.
MEG is often difficult to crystallize when it is cooled; it forms a highly viscous, super-cooled mass that
finally solidifies to produce a glass-like substance.
The use of MEG as antifreeze is based on its ability to lower freezing point when mixed with water.
Sr.
no.
Physical Properties
1. Formula C2H6O2
2. Mol weight 62
3. Specific gravity at 20o
C 1.1135
4. Boiling point at 101.3 KPa 197.60 degree C
5. Freezing point o
C -13
6. Heat of vaporization at 101.3 KPa; KJ/mol 52.24
7. Heat of combustion (25o
C) MJ/mol 19.07
8. Critical Temperature o
C 372
9. Critical pressure 6513.73 KPa
10. Critical volume, L/mol 0.1861
11. Refractive Index, ŋ 1.4318
12. expansion coefficient at 20 o
C, K-1
0.62 × 10-3
13. Viscosity at 20o
C 19.83 mPa S
10
14. Liquid density (20o
C) gm/cm3
1.1135
15. Flash point 111o
C
16. Auto-ignition temp in air 410o
C
17. Flammability limits in air;
Upper 53 vol%
Lower 3.2 vol%
11
CHEMICALPROPERTIES
MEG contains two primary -OH groups.Usually, one –OH group is attacked completely before other one
reacts.
 Dehydration
 With Zinc chloride, it yields
Acetaldehyde

 HOCH2CH2OH
 (MEG)
 CH3CHO +
H2O
 (Acetaldehyd
es)
 On heating alone at 500 o
C, it yields Ethyleneoxide.
 Chemical reaction with H2SO4 it gives dioxane which is an important compound.
 The hydroxyl groups on MEG undergo the usual alcohol chemical reactions giving a wide variety of
possibleglycol derivatives. Hydroxyls can be converted to many products such as aldehydes, alkyl
halides, amides, amines, azides, carboxylic acids, ethers, mercaptans, nitrate esters, nitriles and
nitrite.
 Chemical reaction with Na at 50 o
C to form monoalkoxide and dialkoxide when the temperature is
high.
Na at50 o
C Na at 160o
C
HOCH2CH2OH HOCH2CH2ONa NaOCH2CH2ONa
(EthyleneGlycol) (Mono Alkoxide) (DiAlkoxide)
 The most commercial use of MEG is its chemical reaction with dicarboxylic acids (1) to form linear
polyesters(PET) (2) is produced by esterification of terephthalic acid to form BisHydroxyEthyl
Terephthalate (BHET) (3). BHET polymerizes in a transesterification chemical reaction by
antimony oxide acting as a catalyst to form PET.
 MEG esterification of BHET is taken to completion by heating and removal of the water formed.
PET is also formed using the same method starting with dimethyl Terephthalate and MEG to form
BHET using antimony oxide as a catalyst.
 MEG produces 1, 4-dioxane by acid-catalyzed dehydration reaction to Di-ethylene glycol followed
by cyclization. Breaking of Triethylene andglycol derivatives with strong acids also produces 1,4-
dioxane by catalyzed ether hydrolysis with further cyclization of the Di-etylene glycol fragment.
12
ECONOMICS
MEG is one of the major products of the chemical industry. Its economic importance is founded
on its two major commercial uses as antifreeze and for fibre production. Since MEG is currently produced
exclusively from ethylene oxide, the production plant is always located close to a plant that produces
ethylene oxide. The proportion of ethylene oxide that is converted to MEG depends on the local condition,
such as retail situation and transport facilities. About 60% of total world production is converted to MEG.
About 50% of the MEG that is used as antifreeze. Another 40% is used in the fibre industry. Consequently,
the MEG demand is closely connected to the development of these two sectors. Because of the increasing
price of crude oil, alternative production method based on synthesis gas is likely to become more important
and increasingly competitive.
 BASF, Geismer, La.(America).
 DOW, Plaquemine, La.(America)
 OXYPETROCHEMICALS, Bayport, Tex .(America)
 PD Glycol ,Beaumont, Tex.(America)
 SHELL, Geismer,La.(America)
 TEXACO ,Port Neches,Tex.(America)
 UNION CARBIDE, Taft,La.(America)
 BP Chemicals, Belgium, (WestEurope).
 IMPERIAL Chemicals Ind. United Kingdom, (WestEurope)
 BPC (NAPTHACHIMIE),France , (WestEurope)
 STATE COMPLEXES ,USSR, (WestEurope)
 PAZINKA, Yugoslavia, (WestEurope)
 EASTERN PETROCHEMICAL CO. Saudi Arabia, (MiddleEast)
 National Organic Chemical, India,(Asia).
 Mitsubishis Petrochemicals, (Japan)
LEADING PRODUCER IN INDIA:
 India Glycol, (Uttarakhand).
 Reliance Industries Ltd. Hazira (Gujarat)
 Indian Petrochemical Corporation Ltd, Baroda(Gujarat).
 NOCIL,Thane (Maharashtra).
 SM Dye chem.Pune (Maharashtra).
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MEG PRICE TREND:
Table: MEG Price Trend
Sr. No. Year Month Price(US$/MT)
1. 2004 November 1095
2. December 988
3. 2005 January 1045
4. February 1095
5. March 1095
6. April 971
7. May 734
8. June 736
9. July 808
10. August 836
11. September 883
12. October 883
13. November 1st
week 830
14. 2nd
week 822
DEMAND SUPPLY BALANCE (INKT):
Table: Demand supply balance (In KT)
MEG 2002 2003 2004 2005 2006
Capacity 590 615 654 830 830
Production 548 647 691 833 830
Imports 11 64 106 103 90
Exports 8 29 104 133 60
Demand 551 682 750 803 860
Demand Growth % 24% 10% 7% 7%
Since MEG is produced in commonly high faultlessness contrast in quality are not recognized. The
truly consolidated thing fulfils magnificent necessities (fibre grade).
The MEG produces in the garments washer water that is used during ethylene oxide creation is
ordinarily of a somewhat unremarkable quality (radiator liquid assessment). The quality specifics
for ethylene glycol are gathering in table
DESCRIPTION FIBER GRADE INDUSTRIAL GRADE
Color, Pt-Co, max 5 10
Suspended matter Substantially free Substantially free
Di-etylene glycol, wt.% max 0.08 0.6
Acidity, as acetic acid, wt%
max
0.005 0.02
Ash, wt% max 0.005 0.005
Water, wt% max 0.08 0.3
14
Iron, ppm wt max 0.07 0.05
Chlorides, ppm wt max
Distillation range, ASTM at
760mm Hg:
IBP, C min 1 in96 196
DP, C max 200 199
Odor Practically none
UV transmittance, % min at:
220 nm 70 70
250 nm 90
275 nm 90 95
350 nm 98 99
Specific gravity, 20/20C 1.1151-1.1156 1.1151-1.1156
Water solubility, 25C Completely miscible
In the glycol product group, monoethylene glycol (MEG) is by far the largest-volume product, accounting for
more than 90% of the overall MEGs retail. MEG is used for primarily in the production of polyester
(polyethylene terephthalate [PET]), which is subsequently used for the production of fibers, films, solid- state
resins, and other consumables.
The rapid growth of the PET retail (solid-state polyester resin, polyester fibers, and polyester film) triggered
a rapid rise in MEG consumption, and new capacities have been started up to serve this growing retail. The
share of MEG used to produce PET has grown significantly over the past three decades. Antifreeze is the
second-largest application for MEG, but the retail is significantly smaller (7% of the total in 2019) than that
for PET. MEG consumption in antifreeze is influenced by automobile production, weather conditions, and
substitution by other products.
Asia’s MEGretail was projected to be 16.38 MMT in terms of demand in 2017 and is expected to grow at a
CAGR(compound annual growth rate) of 4.5% during 2018 – 2023. China accounts the major share in
MEGretail when compared with other national economies. Among the various types of MEG, monoethylene
glycol was projected to be 14.83 MMT in 2017 and is projected to rise with a CAGR of 4.7%during 2018 –
2023.The MEGretail in Asia is rising due to increasing demand for PET resins and polyester fibers in
packaging and textile industries.
This pie chart shows worldwide consumption of monoethylene glycol:
15
Over the last decade, new monoethylene glycol (MEG) capacities have started up in cost-advantaged regions
(Middle East) or where demand has been booming (Northeast Asia), while other regions have rationalized
their MEG capacity (Europe and Japan). In the Middle East, the abundance of competitively priced ethane
has provided a significant cost advantage for regional ethylene and ethylene derivative manufacturers,
creating the foundation for the most cost-competitive MEG production in the world.
In Northeast Asia—particularly China—the development of the textile industry, as well as the growing
dominance of polyester fibers within the textile fibers mix, has driven the construction of large-scale MEG
plants. Together, the Middle East and Northeast Asia have accounted for more than 85% of the MEG capacity
additions over the last 15 years.
A recent game changer in the MEG producing landscape has been the gradual emergence of the newer coal-
to-MEG (CTM) routes. These technologies have been developed in China, where the country is capitalizing
on the abundance of its coal resources to produce chemicals. Nevertheless, the operating rates of the CTM
plants are still relatively low, as these units are struggling with issues of process reliability.
As with all other petrochemicals, the EG industry is cyclical, with the equilibrium between supply and
demand determining the state of the industry. In times of large concomitant new capacity commissioning,
operating rates generally decline (typically below 85%) and margins shrink because of increased competition
among producers. As margins remain under pressure, no new capacity additions are undertaken. As demand
gradually catches up with production, operating rates firm up and margins expand (during peak conditions,
operating rates typically go above 86–87%). This is when the next wave ofcapacity is generally planned.
16
MEG consumption grew at an average annual rate of 5% during 2014–19 and is estimated to slow to about
3.9% during 2019–24. This is primarily because of growing global PET polymer capacity. China will
remain the dominant consumer of MEGin the medium term.
The competitive expanse of this business has been flawlessly categorized into companies such as:
Retail Segment Analysis
The research report includes specific segments by Type and by Application. This study provides information
about the sales and revenue during the historic and estimateded period of 2015 to 2026. Understanding the
segments helps in identifying the importance of different factors that aid the retail growth.
Segment by Type, the MEG Solutions retail is segmented into:
 Monoethylene glycol (MEG)
 Tri-ethylene glycol (TEG)
 Di-etylene glycol (DEG)
 Other
Segment by Application
 Oil and Gas
 Automotive & Electronic Products
 Pharmaceutical
 Chemicals
 Inks and Dyes
 Clothing
 Others
Global MEG Solutions Retail: Regional Analysis
The MEG Solutions retail is analysed and retail size information is provided by regions (national
economies). The report includes country-wise and region-wise retail size for the period 2015-2026. It also
includes retail size and estimated by Type and by Application segment in terms of sales and revenue for the
period 2015-2026.
The following national economies are the major consumer and producers of the MEG worldwide:
North America, U.S., Canada, Germany, France, U.K., Italy, Russia, Asia-Pacific, China, Japan, South
Korea, India, Australia, Taiwan, Indonesia, Thailand, Malaysia, Philippines, Vietnam, Latin America,
Mexico, Brazil, Argentina, Middle East & Africa, Turkey, Saudi Arabia, UAE.
INDUSTRY INSIGHTS
The global MEGs retail demand was 16,511.0 kilo tons in 2013. It is projected to expand at a CAGR of
4.7% from 2014 to 2020.
17
The global bulk chemicals retail has been experiencing significant growth due to its increased use in the
downstream retail applications, especially the booming textile industry and PET resin products industry. Its
applications include consumer goods oriented or purely industrial in nature owing to the harmful properties
of these chemicals. With its fast-growing textile retails, Asia Pacific has been rapidly emerging as a major
consumer retail for MEGs (polyester fibers and fabrics).
Optimized processes, equipment, and catalysts are essential to overcome the price volatility caused by crude
oil and its resultant upward trend of prices of MEG-based products. This increase in prices for buyers is
expected to be a hurdle in retail growth. Apart from this, guidelines for safe handling, production,
transportation, use, storage, and disposal of MEGs need to be adhered to considering the major health and
environment threats posed by glycols.
18
DEMAND AND SUPPLY
1 Billion by 2027, growing at a CAGR of 3.1% over the analysis period 2020-2027. Monoethylene glycol
(MEG) is projected to record a 3.3% CAGR and reach US$32.8 Billion by the end of the analysis period.
After an early analysis of the business implications of the pandemic and its induced economic crisis, growth
in the Di-etylene glycol (DEG) segment is readjusted to a revised 2.2% CAGR for the next 7-year period.
The U.S. Retail is projected at $8.3 Billion, While China is estimated to Grow at 5.8% CAGR The
MEGretail in the U.S. is projected at US$8.3 Billion in the year 2020. China, the world`s second greatest
economy, is estimated to reach a projected retail size of US$7.8 Billion by the year 2027 trailing a CAGR of
5.8% over the analysis period 2020 to 2027. Among the other noteworthy geographic retails are Japan and
Canada, each estimated to grow at 0.8% and 2.3% respectively over the 2020-2027 period. Within Europe,
Germany is estimated to grow at approximately 1.5% CAGR.
Tri-ethylene glycol (TEG) Segment to Record 1.7% CAGR. These regional retails accounting for a combined
retail size of US$1.1 Billion in the year 2020 will reach a projected size of US$1.3 Billion by the close of the
analysis period. China will remain among the fastest growing in this cluster of regional retails.
Competitors identified in this retail include, among others
 Akzo Nobel NV
 BASF SE
 China Petrochemical Corporation (Sinopec Group)
 Clariant AG
 DowDupont Inc.
 Exxon Mobil Corporation
 Formosa Plastics Corporation
 Huntsman International LLC
 Ineos Oxide
 Kuwait Petroleum Corporation
 Lotte Chemical Corporation
 LyondellBasell Industries NV
 Reliance Industries Ltd.
 Royal Dutch Shell plc
 SABIC (Saudi Basic Industries Corporation)
19
 UltraparParticipacoes S.A.
MEG: India Capacity and Demand Supply
Capacity and Demand Supply
2017-18 2018-19 2019-20 2020-21
Capacity 1522 2215 2215 2215
Production 1522 2072 2082 2130
Imports 1066 652 660 720
Exports 139 233 177 148
Apparent Demand 2399 2503 2565 2702
Demand Growth (%) 11.7% 4.3% 2.5% 5.3%
In 2018, the world imports of "MEG (ethanediol)" exceeded $14.9 billion (according to the external trade
statistics of 126 national economies). It was $13.1 billion in the previous year (according to the
merchandise trade statistics of 140 national economies).
Top importers of MEG (ethanediol) in 2018
The world's largest importers of this commodity group in 2018 were
 China - 60% of the world imports ($9.08 billion)
 USA - 5.39% ($806 million)
 India - 4.04% ($605 million)
 Indonesia - 2.96% ($443 million)
 Belgium - 2.55% ($381 million)
MEG (ethanediol) accounted for a substantial share of total imports of
 Lithuania - 0.635% of Lithuania's total imports in 2018 ($232 million of $36 billion)
 Pakistan - 0.554% ($333 million of $60 billion)
 China - 0.425% ($9.08 billion of $2.13 trillion)
 Saudi Arabia - 0.381% ($1.12 billion of $294 billion)
 Other Asia, nes - 0.372% ($1.25 billion of $335 billion)
 Canada - 0.243% ($1.09 billion of $450 billion)
 Singapore - 0.242% ($999 million of $411 billion)
 Indonesia - 0.235% ($443 million of $188 billion)
 Belarus - 0.163% ($62 million of $38 billion)
 Belgium - 0.148% ($695 million of $468 billion)
According to statistics provided by the major importers, the largest flows of imports of MEG
(ethanediol) in 2018 were
 Imports to China from Canada (5.57% of the world imports, $833 million according to the external
trade statistics of China)
 Imports to China from Iran (1.76% of the world imports, $264 million according to the external
trade statistics of China)
20
 Imports to China from Korea (3.16% of the world imports, $473 million according to the external
trade statistics of China)
 Imports to China from Kuwait (3.66% of the world imports, $548 million according to the external
trade statistics of China)
 Imports to China from Other Asia, nes (7.9% of the world imports, $1.18 billion according to the
external trade statistics of China)
 Imports to China from Saudi Arabia (25% of the world imports, $3.82 billion according to the
external trade statistics of China)
 Imports to China from Singapore (4.65% of the world imports, $695 million according to the
external trade statistics of China)
 Imports to China from United Arab Emirates (3.88% of the world imports, $581 million according
to the external trade statistics of China)
 Imports to India from Kuwait (1.97% of the world imports, $295 million according to the external
trade statistics of India)
 Imports to USA from Canada (3.45% of the world imports, $516 million according to the external
trade statistics of USA)
In 2018, the world exports of "MEG (ethanediol)" exceeded $8.67 billion (according to the external trade
statistics of 79 national economies). It was $8.13 billion in the previous year (according to the merchandise
trade statistics of 82 national economies).
Top exporters of MEG (ethanediol) in 2018
The world's largest exporters of this commodity group in 2018 were
 Other Asia, nes - 14.4% of the world exports ($1.25 billion)
 Kuwait - 13.3% ($1.15 billion)
 Saudi Arabia - 12.9% ($1.12 billion)
 Canada - 12.6% ($1.09 billion)
 Singapore - 11.5% ($999 million)
 Belgium - 8.01% ($695 million)
MEG (ethanediol) accounted for a substantial share of total exports of
 Kuwait - 1.6% of Kuwait's total exports in 2018 ($1.15 billion of $71 billion)
 Lithuania - 0.635% ($232 million of $36 billion)
 Pakistan - 0.554% ($333 million of $60 billion)
 China - 0.425% ($9.08 billion of $2.13 trillion)
 Saudi Arabia - 0.381% ($1.12 billion of $294 billion)
 Other Asia, nes - 0.372% ($1.25 billion of $335 billion)
 Canada - 0.243% ($1.09 billion of $450 billion)
 Singapore - 0.242% ($999 million of $411 billion)
 Indonesia - 0.235% ($443 million of $188 billion)
 Belarus - 0.163% ($62 million of $38 billion)
According to statistics provided by the major exporters, the largest flows of exports of MEG (ethanediol) in
2018 were
 Exports from Belgium to Germany: (3.38% of the world exports, $293 million according to the
external trade statistics of Belgium)
 Exports from Canada to China: (6.67% of the world exports, $579 million according to the external
trade statistics of Canada)
 Exports from Canada to USA: (5.94% of the world exports, $515 million according to the external
trade statistics of Canada)
21
 Exports from Korea to China: (5.1% of the world exports, $442 million according to the external
trade statistics of Korea)
 Exports from Kuwait to China: (3.35% of the world exports, $291 million according to the external
trade statistics of Kuwait)
 Exports from Kuwait to India: (3.59% of the world exports, $311 million according to the external
trade statistics of Kuwait)
 Exports from Other Asia, nes to China: (13.1% of the world exports, $1.13 billion according to the
external trade statistics of Other Asia, nes)
 Exports from Saudi Arabia to China: (8.3% of the world exports, $720 million according to the
external trade statistics of Saudi Arabia)
 Exports from Singapore to China: (7.75% of the world exports, $672 million according to the
external trade statistics of Singapore)
 Exports from USA to Mexico: (2.89% of the world exports, $250 million according to the external
trade statistics of USA)
India’s Exports: USD: HS: 29053100: MEG (Ethanediol) data was reported at 140.230 USD mn in 2018.
This records an increase from the previous number of 68.090 USD mn for 2017. India’s Exports: USD: HS:
29053100: MEG (Ethanediol) data is updated yearly, averaging 44.560 USD mn from Mar 1997 to 2018,
with 22 observations. The data reached an all-time high of 140.230 USD mn in 2018 and a record low of
0.110 USD mn in 1997. India’s Exports: USD: HS: 29053100: MEG (Ethanediol) data remains active status
in CEIC and is reported by Ministry of Commerce and Industry. The data is categorized under India
Premium Database’s Chemical and Petrochemical Sector – Table IN.RHG005: Chemical and
PetrochemicalExports: Harmonized System: HS29: Organic Chemicals: USD.
Total imports of India for last Decade
The value of imports of commodity group 290531 "MEG (ethanediol)" to India from Kuwait totalled $219
million in 2019. Sales of commodity group 290531 to India from Kuwait declined by 25% compared to
2018.imports of commodity group 290531 "MEG (ethanediol)" decreased by $ 76 million (the value of
sales of commodity group 290531 to India from Kuwait was equal to $295 million in 2018) the flowing
graph provides the schematic view:
$500
419.4675
$400 370.2193
307.8751 317.8597
295.9901
$300 259.2522
219.7524
$200
115.6333 105.6891
134.1121 125.843
$100 62.5301
$0
2008 2009 2010 2011 2012 2013 2014 2015 2016 2017 2018 2019
MILLIONS
22
India MEG retail witnessed boom in recent years on account of growing demand from the industrial sector,
the country has emerged as the second main consumption hub with its built up second largest downstream
polyester capacities. Because of varied applications across industries such as automobile industry, textile
industry and paint industry the demand for monoethylene glycol (MEG) has fuelled at a faster rate as
compared to the overall retail. The increase in the demand for decomposable MEG and fluctuating price of
crude oil could dampen the growth prospects of MEGretail in India.
According to 6Wresearch, India MEGRetail is anticipated to register growth during 2020-2026. Poly-MEG
helps in increasing the shelf life as well as stability of the dental products, owing to which the demand for
poly-MEG is expected to increase in the medical and healthcare sector over the estimated period.
Additionally, the Government of India has come up with initiatives to lift anti-dumping duty on polyester,
which would support MSME industries to produce more domestically and in turn would further create
abundant opportunities for MEGretail in India.
By Application, Polyethylene Terephthalate or PET, is the largest consumer of MEG, accounting for
significant share in the domestic retail. Further, MEG is also used in applications that require chemical
intermediates for resins, solvent couplers, freezing point depressors, solvents, humectants and chemical
intermediates.
The India MEGretail report thoroughly covers the retail by product types, applications. India MEGretail
outlook report provides an unbiased and detailed analysis of the on-going India MEGretail trends,
opportunities/high growth areas and retail drivers which would help the stakeholders to devise and align
their retail strategies according to the current and future retail dynamics.
23
MANUFACTURING PROCESSES
By to the end of 1981, only two processes for manufacturing MEG have been accepted at commercial level.
The process of hydration of ethylene oxide, is by far the most important, and from 1968 through 1981 has
been the basis for all of the MEG production. The manufacturing process involves laboratory methods and
industrial methods.
Laboratory methods
 By passing Ethylene into a cold dilute Alkaline permanganate solution.
i.e Oxidation of Ethylene to Glycol
 Hydrolysis of Ethylene Bromide by boiling under
reflux with aqueous sodium carbonate solution. This chemical reaction mixture is refluxed till the time an
oily globule of ethylene bromide disappears. The resulting solution is evaporated using a water bath and the
semi-solid residue is extracted by using ether-alcohol mixture. Recovery of Glycol from the solution is done
by distillation. The best yield of glycol which is about 83- 84% can be obtained by heating ethylene
bromide with potassium acetate in Glacial acetic acid.
 MEG can also be produced by an electrohydrodimerization of formaldehyde.
 An early source of glycols was from the hydrogenation of sugars obtained from formaldehyde
condensation. Selectivity to MEG was low with several other glycols and polyols produced in the
process. Biomass continues to beresearced upon for ethylene glycol yield.
Industrial methods:
 The production of MEG by the hydration of ethylene oxide is simple, and can be summarized in the
following steps: ethylene oxide reacts with water to form glycol, and then further reacts with MEG.
 Ethylene oxide hydrolysis begins with either acid or base catalysis or uncatalyzed in neutral
medium. Neutral hydrolysis (pH 6-10), conducted in the presence of a excess moles of water at high
temperatures and pressures, increases the selectivity of MEG to 89-91%. In all of these ethylene
oxide hydrolysis processes, the principal byproduct is Di-etylene glycol. Theglycol derivatives, i.e.,
Triethylene and Tri-ethylene glycols, account for the remainder.
 Even if catalytic hydration of ethylene oxide to maximize MEG production has been studied by
many companies with numerous materials patented as catalysts, there has been no reported
industrial manufacture of MEG via catalytic ethylene oxide hydrolysis. The studied catalyst includes
various catalysts such as sulfonic acids, carboxylic acids and salts, cation-exchange resins, acidic
zeolites, halides, anion- exchange resins, metals, metal oxide and metal salts. Carbon dioxide which
acts as a co-catalyst with many of the same materials has also received extensive study.
24
PROCESS FLOW DIAGRAM:
25
COMPARISON OF MANUFACTURING
PROCESSES
SR.
NO
PROCESSES PARAMETER CATALYST ADVANTAGES/
DISADVANTAGES
1. Hydrolysis of
EthyleneOxide
No. of unit
operations: 4
1) Non-
catalyticYield :
98%
Selectivity: 98%
Temp:105o
C
Pressure :
1.5MPa
2) catalytic:Yield
: 95%
Selectivity: 90%
Temp:200o
C
Pressure:
1-30 bar
1)Non
Catalytic
2) Catalytic:
Sulphuracids,
Ion-exchange
resins, Acidic
zeolites,
halides, Metal
oxideand
Metal salts.
91491.47
(Rs/m3
)
Use excess moles
water to increase the
yield which leads to
high
energyconsumption
1) Use less of water
which leads to low
energyconsumption
2) High yield
&selectivity
3) permit use of low
temp &pressure
4) Acid catalyst makes
the chemical
reactionsolution
highly corrosive.
2. MEGfrom
Ethylene
Chlorohydrins
No. of unit
operations: variable
Yield :50%
Selectivity: 75%
Non Catalytic very low
yield&
selectivit
y verycostly
3. MEG from
CO,H2,CH3OH
&
Formaldehyde
Yield : 90-95%
Temp: 200o
C
Pressure:
100atm
Cromate Catalyst
Bis(triphenylsilyl)
chromate 96% pure
= $55.3/gram
High
pressure process
Discontinued now
aday
Lowselectivity
26
No. of unit
operations: 1
(dielectric barrier
discharge)
4. MEG from ethylene
carbonate
No. of unit
operations: 2
Yield :98%
Selectivity: 95%
Temp:180o
C
Pressure:13bar
Alkali halide or
ammonium salt.
Ammonium
Chloride = 400
rupees/kg
Give high yield and
selectivity
Utilitysaving
Extra
purification cost
5. Transesterification
of ethylene
carbonate.
No. of unit
operations: 3
Low yield Zirconium &
Titanium
Titanium Grade
12(USA origin) =
75000 rupees/kg
Produced large
Amount of byproducts
27
PROCESS DESCRIPTION
This process manufactures Ethylene Glycol by the catalytic hydrolysis of ethylene oxide using less excess of water.
After the completion of the reaction, the MEG is separated from the water and refined to give the final aqueous
Mono-ethylene glycol.
MEG chemical reaction unit:
1) Ethylene oxide is mixed with recycle and fresh water and pumped to reactor where it is reacts with water at
105℃&1.5 MPa in the presence of an ionite catalyst.
2) Reactor is a Catalytic Plug Flow Fixed Bed of Cross-linked Styrene DiVinylBenzene anion exchange resin.
3) The reaction involves two phases: Liquid Phase and Ionite Phase, the distribution of reaction mixture
between these phases is a result of rapid equilibrium.
4) The catalytic hydration of ethylene oxide takes place in the ionite phase.
5) The reactor effluent goes to the evaporation unit for the evaporation of excess water.
MEG evaporation unit:
1) The Ethylene Glycol evaporation unit has Three Effects in which the content of water finally gets reduced to
15%
2) Effluent to be evaporated flows by the pressure difference from one evaporator effect to the next effect.
3) Pressure of the evaporator system is such that the effluent is maintained as a liquid and is fed into the first
effect evaporator.
4) Evaporation in the first effect is accomplished by 12Kg/cm2 (g) (11.6141 atm) pressure steam.
5) The overhead vapours from the first effect are used for the need of heating media in the second
effect and overhead vapours from the second effect are used as heating media.
6) The third evaporation effect is operated under vacuum which is maintained by steam jet ejector nozzle.
7) Top products from all the effects is sent to the recovery column to recover any glycol evaporated with the
water.
MEG drying unit:
1) All of the remaining water is removed from the aqueous MEG solution in the drying distillation
column.
2) A steam jet ejector maintains the vacuum in a drying column.
3) Pure aqueous ethylene glycol which is collected from the tower bottom is pumped to the refining
tower.
4) Water vapours leaving the top of the drying column are fed to MEG recovery unit.
MEG refining unit:
1) Ethylene glycol is withdrawn from the top of the refining column.
2) Some MEG is purged in the overhead of the column to the vacuum jets for reducing the aldehydes
in the product.
3) The bottoms (dietylene glycol and triethylene glycol) are stored in a tank after cooling.
4) Vacuum is maintained by steam jet ejector.
MEG recovery unit:
1) The MEG leaving from the Top of evaporator effects and the drying column are recovered in the Recovery
28
Column it is a PLATE COLUMN.
2) The refining column operated under Atmospheric pressure.
3) MEG leaving from the bottom and the water leaving from the top of the recovery column are Recycled to the
ethylene glycol reactor.
29
MATERIAL BALANCE
Basis: 100000TPA
The process is a continuous process. The plant operates for 24 Hours a day and 333
days out of 365 days per year.
No of working days = 333days
Capacity =
1000000
333
= 300.3 T/days
= 201.8147 kmol / hr.
=the MEG obtained from distillation column,
MOLECULAR WEIGHT (KG /KMOL):
Ethylene Glycol 62
Water 18
Ethylene oxide 44.05
Carbon dioxide 44.01
Nitrogen 28
MATERIAL BALANCE OF INDIVIDUAL EQUIPMENT:
assuming 99% of MEG in the feed to the Refining Column is obtained in distillate and
93% of MEG of feed to the Recovery Column is recovered from it.
kmol of MEG in feed to the distillation column= 204.7 kmol / hr.
Reactor:
30
Ethylene Oxide = 9190.54 kg
= 208.876 kmols
Ethylene glycol = 204.7 kmols
= 12691.4kg
Water = 37597.68 kg
=2088.76 kmols
Water = 1881.972 kmols
= 33875.496 kg
Higher glycol = 2.088 kmol
=221.328 kg
REACTOR
Temp. = 373K
Conversion = 100 %
Pressure = 15 atm
31
In the reactor following chemical reactions take place
C2H4O + H2O HOCH2CH2OH -----------------(1)
(Ethylene oxide) (Water) (Mono Ethylene Glycol)
C2H4O + HOCH2CH2OH HOCH2CH2OH------------(2)
(Ethylene oxide) (Mono ethylene glycol) (Higher Glycol)
As selectivity = 98%
Moles of undesired product formed =
204.70
98
= 2.088 kmol
Moles of MEG to be produced from reactor = 204.7+2.088
= 206.788 kmol
Moles of ethylene oxide reacted by chemical reaction –(1)
= 206.788 kmol.
Moles of ethylene oxide reacted by chemical reaction –(2)
= 2.088 kmol.
Total EO reacted = 206.788 + 2.088
As conversion = 100%
= 208.876 kmol
Moles of ethylene oxide charged to reactor = 208.876kmol
From the literature we know that the ratio of WATER TO ETHYLENE OXIDE
=10:1
Kmol of water feed to EO reactor = 2088.76 kmol. (Including excess)
From the chemical reaction (1) moles of water reacted = 206.788 kmol.
M.B OF WATER:
Moles of water in = Moles reacted + Moles unreacted
2088.76 = 206.788 + Moles unreacted
Moles of water unreacted = 1881.972 kmol
32
M.B OF MEG:
Here, moles of MEG contained in product = 206.788 – 2.088
= 204.7 kmol
Material balance over reactor
Component In, kg/hr In, kg/s Out, kg/hr Out, kg/s
Ethylene oxide 9190.54 2.55292 - -
Water 37597.68 10.4438 33875.496 9.40986
Ethylene glycol - - 12691.4 3.52538
Higher Glycol - - 221.328 0.06148
Triple Effect Evaporator:
Consider the water content of glycol is reduced to 15% in evaporator i.e. 85% of
water is removed.
Considering triple effect evaporator as single
unit.
Amount of water removed = 0.85×1881.972
= 1599.6762 kmol.
= 28794.1715 kg
Total water moles at the top of the column = 1599.6762 kmol.
= 28794.1716 kg.
15% water is still in the bottom with the MEG and other glycol.
Amount of water in the bottoms = 1881.972-1599.6762
= 282.2958 kmol.
= 5081.324 kg
some quantity of glycol carries over from the top product of evaporator.
Amount of glycol carry over along with water from 1st
effect = 165.58 kg
33
F = 2088.76 kmol
= 46788.224 kg
M.E.G = 204.7 kmol
= 12691.4 kg
Water 1881.972 kmol
=33875.496 kg
W1 = 8285.66 kg
MEG = 165.58 kg
H2O = 8120.08 kg
To 2nd
effect evaporator
Amount of glycol carry over along with water from 2nd
effect evaporator = 189.139 kg
W2 = 9689.31 kg
MEG 189.139 kg
H2o = 9500.171 kg
From 2nd
effect
evaporator
To 3rd
effect evaporator
To MEG Recovery column
Y = 1610.8012 kmol
Amount of glycol carry over with water from 3nd
effect evaporator = 335.064 kg
2nd
effect evaporator
Pressure = 3.38 atm
Temp = 414K
1st
effect evaporator
Pressure = 6.77 atm
Temp = 432K
W3 = 11508.96 kg
MEG = 335.064 kg
H2o 11173.89 kg
From 3rd
effect evaporator
To MEG Refining
column
X = 477.9588 kmol
To MEG recovery column
Y = 1610.8012 kmol
(Using VLE calculation)
Total amount of glycol carry over along with water = 689.783 kg.
=11.125 kmol
Total (water +MEG) leaving top of evaporator effect =1599.6762 +11.125
Y = 1610.8012 kmol.
TAKING OVERALL M.B
F = Y +X
2088.76 =1610.8012+X
X = 477.9588 kmol.
(quantity leaving from bottoms of last evaporator effect)
Material balance over Triple effect evaporator
Component In, kg/hr In, kg/s Out, kg/hr Out, kg/s
Liquid
phase
Vapor
phase
Liquid
phase
Vapor
phase
Water 33875.496 9.40986 5081.355 28794.141 1.4114875 7.9983725
MEG 12691.4 3.52538 12001.617 689.783 3.3337825 0.191606
HG 221.328 0.06148 221.328 - 0.06148 -
Drying column:
Y = 289.295 kmol
34
=5537.385 kg
MEG = 456.061 kg
3rd
effect evaporator
Pressure = 0.24 atm
Temp = 391K
35
F = 477.958 kmol
=17304.258 kg
MEG = 12001.606 kg
H2O = 5081.324 kg
HG = 221.328 kg
Consider all the remaining water are removed in the drying column.
Amount of water removed =5018.32 kg
= 282.295 kmol.
Kmol of glycol carrying along with water from drying column top = 456.061kg
(Using VLE calculation)
=7.3558 kmol.
Total quantity leaving from top of drying column
= (Amount of water +Amount of MEG)
= 282.295 +7.3558
= 289.65 kmol.
TAKING OVERALL M.B
F = Y + X
477.9588 = 289.65 + X
X = 188.306 kmol.
(quantity leaving bottom of drying distillation column)
36
Now
Total amount of MEG leaving along with water
= (MEG leaving from top of Triple Effect Evaporator + MEG leaving from top of drying column)
= 689.783+456.061
= 1145.844 kg.
= 18.4813 kmol.
Amount of feed to MEG Recovery column
= (Amount of MEG leaving with water during evaporation + Amount of water expelled)
= 18.4813+1881.973
= 1900.451 kmol.
Material balance over drying column
Component In, kg/hr In, kg/s Out, kg/hr Out, kg/s
Liquid
phase
Vapor
phase
Liquid
phase
Vapor
phase
Water 5081.324 1.411478 - 5081.324 - 1.411478
MEG 12001.606 3.333779 11545.3545 456.061 3.2070429 0.1266836
HG 221.328 0.06148 221.328 - 0.06148 -
MEG Refining Column (Packed Column):
D = 184.54 kmol
= 11448.8616 kg
F = 188.306 kmol
= 11766.873 kg
MEG = 186.218 kmol
= 11545 kg
HG = 2.088 kmol
= 221.328 kg
MEG = 184.355 kmol (0.999
high purity)
HG =0.18454 kmol
W = 3.766 kmol
= 317.664 kg
MEG = 1.8523 kmol
HG = 1.9136 kmol
MEG refining column
Pressure = 0.0131 atm
Temp = 366.2 K
37
Distillate:
F = D + W
Take 99% recovery, of MEG fed to distillation column
MEG obtained in Distillate = 188.306 × 0.99 × 0.98891
= 184.355 kmol / hr.
= 11431.0818 kg/hr.
Total kmols of Distillate = 184.355 / 0.999
= 184.54 kmol / hr.
Avg. M.W. (distillate) = (0.999 x 62) + (0.001 x 106)
= 62.044 kg / kmol.
Amt. of Distillate (D) = 184.54 x 62.04
= 11448.8618 kg / hr.
Amt. of HG in Distillate = 184.54 x 0.001
= 0.18454 kmol / hr.
= 0.18454 x 106
= 19.561 kg / hr.
kmol of feed (F) = 188.306 kmol / hr.
= 11766.873 kg / hr
TAKING OVERALL M.B.
188.306 = 184.54 + W
W = 3.766 kmol/hr.
M.B. OF MEG
F x (Xf MEG) = D x (Xd MEG) + W x (Xb MEG)
188.306 x 0.9889 = 184.54 x 0.999 + 3.766 x Xb MEG
Xb MEG = 0.4918 (mol.fr.of MEG in Bottoms)
XbHG = (1- 0.4918)
= 0.5081 (mol.fr.of HG in Bottoms)
kmol of MEG in Bottoms = 0.4918 x 3.766 =1.8521 kmol / hr
Molar Wt of MEG = 62 kg / kmol = 114.831 kg/hr.
amount of HG in Bottom product = 0.5081 x 3.766
=1.9135kmol / hr.
38
Mol. Weight of HG =106 kg / kmol
= 1.9135 x 106
= 202.83kg/hr.
Material balance over Refining packed column
Component In, kg/hr In, kg/s Out, kg/hr Out, kg/s
Liquid
phase
Vapor
phase
Liquid
phase
Vapor
phase
MEG 11545.545 3.207095 114.8426 11430.01 0.03190 3.1750027
HG 221.328 0.06148 202.8416 19.56124 0.0563448 0.00543367
39
99
MEG recovery column
Plate column
MEG recovery column (Plate column):
F = 1900.45 kmol
= 35021.339 kg
MEG = 18.481 kmol
= 1145.844 kg
H2O = 1881.97 kmol
= 33875.496 kg
D = 1881.97 kmol
= 11766.873 kg
MEG = 1.88 kmol
H2O = 1880.08 kmol
99% water in D
W = 18.481 kmol
=1205.55kg
MEG = 17.122 kmol
H2O = 1.3584 kmol
kmol of Water in Distillate = 1881.97 x 0.9
= 1880.08 kmol / hr
kmol of Distillate (D) = 1880.08 / 0.999
= 1881.97 kmol / hr.
Avg. M.W. of distillate = (0.999 x 18) + (0.001 x 62)
= 18.044 kg / kmol.
Amt. of Distillate (D) = 1881.97 x 18.044
= 33958.266 kg /hr
Amt. of MEG in Distillate = 1881.97 x 0.001
= 1.88 kmol / hr
= 1.88 x 62
= 116.56 kg/ hr.
Amount of feed (F) = 1900.451 kmol / hr
= 35021.339 kg/hr.
40
OVERALL M.B.
F = D+ W
1900.451 = 1881.47 + W
W = 18.481 kmol / hr
M.B. OF WATER
F x (Xf H) = D x (Xd H) + W x (Xb H)
1900.451 x 0.99 = 1881.97 x 0.999 + 18.481 x Xb W
Xb W = 0.0735 (mol.fr.of Water in Bottoms)
Xb MEG = 1- 0.0735
= 0.9264 (mol.fr.of MEG in Bottoms)
Kmols MEG in Bottom = 18.481 x 0.9264
= 17.122 kmol /hr
= 17.122 x 62
= 1061.56 kg/hr.
amount of Water in Bottoms = 18.481 – 17.130
= 1.3584 kmol / hr
= 1.3584 x 18
= 143.99 kg/ hr.
Material balance over Recovery plate column
Component In, kg/hr In, kg/s Out, kg/hr Out, kg/s
Liquid
phase
Vapor
phase
Liquid
phase
Vapor
phase
Water 33875.496 9.40986 24.4512 33841.44 0.006792 9.4004
MEG 1145.844 0.31829 1061.546 116.56 0.294874 0.032378
Overall material balances
41
Equipment Component In, kg/hr In, kg/s Out, kg/hr Out, kg/s
Liquid
phase
Vapor
phase
Liquid
phase
Vapor
phase
Reactor Ethylene
oxide
9190.54 2.552927778 - - - -
Water 37597.68 10.4438 33875.496 - 9.40986 -
MEG - - 12691.4 - 3.525388889 -
HG - - 221.328 - 0.06148 -
Triple
effect
evaporator
Water 33875.496 9.40986 5081.355 28794.14
1
1.4114875 7.9983725
MEG 12691.4 3.525388889 12001.617 689.783 3.3337825 0.191606389
HG 221.328 0.06148 221.328 - 0.06148 -
Drying
column
Water 5081.324 1.411478889 5081.324 1.411478889
MEG 12001.606 3.333779444 11545.3545 456.061 3.207042917 0.126683611
HG 221.328 0.06148 221.328 - 0.06148 -
MEG
refining
column
MEG 11545.545 3.207095833 114.8426 11430.01 0.031900722 3.175002778
HG 221.328 0.06148 202.8416 19.56124 0.056344889 0.005433678
MEG
recovery
column
Water 33875.496 9.40986 24.4512 33841.44 0.006792 9.4004
MEG 1145.844 0.31829 1061.546 116.56 0.294873889 0.032377778
42
MSDS Data sheet for Ethylene Oxide
CAS number: 75-21-8
GHS Category table for reference:
Study/hazard
statement
Category 1 Category2 Category 3 Category 4 Category 5
Acute Oral
LD50
<5 mg/kg > 5 <50 mg/kg > 50 < 300 >300<2000 >2000<
Fatal if
swallowed
Fatal if
swallowed
mg/kg Toxic if
swallowed
mg/kg Harmful
if swallowed
5000mg/kg
May be
harmful if
swallowed
Acute Dermal
LD50
< 50 mg/kg >50<200mg/kg >200<1000 >1000<2000 >2000<5000
Fatal in contact
with skin
Fatal in contact
with skin
mg/kg
Toxic in
contact with
skin
mg/kg
Harmful in
contact with
skin
mg/kg May
be harmful in
contact with
skin
Acute
Inhalation
Dust LC50
Gases LC50
Vapours LC50
< 0.05 mg/L > 0.05 < 0.5 >0.5<1.0mg/L >1.0<5mg/L
See footnote
below this
<100ppm/V mg/L >500<2500 >2500<20000 table
<0.5 mg/L Fatal >100<500ppm/ ppm/V ppm/V
if inhaled V
>0.5<2.0mg/L
Fatal if inhaled
>2.0<10mg/L
Toxic if
inhaled
>10<20mg/L
Harmful if
inhaled
Flammable
liquids
Flashpoint<23
degrees C and
initial boiling
point<35 degrees
C. Extremely
flammable liquid
and
vapour
Flashpoint<23
degrees C and
initial boiling
point
> 35 degrees C.
Highly
flammable
liquid and
vapour
Flashpoint>23
degrees C<60
degree sC.
Flammable
liquid and
vapour
Flash point > 60
degrees C < 93
degrees C.
Combustible
liquid
Not
Applicable
Note: Gases concentration are expressed in parts per million per volume(ppmV).
NOTE1:Category 5 is for mixtures which are of relatively low acute toxicity but which under
certain circumstances may pose a hazard to vulnerable populations. These mixtures are
anticipated to have an oral or dermal LD50 value in the range of 2000-5000 mg/kg bodyweight
or equivalent dose for other routes of exposure. In light of animal welfare considerations,
testing in animals in Category5 ranges is discouraged and should only be considered when
there is a strong likelihood that results of such testing would have a direct relevance for
protecting human health.
NOTE 2: These values are designed to be used in the calculation of the ATE for classification
of a mixture based on its ingredients and do not represent test results. The values are
conservatively set at the lower end of the range of Categories1 and2,and at a point
approximately1/10th from the lower end of the range for Categories3–5.
43
GHS Category table for reference: Continued
Study/hazar
d statement
Category 1 Category2 Category 3
Eye Irritation Effects on the cornea, iris
or conjunctiva that are not
expected to reverse or that
have not fully
reversedwithin21days.
Causes severe eye damage.
2A:Effects on the cornea, iris
or conjunctiva that fully
reverse within 21days.
Causes severe eye irritation.
2B:Effects on the cornea ,iris
or conjunctiva that fully
reverse within7 days.
Causes eye irritation.
Not applicable
Skin
Irritation
Destruction of skin tissue
,with sub categorization
based on exposure of upto
3 minutes(A),1 hour(B),or
4 hours(C).
Causes severe skin burns
and eye damage.
Mean value of>2.3>4.0for
erythema/ escharoredemain
atleast 2 of 3tested animals
from gradings at24,48,and72
hours(or on 3 consecutive
days after onset if chemical
chemical reactions are
delayed); inflammation that
persists to end of the
(normally14-day)observation
period. Causes skin irritation.
Mean value of>1.5<2.3
for erythema/escharor
edemain atleast2of3
Tested animals from
gradings
at24,48,and72hours(oro
n3 consecutive days
after onset if chemical
chemical reactions are
delayed).
Causes mild skin
irritation.
Environment:
Acute
Toxicity
Category
96hrLC50(fish)<1mg/L48h
rEC50(crustacea)<1mg/L,7
2/96 hrErC50(aquatic
plants)<1mg/L Very toxic
to aquatic life
96hrLC50(fish)>1<10mg/L48
hrEC50(crustacea)>1<10mg/
L72/96hrErC50(aquaticplants
)>1<10mg/L Toxic to aquatic
life
96hrLC50(fish)>10<10
0
mg/L 48 hr EC50
(crustacea)
>10<100mg/L72/96hrE
rC50(aquatic
plants)>10<100mg/L
Harmful to aquatic life
Flammable
Aerosol
Extremely flammable
aerosol
Flammable aerosol Not Applicable
Flammable
solids
Using the burning rate test,
substances or mixtures
other than metal powders:
(a) wetted zone does not
stop fire and
(b)burning time<45seconds
or burning
rate>2.2mm/second Using
the burning rate test, metal
powders that have burning
time<5 minutes
Flammable solid
Using the burning rate test,
substances or mixtures other
than metal powders:
(a)wetted zone does not stop
fire for atleast 4 minutes
and(b)burning time<
45seconds or burning rate>2.2
mm/second Using the burning
rate test, metal powders that
have burning time>
5<10minutes
Flammable solid
Not Applicable
Flammable
gases
Gases,which at 20 degrees
C and a standard pressure
of 101.3kPA:
) are ignitable when in a
mixture of 13% or less by
volume in air; or
) have a flammable range
with air of at least 12
percentage points
Gases,other than those of
category1, which, at 20
degrees C and a standard
pressure of101.3kPA,have a
flammable range while mixed
in air. Flammable gas
Not Applicable
44
regardless of the lower
flammable limit.
Extremely flammable gas

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G24 Ethylene Glycol Updated.docx edited.docx

  • 1. 1 PROJECT REPORT “Manufacture of Ethylene Glycol” Submitted in partial fulfillment of the requirements of the degree of Bachelor of Engineering (Chemical Engineering) Name SAP ID Palak Kothari 60011200013 Rutuj Tatu 60011200009 Department of Chemical Engineering Dwarkadas J. Sanghvi College of Engineering 2023-24
  • 2. 2 Project Report Approval This project report entitled “Manufacture of MEG” by Palak Kothari, Aryan Bhatia, Rutuj Tatu is approved for the term work. Professor-in-charge: Prof. Vishal Shah Department of Chemical Engineering DJSCE Date: Place: Vile Parle(W), Mumbai.
  • 3. 3 Declaration I declare that this written submission represents my ideas in my own words and where others' ideas or words have been included, I have adequately cited and referenced the original sources. I also declare that I have adhered to all principles of academic honesty and integrity and have not misrepresented or fabricated or falsified any idea/data/fact/source in my submission. I understand that any violation of the above will be cause for disciplinary action by the Institute andcanalsoevokepenalactionfromthesourceswhichhavethusnotbeenproperlycitedorfrom whom proper permission has not been taken whenneeded. Date:
  • 4. 4 Acknowledgements We, Palak Kothari, Aryan Bhatia, Rutuj Tatu present before you the project report entitled “Manufacture of MEG”. This report is the result of constant inspiration, encouragement and valuable guidance provided by Prof. Vishal Shah. We also thank her for her continuous guidance whenever we needed in course of our complete project. Overall, it was a learning experience and we are sure it’ll help us in our future life as Chemical Engineers when we pass out of the college.
  • 5. 5 CERTIFICATE DWARKADAS J. SANGHVI COLLEGE OF ENGINEERING VILE PARLE WEST, MUMBAI-400 056 This is to certify that the project report entitled “Manufacture of MEG” is submitted to the University of Mumbai in the partial fulfillment of the requirement for the degree of ‘’BACHELOR OF ENGINEERING IN CHEMICAL ENGINEERING” for the academic year 2023-2024. By, Name SAP ID Palak Kothari 60011200013 Aryan Bhatia 60011210001 Rutuj Tatu 60011200009 Prof. Vishal Shah Dr. Rupali D Karande Dr. Hari Vasudevan (InternalGuide) (Head ofDept,Chemical) (Principal)
  • 6. 6 INDEX Sr.No Particulars Page No. 1. History 8 2. Chemistry 9 3. Physical Properties 10 4. Chemical Properties 12 5. Economics 19 6. Demand Supply 25 7. Manufacturing Processes 31 8. Comparison of Manufacturing Processes 36 9. Process description 38 10. Material Balance 40 11. MSDS Data Sheet for Ethylene Oxide 55
  • 7. 7 HISTORY Ethylene Glycol / Mono-Ethylene Glycol (MEG), HOCH2CH2OH is a Diol. Di-etylene glycol and Tri-ethylene glycol are homologues of Ethylene glycol. Wurtz was the first to prepare MEG in 1859. MEG was synthesized only after World War I from ethylene dichloride. It was used as an alternative antifreeze to glycerol. It was also used as an intermediate to explosives. It was patented as an antifreeze in the US in 1917, but its commercial use as an antifreeze began after 1925. by National Carbon Co. (Now Union Carbide Corp.) introduced MEG in the antifreeze retail by the name ‘Prestone’. . In 1937 Carbide started up the first plant-based on Lefort’s process for vapour phase oxidation of ethylene oxide. In 1940 DuPont set up an MEG plant in West Virginia based on the formaldehyde methanol process. Today the worldwide capacity for production of MEG via hydrolysis of ethylene oxide is projected to be 7×106 ton/annum.
  • 8. 8 ABOUT MEG Compounds containing more than one –OH group are called Polyhydric Alcohol (Dihydric alcohol) or polyols. Diols are called as Glycols because they have a sweet taste (Greek, glycys= Sweet). Compounds contain two –OH groups on one carbon are rarely encountered. This happens because they are unstable and undergo spontaneous decomposition to give corresponding carbonyl compound and water. For IUPAC system of nomenclature, IUPAC name of glycol is obtained by adding suffix Diol to the name of parent alkanes. Formula Common name IUPAC name CH2OHCH2OH Ethylene Glycol Ethane-1, 2-Diol
  • 9. 9 PHYSICAL PROPERTIES  Monoethylene glycol and lower poly-glycols associated with MEG are clear, odourless, colourless, syrupy liquid with a sweet taste.  It is completely miscible with polar solvents, such as water, alcohols, glycol ethers, and acetone.  However in non-polar solvents, such as benzene, toluene, dichloromethane, and chloroform its solubility is very low.  It is miscible in ethanol in all proportion, completely miscible with many polar solvents such as water, alcohols, glycol ethers and acetone. It is insoluble in ether and it has low solubility in nonpolar solvents, such as benzene, toluene, dichloromethane and chloroform.  When taken orally it is as toxic as methyl alcohol. MEG is often difficult to crystallize when it is cooled; it forms a highly viscous, super-cooled mass that finally solidifies to produce a glass-like substance. The use of MEG as antifreeze is based on its ability to lower freezing point when mixed with water. Sr. no. Physical Properties 1. Formula C2H6O2 2. Mol weight 62 3. Specific gravity at 20o C 1.1135 4. Boiling point at 101.3 KPa 197.60 degree C 5. Freezing point o C -13 6. Heat of vaporization at 101.3 KPa; KJ/mol 52.24 7. Heat of combustion (25o C) MJ/mol 19.07 8. Critical Temperature o C 372 9. Critical pressure 6513.73 KPa 10. Critical volume, L/mol 0.1861 11. Refractive Index, ŋ 1.4318 12. expansion coefficient at 20 o C, K-1 0.62 × 10-3 13. Viscosity at 20o C 19.83 mPa S
  • 10. 10 14. Liquid density (20o C) gm/cm3 1.1135 15. Flash point 111o C 16. Auto-ignition temp in air 410o C 17. Flammability limits in air; Upper 53 vol% Lower 3.2 vol%
  • 11. 11 CHEMICALPROPERTIES MEG contains two primary -OH groups.Usually, one –OH group is attacked completely before other one reacts.  Dehydration  With Zinc chloride, it yields Acetaldehyde   HOCH2CH2OH  (MEG)  CH3CHO + H2O  (Acetaldehyd es)  On heating alone at 500 o C, it yields Ethyleneoxide.  Chemical reaction with H2SO4 it gives dioxane which is an important compound.  The hydroxyl groups on MEG undergo the usual alcohol chemical reactions giving a wide variety of possibleglycol derivatives. Hydroxyls can be converted to many products such as aldehydes, alkyl halides, amides, amines, azides, carboxylic acids, ethers, mercaptans, nitrate esters, nitriles and nitrite.  Chemical reaction with Na at 50 o C to form monoalkoxide and dialkoxide when the temperature is high. Na at50 o C Na at 160o C HOCH2CH2OH HOCH2CH2ONa NaOCH2CH2ONa (EthyleneGlycol) (Mono Alkoxide) (DiAlkoxide)  The most commercial use of MEG is its chemical reaction with dicarboxylic acids (1) to form linear polyesters(PET) (2) is produced by esterification of terephthalic acid to form BisHydroxyEthyl Terephthalate (BHET) (3). BHET polymerizes in a transesterification chemical reaction by antimony oxide acting as a catalyst to form PET.  MEG esterification of BHET is taken to completion by heating and removal of the water formed. PET is also formed using the same method starting with dimethyl Terephthalate and MEG to form BHET using antimony oxide as a catalyst.  MEG produces 1, 4-dioxane by acid-catalyzed dehydration reaction to Di-ethylene glycol followed by cyclization. Breaking of Triethylene andglycol derivatives with strong acids also produces 1,4- dioxane by catalyzed ether hydrolysis with further cyclization of the Di-etylene glycol fragment.
  • 12. 12 ECONOMICS MEG is one of the major products of the chemical industry. Its economic importance is founded on its two major commercial uses as antifreeze and for fibre production. Since MEG is currently produced exclusively from ethylene oxide, the production plant is always located close to a plant that produces ethylene oxide. The proportion of ethylene oxide that is converted to MEG depends on the local condition, such as retail situation and transport facilities. About 60% of total world production is converted to MEG. About 50% of the MEG that is used as antifreeze. Another 40% is used in the fibre industry. Consequently, the MEG demand is closely connected to the development of these two sectors. Because of the increasing price of crude oil, alternative production method based on synthesis gas is likely to become more important and increasingly competitive.  BASF, Geismer, La.(America).  DOW, Plaquemine, La.(America)  OXYPETROCHEMICALS, Bayport, Tex .(America)  PD Glycol ,Beaumont, Tex.(America)  SHELL, Geismer,La.(America)  TEXACO ,Port Neches,Tex.(America)  UNION CARBIDE, Taft,La.(America)  BP Chemicals, Belgium, (WestEurope).  IMPERIAL Chemicals Ind. United Kingdom, (WestEurope)  BPC (NAPTHACHIMIE),France , (WestEurope)  STATE COMPLEXES ,USSR, (WestEurope)  PAZINKA, Yugoslavia, (WestEurope)  EASTERN PETROCHEMICAL CO. Saudi Arabia, (MiddleEast)  National Organic Chemical, India,(Asia).  Mitsubishis Petrochemicals, (Japan) LEADING PRODUCER IN INDIA:  India Glycol, (Uttarakhand).  Reliance Industries Ltd. Hazira (Gujarat)  Indian Petrochemical Corporation Ltd, Baroda(Gujarat).  NOCIL,Thane (Maharashtra).  SM Dye chem.Pune (Maharashtra).
  • 13. 13 MEG PRICE TREND: Table: MEG Price Trend Sr. No. Year Month Price(US$/MT) 1. 2004 November 1095 2. December 988 3. 2005 January 1045 4. February 1095 5. March 1095 6. April 971 7. May 734 8. June 736 9. July 808 10. August 836 11. September 883 12. October 883 13. November 1st week 830 14. 2nd week 822 DEMAND SUPPLY BALANCE (INKT): Table: Demand supply balance (In KT) MEG 2002 2003 2004 2005 2006 Capacity 590 615 654 830 830 Production 548 647 691 833 830 Imports 11 64 106 103 90 Exports 8 29 104 133 60 Demand 551 682 750 803 860 Demand Growth % 24% 10% 7% 7% Since MEG is produced in commonly high faultlessness contrast in quality are not recognized. The truly consolidated thing fulfils magnificent necessities (fibre grade). The MEG produces in the garments washer water that is used during ethylene oxide creation is ordinarily of a somewhat unremarkable quality (radiator liquid assessment). The quality specifics for ethylene glycol are gathering in table DESCRIPTION FIBER GRADE INDUSTRIAL GRADE Color, Pt-Co, max 5 10 Suspended matter Substantially free Substantially free Di-etylene glycol, wt.% max 0.08 0.6 Acidity, as acetic acid, wt% max 0.005 0.02 Ash, wt% max 0.005 0.005 Water, wt% max 0.08 0.3
  • 14. 14 Iron, ppm wt max 0.07 0.05 Chlorides, ppm wt max Distillation range, ASTM at 760mm Hg: IBP, C min 1 in96 196 DP, C max 200 199 Odor Practically none UV transmittance, % min at: 220 nm 70 70 250 nm 90 275 nm 90 95 350 nm 98 99 Specific gravity, 20/20C 1.1151-1.1156 1.1151-1.1156 Water solubility, 25C Completely miscible In the glycol product group, monoethylene glycol (MEG) is by far the largest-volume product, accounting for more than 90% of the overall MEGs retail. MEG is used for primarily in the production of polyester (polyethylene terephthalate [PET]), which is subsequently used for the production of fibers, films, solid- state resins, and other consumables. The rapid growth of the PET retail (solid-state polyester resin, polyester fibers, and polyester film) triggered a rapid rise in MEG consumption, and new capacities have been started up to serve this growing retail. The share of MEG used to produce PET has grown significantly over the past three decades. Antifreeze is the second-largest application for MEG, but the retail is significantly smaller (7% of the total in 2019) than that for PET. MEG consumption in antifreeze is influenced by automobile production, weather conditions, and substitution by other products. Asia’s MEGretail was projected to be 16.38 MMT in terms of demand in 2017 and is expected to grow at a CAGR(compound annual growth rate) of 4.5% during 2018 – 2023. China accounts the major share in MEGretail when compared with other national economies. Among the various types of MEG, monoethylene glycol was projected to be 14.83 MMT in 2017 and is projected to rise with a CAGR of 4.7%during 2018 – 2023.The MEGretail in Asia is rising due to increasing demand for PET resins and polyester fibers in packaging and textile industries. This pie chart shows worldwide consumption of monoethylene glycol:
  • 15. 15 Over the last decade, new monoethylene glycol (MEG) capacities have started up in cost-advantaged regions (Middle East) or where demand has been booming (Northeast Asia), while other regions have rationalized their MEG capacity (Europe and Japan). In the Middle East, the abundance of competitively priced ethane has provided a significant cost advantage for regional ethylene and ethylene derivative manufacturers, creating the foundation for the most cost-competitive MEG production in the world. In Northeast Asia—particularly China—the development of the textile industry, as well as the growing dominance of polyester fibers within the textile fibers mix, has driven the construction of large-scale MEG plants. Together, the Middle East and Northeast Asia have accounted for more than 85% of the MEG capacity additions over the last 15 years. A recent game changer in the MEG producing landscape has been the gradual emergence of the newer coal- to-MEG (CTM) routes. These technologies have been developed in China, where the country is capitalizing on the abundance of its coal resources to produce chemicals. Nevertheless, the operating rates of the CTM plants are still relatively low, as these units are struggling with issues of process reliability. As with all other petrochemicals, the EG industry is cyclical, with the equilibrium between supply and demand determining the state of the industry. In times of large concomitant new capacity commissioning, operating rates generally decline (typically below 85%) and margins shrink because of increased competition among producers. As margins remain under pressure, no new capacity additions are undertaken. As demand gradually catches up with production, operating rates firm up and margins expand (during peak conditions, operating rates typically go above 86–87%). This is when the next wave ofcapacity is generally planned.
  • 16. 16 MEG consumption grew at an average annual rate of 5% during 2014–19 and is estimated to slow to about 3.9% during 2019–24. This is primarily because of growing global PET polymer capacity. China will remain the dominant consumer of MEGin the medium term. The competitive expanse of this business has been flawlessly categorized into companies such as: Retail Segment Analysis The research report includes specific segments by Type and by Application. This study provides information about the sales and revenue during the historic and estimateded period of 2015 to 2026. Understanding the segments helps in identifying the importance of different factors that aid the retail growth. Segment by Type, the MEG Solutions retail is segmented into:  Monoethylene glycol (MEG)  Tri-ethylene glycol (TEG)  Di-etylene glycol (DEG)  Other Segment by Application  Oil and Gas  Automotive & Electronic Products  Pharmaceutical  Chemicals  Inks and Dyes  Clothing  Others Global MEG Solutions Retail: Regional Analysis The MEG Solutions retail is analysed and retail size information is provided by regions (national economies). The report includes country-wise and region-wise retail size for the period 2015-2026. It also includes retail size and estimated by Type and by Application segment in terms of sales and revenue for the period 2015-2026. The following national economies are the major consumer and producers of the MEG worldwide: North America, U.S., Canada, Germany, France, U.K., Italy, Russia, Asia-Pacific, China, Japan, South Korea, India, Australia, Taiwan, Indonesia, Thailand, Malaysia, Philippines, Vietnam, Latin America, Mexico, Brazil, Argentina, Middle East & Africa, Turkey, Saudi Arabia, UAE. INDUSTRY INSIGHTS The global MEGs retail demand was 16,511.0 kilo tons in 2013. It is projected to expand at a CAGR of 4.7% from 2014 to 2020.
  • 17. 17 The global bulk chemicals retail has been experiencing significant growth due to its increased use in the downstream retail applications, especially the booming textile industry and PET resin products industry. Its applications include consumer goods oriented or purely industrial in nature owing to the harmful properties of these chemicals. With its fast-growing textile retails, Asia Pacific has been rapidly emerging as a major consumer retail for MEGs (polyester fibers and fabrics). Optimized processes, equipment, and catalysts are essential to overcome the price volatility caused by crude oil and its resultant upward trend of prices of MEG-based products. This increase in prices for buyers is expected to be a hurdle in retail growth. Apart from this, guidelines for safe handling, production, transportation, use, storage, and disposal of MEGs need to be adhered to considering the major health and environment threats posed by glycols.
  • 18. 18 DEMAND AND SUPPLY 1 Billion by 2027, growing at a CAGR of 3.1% over the analysis period 2020-2027. Monoethylene glycol (MEG) is projected to record a 3.3% CAGR and reach US$32.8 Billion by the end of the analysis period. After an early analysis of the business implications of the pandemic and its induced economic crisis, growth in the Di-etylene glycol (DEG) segment is readjusted to a revised 2.2% CAGR for the next 7-year period. The U.S. Retail is projected at $8.3 Billion, While China is estimated to Grow at 5.8% CAGR The MEGretail in the U.S. is projected at US$8.3 Billion in the year 2020. China, the world`s second greatest economy, is estimated to reach a projected retail size of US$7.8 Billion by the year 2027 trailing a CAGR of 5.8% over the analysis period 2020 to 2027. Among the other noteworthy geographic retails are Japan and Canada, each estimated to grow at 0.8% and 2.3% respectively over the 2020-2027 period. Within Europe, Germany is estimated to grow at approximately 1.5% CAGR. Tri-ethylene glycol (TEG) Segment to Record 1.7% CAGR. These regional retails accounting for a combined retail size of US$1.1 Billion in the year 2020 will reach a projected size of US$1.3 Billion by the close of the analysis period. China will remain among the fastest growing in this cluster of regional retails. Competitors identified in this retail include, among others  Akzo Nobel NV  BASF SE  China Petrochemical Corporation (Sinopec Group)  Clariant AG  DowDupont Inc.  Exxon Mobil Corporation  Formosa Plastics Corporation  Huntsman International LLC  Ineos Oxide  Kuwait Petroleum Corporation  Lotte Chemical Corporation  LyondellBasell Industries NV  Reliance Industries Ltd.  Royal Dutch Shell plc  SABIC (Saudi Basic Industries Corporation)
  • 19. 19  UltraparParticipacoes S.A. MEG: India Capacity and Demand Supply Capacity and Demand Supply 2017-18 2018-19 2019-20 2020-21 Capacity 1522 2215 2215 2215 Production 1522 2072 2082 2130 Imports 1066 652 660 720 Exports 139 233 177 148 Apparent Demand 2399 2503 2565 2702 Demand Growth (%) 11.7% 4.3% 2.5% 5.3% In 2018, the world imports of "MEG (ethanediol)" exceeded $14.9 billion (according to the external trade statistics of 126 national economies). It was $13.1 billion in the previous year (according to the merchandise trade statistics of 140 national economies). Top importers of MEG (ethanediol) in 2018 The world's largest importers of this commodity group in 2018 were  China - 60% of the world imports ($9.08 billion)  USA - 5.39% ($806 million)  India - 4.04% ($605 million)  Indonesia - 2.96% ($443 million)  Belgium - 2.55% ($381 million) MEG (ethanediol) accounted for a substantial share of total imports of  Lithuania - 0.635% of Lithuania's total imports in 2018 ($232 million of $36 billion)  Pakistan - 0.554% ($333 million of $60 billion)  China - 0.425% ($9.08 billion of $2.13 trillion)  Saudi Arabia - 0.381% ($1.12 billion of $294 billion)  Other Asia, nes - 0.372% ($1.25 billion of $335 billion)  Canada - 0.243% ($1.09 billion of $450 billion)  Singapore - 0.242% ($999 million of $411 billion)  Indonesia - 0.235% ($443 million of $188 billion)  Belarus - 0.163% ($62 million of $38 billion)  Belgium - 0.148% ($695 million of $468 billion) According to statistics provided by the major importers, the largest flows of imports of MEG (ethanediol) in 2018 were  Imports to China from Canada (5.57% of the world imports, $833 million according to the external trade statistics of China)  Imports to China from Iran (1.76% of the world imports, $264 million according to the external trade statistics of China)
  • 20. 20  Imports to China from Korea (3.16% of the world imports, $473 million according to the external trade statistics of China)  Imports to China from Kuwait (3.66% of the world imports, $548 million according to the external trade statistics of China)  Imports to China from Other Asia, nes (7.9% of the world imports, $1.18 billion according to the external trade statistics of China)  Imports to China from Saudi Arabia (25% of the world imports, $3.82 billion according to the external trade statistics of China)  Imports to China from Singapore (4.65% of the world imports, $695 million according to the external trade statistics of China)  Imports to China from United Arab Emirates (3.88% of the world imports, $581 million according to the external trade statistics of China)  Imports to India from Kuwait (1.97% of the world imports, $295 million according to the external trade statistics of India)  Imports to USA from Canada (3.45% of the world imports, $516 million according to the external trade statistics of USA) In 2018, the world exports of "MEG (ethanediol)" exceeded $8.67 billion (according to the external trade statistics of 79 national economies). It was $8.13 billion in the previous year (according to the merchandise trade statistics of 82 national economies). Top exporters of MEG (ethanediol) in 2018 The world's largest exporters of this commodity group in 2018 were  Other Asia, nes - 14.4% of the world exports ($1.25 billion)  Kuwait - 13.3% ($1.15 billion)  Saudi Arabia - 12.9% ($1.12 billion)  Canada - 12.6% ($1.09 billion)  Singapore - 11.5% ($999 million)  Belgium - 8.01% ($695 million) MEG (ethanediol) accounted for a substantial share of total exports of  Kuwait - 1.6% of Kuwait's total exports in 2018 ($1.15 billion of $71 billion)  Lithuania - 0.635% ($232 million of $36 billion)  Pakistan - 0.554% ($333 million of $60 billion)  China - 0.425% ($9.08 billion of $2.13 trillion)  Saudi Arabia - 0.381% ($1.12 billion of $294 billion)  Other Asia, nes - 0.372% ($1.25 billion of $335 billion)  Canada - 0.243% ($1.09 billion of $450 billion)  Singapore - 0.242% ($999 million of $411 billion)  Indonesia - 0.235% ($443 million of $188 billion)  Belarus - 0.163% ($62 million of $38 billion) According to statistics provided by the major exporters, the largest flows of exports of MEG (ethanediol) in 2018 were  Exports from Belgium to Germany: (3.38% of the world exports, $293 million according to the external trade statistics of Belgium)  Exports from Canada to China: (6.67% of the world exports, $579 million according to the external trade statistics of Canada)  Exports from Canada to USA: (5.94% of the world exports, $515 million according to the external trade statistics of Canada)
  • 21. 21  Exports from Korea to China: (5.1% of the world exports, $442 million according to the external trade statistics of Korea)  Exports from Kuwait to China: (3.35% of the world exports, $291 million according to the external trade statistics of Kuwait)  Exports from Kuwait to India: (3.59% of the world exports, $311 million according to the external trade statistics of Kuwait)  Exports from Other Asia, nes to China: (13.1% of the world exports, $1.13 billion according to the external trade statistics of Other Asia, nes)  Exports from Saudi Arabia to China: (8.3% of the world exports, $720 million according to the external trade statistics of Saudi Arabia)  Exports from Singapore to China: (7.75% of the world exports, $672 million according to the external trade statistics of Singapore)  Exports from USA to Mexico: (2.89% of the world exports, $250 million according to the external trade statistics of USA) India’s Exports: USD: HS: 29053100: MEG (Ethanediol) data was reported at 140.230 USD mn in 2018. This records an increase from the previous number of 68.090 USD mn for 2017. India’s Exports: USD: HS: 29053100: MEG (Ethanediol) data is updated yearly, averaging 44.560 USD mn from Mar 1997 to 2018, with 22 observations. The data reached an all-time high of 140.230 USD mn in 2018 and a record low of 0.110 USD mn in 1997. India’s Exports: USD: HS: 29053100: MEG (Ethanediol) data remains active status in CEIC and is reported by Ministry of Commerce and Industry. The data is categorized under India Premium Database’s Chemical and Petrochemical Sector – Table IN.RHG005: Chemical and PetrochemicalExports: Harmonized System: HS29: Organic Chemicals: USD. Total imports of India for last Decade The value of imports of commodity group 290531 "MEG (ethanediol)" to India from Kuwait totalled $219 million in 2019. Sales of commodity group 290531 to India from Kuwait declined by 25% compared to 2018.imports of commodity group 290531 "MEG (ethanediol)" decreased by $ 76 million (the value of sales of commodity group 290531 to India from Kuwait was equal to $295 million in 2018) the flowing graph provides the schematic view: $500 419.4675 $400 370.2193 307.8751 317.8597 295.9901 $300 259.2522 219.7524 $200 115.6333 105.6891 134.1121 125.843 $100 62.5301 $0 2008 2009 2010 2011 2012 2013 2014 2015 2016 2017 2018 2019 MILLIONS
  • 22. 22 India MEG retail witnessed boom in recent years on account of growing demand from the industrial sector, the country has emerged as the second main consumption hub with its built up second largest downstream polyester capacities. Because of varied applications across industries such as automobile industry, textile industry and paint industry the demand for monoethylene glycol (MEG) has fuelled at a faster rate as compared to the overall retail. The increase in the demand for decomposable MEG and fluctuating price of crude oil could dampen the growth prospects of MEGretail in India. According to 6Wresearch, India MEGRetail is anticipated to register growth during 2020-2026. Poly-MEG helps in increasing the shelf life as well as stability of the dental products, owing to which the demand for poly-MEG is expected to increase in the medical and healthcare sector over the estimated period. Additionally, the Government of India has come up with initiatives to lift anti-dumping duty on polyester, which would support MSME industries to produce more domestically and in turn would further create abundant opportunities for MEGretail in India. By Application, Polyethylene Terephthalate or PET, is the largest consumer of MEG, accounting for significant share in the domestic retail. Further, MEG is also used in applications that require chemical intermediates for resins, solvent couplers, freezing point depressors, solvents, humectants and chemical intermediates. The India MEGretail report thoroughly covers the retail by product types, applications. India MEGretail outlook report provides an unbiased and detailed analysis of the on-going India MEGretail trends, opportunities/high growth areas and retail drivers which would help the stakeholders to devise and align their retail strategies according to the current and future retail dynamics.
  • 23. 23 MANUFACTURING PROCESSES By to the end of 1981, only two processes for manufacturing MEG have been accepted at commercial level. The process of hydration of ethylene oxide, is by far the most important, and from 1968 through 1981 has been the basis for all of the MEG production. The manufacturing process involves laboratory methods and industrial methods. Laboratory methods  By passing Ethylene into a cold dilute Alkaline permanganate solution. i.e Oxidation of Ethylene to Glycol  Hydrolysis of Ethylene Bromide by boiling under reflux with aqueous sodium carbonate solution. This chemical reaction mixture is refluxed till the time an oily globule of ethylene bromide disappears. The resulting solution is evaporated using a water bath and the semi-solid residue is extracted by using ether-alcohol mixture. Recovery of Glycol from the solution is done by distillation. The best yield of glycol which is about 83- 84% can be obtained by heating ethylene bromide with potassium acetate in Glacial acetic acid.  MEG can also be produced by an electrohydrodimerization of formaldehyde.  An early source of glycols was from the hydrogenation of sugars obtained from formaldehyde condensation. Selectivity to MEG was low with several other glycols and polyols produced in the process. Biomass continues to beresearced upon for ethylene glycol yield. Industrial methods:  The production of MEG by the hydration of ethylene oxide is simple, and can be summarized in the following steps: ethylene oxide reacts with water to form glycol, and then further reacts with MEG.  Ethylene oxide hydrolysis begins with either acid or base catalysis or uncatalyzed in neutral medium. Neutral hydrolysis (pH 6-10), conducted in the presence of a excess moles of water at high temperatures and pressures, increases the selectivity of MEG to 89-91%. In all of these ethylene oxide hydrolysis processes, the principal byproduct is Di-etylene glycol. Theglycol derivatives, i.e., Triethylene and Tri-ethylene glycols, account for the remainder.  Even if catalytic hydration of ethylene oxide to maximize MEG production has been studied by many companies with numerous materials patented as catalysts, there has been no reported industrial manufacture of MEG via catalytic ethylene oxide hydrolysis. The studied catalyst includes various catalysts such as sulfonic acids, carboxylic acids and salts, cation-exchange resins, acidic zeolites, halides, anion- exchange resins, metals, metal oxide and metal salts. Carbon dioxide which acts as a co-catalyst with many of the same materials has also received extensive study.
  • 25. 25 COMPARISON OF MANUFACTURING PROCESSES SR. NO PROCESSES PARAMETER CATALYST ADVANTAGES/ DISADVANTAGES 1. Hydrolysis of EthyleneOxide No. of unit operations: 4 1) Non- catalyticYield : 98% Selectivity: 98% Temp:105o C Pressure : 1.5MPa 2) catalytic:Yield : 95% Selectivity: 90% Temp:200o C Pressure: 1-30 bar 1)Non Catalytic 2) Catalytic: Sulphuracids, Ion-exchange resins, Acidic zeolites, halides, Metal oxideand Metal salts. 91491.47 (Rs/m3 ) Use excess moles water to increase the yield which leads to high energyconsumption 1) Use less of water which leads to low energyconsumption 2) High yield &selectivity 3) permit use of low temp &pressure 4) Acid catalyst makes the chemical reactionsolution highly corrosive. 2. MEGfrom Ethylene Chlorohydrins No. of unit operations: variable Yield :50% Selectivity: 75% Non Catalytic very low yield& selectivit y verycostly 3. MEG from CO,H2,CH3OH & Formaldehyde Yield : 90-95% Temp: 200o C Pressure: 100atm Cromate Catalyst Bis(triphenylsilyl) chromate 96% pure = $55.3/gram High pressure process Discontinued now aday Lowselectivity
  • 26. 26 No. of unit operations: 1 (dielectric barrier discharge) 4. MEG from ethylene carbonate No. of unit operations: 2 Yield :98% Selectivity: 95% Temp:180o C Pressure:13bar Alkali halide or ammonium salt. Ammonium Chloride = 400 rupees/kg Give high yield and selectivity Utilitysaving Extra purification cost 5. Transesterification of ethylene carbonate. No. of unit operations: 3 Low yield Zirconium & Titanium Titanium Grade 12(USA origin) = 75000 rupees/kg Produced large Amount of byproducts
  • 27. 27 PROCESS DESCRIPTION This process manufactures Ethylene Glycol by the catalytic hydrolysis of ethylene oxide using less excess of water. After the completion of the reaction, the MEG is separated from the water and refined to give the final aqueous Mono-ethylene glycol. MEG chemical reaction unit: 1) Ethylene oxide is mixed with recycle and fresh water and pumped to reactor where it is reacts with water at 105℃&1.5 MPa in the presence of an ionite catalyst. 2) Reactor is a Catalytic Plug Flow Fixed Bed of Cross-linked Styrene DiVinylBenzene anion exchange resin. 3) The reaction involves two phases: Liquid Phase and Ionite Phase, the distribution of reaction mixture between these phases is a result of rapid equilibrium. 4) The catalytic hydration of ethylene oxide takes place in the ionite phase. 5) The reactor effluent goes to the evaporation unit for the evaporation of excess water. MEG evaporation unit: 1) The Ethylene Glycol evaporation unit has Three Effects in which the content of water finally gets reduced to 15% 2) Effluent to be evaporated flows by the pressure difference from one evaporator effect to the next effect. 3) Pressure of the evaporator system is such that the effluent is maintained as a liquid and is fed into the first effect evaporator. 4) Evaporation in the first effect is accomplished by 12Kg/cm2 (g) (11.6141 atm) pressure steam. 5) The overhead vapours from the first effect are used for the need of heating media in the second effect and overhead vapours from the second effect are used as heating media. 6) The third evaporation effect is operated under vacuum which is maintained by steam jet ejector nozzle. 7) Top products from all the effects is sent to the recovery column to recover any glycol evaporated with the water. MEG drying unit: 1) All of the remaining water is removed from the aqueous MEG solution in the drying distillation column. 2) A steam jet ejector maintains the vacuum in a drying column. 3) Pure aqueous ethylene glycol which is collected from the tower bottom is pumped to the refining tower. 4) Water vapours leaving the top of the drying column are fed to MEG recovery unit. MEG refining unit: 1) Ethylene glycol is withdrawn from the top of the refining column. 2) Some MEG is purged in the overhead of the column to the vacuum jets for reducing the aldehydes in the product. 3) The bottoms (dietylene glycol and triethylene glycol) are stored in a tank after cooling. 4) Vacuum is maintained by steam jet ejector. MEG recovery unit: 1) The MEG leaving from the Top of evaporator effects and the drying column are recovered in the Recovery
  • 28. 28 Column it is a PLATE COLUMN. 2) The refining column operated under Atmospheric pressure. 3) MEG leaving from the bottom and the water leaving from the top of the recovery column are Recycled to the ethylene glycol reactor.
  • 29. 29 MATERIAL BALANCE Basis: 100000TPA The process is a continuous process. The plant operates for 24 Hours a day and 333 days out of 365 days per year. No of working days = 333days Capacity = 1000000 333 = 300.3 T/days = 201.8147 kmol / hr. =the MEG obtained from distillation column, MOLECULAR WEIGHT (KG /KMOL): Ethylene Glycol 62 Water 18 Ethylene oxide 44.05 Carbon dioxide 44.01 Nitrogen 28 MATERIAL BALANCE OF INDIVIDUAL EQUIPMENT: assuming 99% of MEG in the feed to the Refining Column is obtained in distillate and 93% of MEG of feed to the Recovery Column is recovered from it. kmol of MEG in feed to the distillation column= 204.7 kmol / hr. Reactor:
  • 30. 30 Ethylene Oxide = 9190.54 kg = 208.876 kmols Ethylene glycol = 204.7 kmols = 12691.4kg Water = 37597.68 kg =2088.76 kmols Water = 1881.972 kmols = 33875.496 kg Higher glycol = 2.088 kmol =221.328 kg REACTOR Temp. = 373K Conversion = 100 % Pressure = 15 atm
  • 31. 31 In the reactor following chemical reactions take place C2H4O + H2O HOCH2CH2OH -----------------(1) (Ethylene oxide) (Water) (Mono Ethylene Glycol) C2H4O + HOCH2CH2OH HOCH2CH2OH------------(2) (Ethylene oxide) (Mono ethylene glycol) (Higher Glycol) As selectivity = 98% Moles of undesired product formed = 204.70 98 = 2.088 kmol Moles of MEG to be produced from reactor = 204.7+2.088 = 206.788 kmol Moles of ethylene oxide reacted by chemical reaction –(1) = 206.788 kmol. Moles of ethylene oxide reacted by chemical reaction –(2) = 2.088 kmol. Total EO reacted = 206.788 + 2.088 As conversion = 100% = 208.876 kmol Moles of ethylene oxide charged to reactor = 208.876kmol From the literature we know that the ratio of WATER TO ETHYLENE OXIDE =10:1 Kmol of water feed to EO reactor = 2088.76 kmol. (Including excess) From the chemical reaction (1) moles of water reacted = 206.788 kmol. M.B OF WATER: Moles of water in = Moles reacted + Moles unreacted 2088.76 = 206.788 + Moles unreacted Moles of water unreacted = 1881.972 kmol
  • 32. 32 M.B OF MEG: Here, moles of MEG contained in product = 206.788 – 2.088 = 204.7 kmol Material balance over reactor Component In, kg/hr In, kg/s Out, kg/hr Out, kg/s Ethylene oxide 9190.54 2.55292 - - Water 37597.68 10.4438 33875.496 9.40986 Ethylene glycol - - 12691.4 3.52538 Higher Glycol - - 221.328 0.06148 Triple Effect Evaporator: Consider the water content of glycol is reduced to 15% in evaporator i.e. 85% of water is removed. Considering triple effect evaporator as single unit. Amount of water removed = 0.85×1881.972 = 1599.6762 kmol. = 28794.1715 kg Total water moles at the top of the column = 1599.6762 kmol. = 28794.1716 kg. 15% water is still in the bottom with the MEG and other glycol. Amount of water in the bottoms = 1881.972-1599.6762 = 282.2958 kmol. = 5081.324 kg some quantity of glycol carries over from the top product of evaporator. Amount of glycol carry over along with water from 1st effect = 165.58 kg
  • 33. 33 F = 2088.76 kmol = 46788.224 kg M.E.G = 204.7 kmol = 12691.4 kg Water 1881.972 kmol =33875.496 kg W1 = 8285.66 kg MEG = 165.58 kg H2O = 8120.08 kg To 2nd effect evaporator Amount of glycol carry over along with water from 2nd effect evaporator = 189.139 kg W2 = 9689.31 kg MEG 189.139 kg H2o = 9500.171 kg From 2nd effect evaporator To 3rd effect evaporator To MEG Recovery column Y = 1610.8012 kmol Amount of glycol carry over with water from 3nd effect evaporator = 335.064 kg 2nd effect evaporator Pressure = 3.38 atm Temp = 414K 1st effect evaporator Pressure = 6.77 atm Temp = 432K
  • 34. W3 = 11508.96 kg MEG = 335.064 kg H2o 11173.89 kg From 3rd effect evaporator To MEG Refining column X = 477.9588 kmol To MEG recovery column Y = 1610.8012 kmol (Using VLE calculation) Total amount of glycol carry over along with water = 689.783 kg. =11.125 kmol Total (water +MEG) leaving top of evaporator effect =1599.6762 +11.125 Y = 1610.8012 kmol. TAKING OVERALL M.B F = Y +X 2088.76 =1610.8012+X X = 477.9588 kmol. (quantity leaving from bottoms of last evaporator effect) Material balance over Triple effect evaporator Component In, kg/hr In, kg/s Out, kg/hr Out, kg/s Liquid phase Vapor phase Liquid phase Vapor phase Water 33875.496 9.40986 5081.355 28794.141 1.4114875 7.9983725 MEG 12691.4 3.52538 12001.617 689.783 3.3337825 0.191606 HG 221.328 0.06148 221.328 - 0.06148 - Drying column: Y = 289.295 kmol 34 =5537.385 kg MEG = 456.061 kg 3rd effect evaporator Pressure = 0.24 atm Temp = 391K
  • 35. 35 F = 477.958 kmol =17304.258 kg MEG = 12001.606 kg H2O = 5081.324 kg HG = 221.328 kg Consider all the remaining water are removed in the drying column. Amount of water removed =5018.32 kg = 282.295 kmol. Kmol of glycol carrying along with water from drying column top = 456.061kg (Using VLE calculation) =7.3558 kmol. Total quantity leaving from top of drying column = (Amount of water +Amount of MEG) = 282.295 +7.3558 = 289.65 kmol. TAKING OVERALL M.B F = Y + X 477.9588 = 289.65 + X X = 188.306 kmol. (quantity leaving bottom of drying distillation column)
  • 36. 36 Now Total amount of MEG leaving along with water = (MEG leaving from top of Triple Effect Evaporator + MEG leaving from top of drying column) = 689.783+456.061 = 1145.844 kg. = 18.4813 kmol. Amount of feed to MEG Recovery column = (Amount of MEG leaving with water during evaporation + Amount of water expelled) = 18.4813+1881.973 = 1900.451 kmol. Material balance over drying column Component In, kg/hr In, kg/s Out, kg/hr Out, kg/s Liquid phase Vapor phase Liquid phase Vapor phase Water 5081.324 1.411478 - 5081.324 - 1.411478 MEG 12001.606 3.333779 11545.3545 456.061 3.2070429 0.1266836 HG 221.328 0.06148 221.328 - 0.06148 - MEG Refining Column (Packed Column): D = 184.54 kmol = 11448.8616 kg F = 188.306 kmol = 11766.873 kg MEG = 186.218 kmol = 11545 kg HG = 2.088 kmol = 221.328 kg MEG = 184.355 kmol (0.999 high purity) HG =0.18454 kmol W = 3.766 kmol = 317.664 kg MEG = 1.8523 kmol HG = 1.9136 kmol MEG refining column Pressure = 0.0131 atm Temp = 366.2 K
  • 37. 37 Distillate: F = D + W Take 99% recovery, of MEG fed to distillation column MEG obtained in Distillate = 188.306 × 0.99 × 0.98891 = 184.355 kmol / hr. = 11431.0818 kg/hr. Total kmols of Distillate = 184.355 / 0.999 = 184.54 kmol / hr. Avg. M.W. (distillate) = (0.999 x 62) + (0.001 x 106) = 62.044 kg / kmol. Amt. of Distillate (D) = 184.54 x 62.04 = 11448.8618 kg / hr. Amt. of HG in Distillate = 184.54 x 0.001 = 0.18454 kmol / hr. = 0.18454 x 106 = 19.561 kg / hr. kmol of feed (F) = 188.306 kmol / hr. = 11766.873 kg / hr TAKING OVERALL M.B. 188.306 = 184.54 + W W = 3.766 kmol/hr. M.B. OF MEG F x (Xf MEG) = D x (Xd MEG) + W x (Xb MEG) 188.306 x 0.9889 = 184.54 x 0.999 + 3.766 x Xb MEG Xb MEG = 0.4918 (mol.fr.of MEG in Bottoms) XbHG = (1- 0.4918) = 0.5081 (mol.fr.of HG in Bottoms) kmol of MEG in Bottoms = 0.4918 x 3.766 =1.8521 kmol / hr Molar Wt of MEG = 62 kg / kmol = 114.831 kg/hr. amount of HG in Bottom product = 0.5081 x 3.766 =1.9135kmol / hr.
  • 38. 38 Mol. Weight of HG =106 kg / kmol = 1.9135 x 106 = 202.83kg/hr. Material balance over Refining packed column Component In, kg/hr In, kg/s Out, kg/hr Out, kg/s Liquid phase Vapor phase Liquid phase Vapor phase MEG 11545.545 3.207095 114.8426 11430.01 0.03190 3.1750027 HG 221.328 0.06148 202.8416 19.56124 0.0563448 0.00543367
  • 39. 39 99 MEG recovery column Plate column MEG recovery column (Plate column): F = 1900.45 kmol = 35021.339 kg MEG = 18.481 kmol = 1145.844 kg H2O = 1881.97 kmol = 33875.496 kg D = 1881.97 kmol = 11766.873 kg MEG = 1.88 kmol H2O = 1880.08 kmol 99% water in D W = 18.481 kmol =1205.55kg MEG = 17.122 kmol H2O = 1.3584 kmol kmol of Water in Distillate = 1881.97 x 0.9 = 1880.08 kmol / hr kmol of Distillate (D) = 1880.08 / 0.999 = 1881.97 kmol / hr. Avg. M.W. of distillate = (0.999 x 18) + (0.001 x 62) = 18.044 kg / kmol. Amt. of Distillate (D) = 1881.97 x 18.044 = 33958.266 kg /hr Amt. of MEG in Distillate = 1881.97 x 0.001 = 1.88 kmol / hr = 1.88 x 62 = 116.56 kg/ hr. Amount of feed (F) = 1900.451 kmol / hr = 35021.339 kg/hr.
  • 40. 40 OVERALL M.B. F = D+ W 1900.451 = 1881.47 + W W = 18.481 kmol / hr M.B. OF WATER F x (Xf H) = D x (Xd H) + W x (Xb H) 1900.451 x 0.99 = 1881.97 x 0.999 + 18.481 x Xb W Xb W = 0.0735 (mol.fr.of Water in Bottoms) Xb MEG = 1- 0.0735 = 0.9264 (mol.fr.of MEG in Bottoms) Kmols MEG in Bottom = 18.481 x 0.9264 = 17.122 kmol /hr = 17.122 x 62 = 1061.56 kg/hr. amount of Water in Bottoms = 18.481 – 17.130 = 1.3584 kmol / hr = 1.3584 x 18 = 143.99 kg/ hr. Material balance over Recovery plate column Component In, kg/hr In, kg/s Out, kg/hr Out, kg/s Liquid phase Vapor phase Liquid phase Vapor phase Water 33875.496 9.40986 24.4512 33841.44 0.006792 9.4004 MEG 1145.844 0.31829 1061.546 116.56 0.294874 0.032378 Overall material balances
  • 41. 41 Equipment Component In, kg/hr In, kg/s Out, kg/hr Out, kg/s Liquid phase Vapor phase Liquid phase Vapor phase Reactor Ethylene oxide 9190.54 2.552927778 - - - - Water 37597.68 10.4438 33875.496 - 9.40986 - MEG - - 12691.4 - 3.525388889 - HG - - 221.328 - 0.06148 - Triple effect evaporator Water 33875.496 9.40986 5081.355 28794.14 1 1.4114875 7.9983725 MEG 12691.4 3.525388889 12001.617 689.783 3.3337825 0.191606389 HG 221.328 0.06148 221.328 - 0.06148 - Drying column Water 5081.324 1.411478889 5081.324 1.411478889 MEG 12001.606 3.333779444 11545.3545 456.061 3.207042917 0.126683611 HG 221.328 0.06148 221.328 - 0.06148 - MEG refining column MEG 11545.545 3.207095833 114.8426 11430.01 0.031900722 3.175002778 HG 221.328 0.06148 202.8416 19.56124 0.056344889 0.005433678 MEG recovery column Water 33875.496 9.40986 24.4512 33841.44 0.006792 9.4004 MEG 1145.844 0.31829 1061.546 116.56 0.294873889 0.032377778
  • 42. 42 MSDS Data sheet for Ethylene Oxide CAS number: 75-21-8 GHS Category table for reference: Study/hazard statement Category 1 Category2 Category 3 Category 4 Category 5 Acute Oral LD50 <5 mg/kg > 5 <50 mg/kg > 50 < 300 >300<2000 >2000< Fatal if swallowed Fatal if swallowed mg/kg Toxic if swallowed mg/kg Harmful if swallowed 5000mg/kg May be harmful if swallowed Acute Dermal LD50 < 50 mg/kg >50<200mg/kg >200<1000 >1000<2000 >2000<5000 Fatal in contact with skin Fatal in contact with skin mg/kg Toxic in contact with skin mg/kg Harmful in contact with skin mg/kg May be harmful in contact with skin Acute Inhalation Dust LC50 Gases LC50 Vapours LC50 < 0.05 mg/L > 0.05 < 0.5 >0.5<1.0mg/L >1.0<5mg/L See footnote below this <100ppm/V mg/L >500<2500 >2500<20000 table <0.5 mg/L Fatal >100<500ppm/ ppm/V ppm/V if inhaled V >0.5<2.0mg/L Fatal if inhaled >2.0<10mg/L Toxic if inhaled >10<20mg/L Harmful if inhaled Flammable liquids Flashpoint<23 degrees C and initial boiling point<35 degrees C. Extremely flammable liquid and vapour Flashpoint<23 degrees C and initial boiling point > 35 degrees C. Highly flammable liquid and vapour Flashpoint>23 degrees C<60 degree sC. Flammable liquid and vapour Flash point > 60 degrees C < 93 degrees C. Combustible liquid Not Applicable Note: Gases concentration are expressed in parts per million per volume(ppmV). NOTE1:Category 5 is for mixtures which are of relatively low acute toxicity but which under certain circumstances may pose a hazard to vulnerable populations. These mixtures are anticipated to have an oral or dermal LD50 value in the range of 2000-5000 mg/kg bodyweight or equivalent dose for other routes of exposure. In light of animal welfare considerations, testing in animals in Category5 ranges is discouraged and should only be considered when there is a strong likelihood that results of such testing would have a direct relevance for protecting human health. NOTE 2: These values are designed to be used in the calculation of the ATE for classification of a mixture based on its ingredients and do not represent test results. The values are conservatively set at the lower end of the range of Categories1 and2,and at a point approximately1/10th from the lower end of the range for Categories3–5.
  • 43. 43 GHS Category table for reference: Continued Study/hazar d statement Category 1 Category2 Category 3 Eye Irritation Effects on the cornea, iris or conjunctiva that are not expected to reverse or that have not fully reversedwithin21days. Causes severe eye damage. 2A:Effects on the cornea, iris or conjunctiva that fully reverse within 21days. Causes severe eye irritation. 2B:Effects on the cornea ,iris or conjunctiva that fully reverse within7 days. Causes eye irritation. Not applicable Skin Irritation Destruction of skin tissue ,with sub categorization based on exposure of upto 3 minutes(A),1 hour(B),or 4 hours(C). Causes severe skin burns and eye damage. Mean value of>2.3>4.0for erythema/ escharoredemain atleast 2 of 3tested animals from gradings at24,48,and72 hours(or on 3 consecutive days after onset if chemical chemical reactions are delayed); inflammation that persists to end of the (normally14-day)observation period. Causes skin irritation. Mean value of>1.5<2.3 for erythema/escharor edemain atleast2of3 Tested animals from gradings at24,48,and72hours(oro n3 consecutive days after onset if chemical chemical reactions are delayed). Causes mild skin irritation. Environment: Acute Toxicity Category 96hrLC50(fish)<1mg/L48h rEC50(crustacea)<1mg/L,7 2/96 hrErC50(aquatic plants)<1mg/L Very toxic to aquatic life 96hrLC50(fish)>1<10mg/L48 hrEC50(crustacea)>1<10mg/ L72/96hrErC50(aquaticplants )>1<10mg/L Toxic to aquatic life 96hrLC50(fish)>10<10 0 mg/L 48 hr EC50 (crustacea) >10<100mg/L72/96hrE rC50(aquatic plants)>10<100mg/L Harmful to aquatic life Flammable Aerosol Extremely flammable aerosol Flammable aerosol Not Applicable Flammable solids Using the burning rate test, substances or mixtures other than metal powders: (a) wetted zone does not stop fire and (b)burning time<45seconds or burning rate>2.2mm/second Using the burning rate test, metal powders that have burning time<5 minutes Flammable solid Using the burning rate test, substances or mixtures other than metal powders: (a)wetted zone does not stop fire for atleast 4 minutes and(b)burning time< 45seconds or burning rate>2.2 mm/second Using the burning rate test, metal powders that have burning time> 5<10minutes Flammable solid Not Applicable Flammable gases Gases,which at 20 degrees C and a standard pressure of 101.3kPA: ) are ignitable when in a mixture of 13% or less by volume in air; or ) have a flammable range with air of at least 12 percentage points Gases,other than those of category1, which, at 20 degrees C and a standard pressure of101.3kPA,have a flammable range while mixed in air. Flammable gas Not Applicable
  • 44. 44 regardless of the lower flammable limit. Extremely flammable gas