Petrochemical

Department

Ethylene Glycol
Plant
SUPERVISERs: dr.Rafie Rishdi

PREPEARED BY:
Zhwan Remedan
2021
Kajin Jalal
Nazik Jebar
Mohamed Abdulmejid
Siver Tehsin
1. Introduction
Ethylene glycol (IUPAC name: ethane-1,2-diol) is an organic compound
with the formula (CH2OH)2. It is mainly used for two purposes, as a raw material
in the manufacture of polyester fibers and for antifreeze formulations. It is an
odorless, colorless, sweet-tasting, viscous liquid. It is an chemical intermediate
used in a large number of industrial processes (e.g. energy, plastics, automobiles,
and chemicals). Indeed, owing to its unique properties and versatile commercial
applications, a variety of chemical systems (e.g., catalytic and non-catalytic) have
been explored for the synthesis of EG, particularly via reaction processes derived
from fossil fuels (e.g., petroleum, natural gas, and coal) and biomass-based
resources. This critical review describes a broad spectrum of properties of EG
and significant advances in the prevalent synthesis and applications of EG, with
emphases on the catalytic reactivity and reaction mechanisms of the main
synthetic methodologies and applied strategies. We also provide an overview
regarding the challenges and opportunities for future research associated with EG
[6].

1.1.History
According to most sources, French chemist Charles-Adolphe Wurtz (1817–
1884) first prepared ethylene glycol in 1856. He first treated "ethylene iodide"
(C2H4I2) with silver acetate and then hydrolyzed the resultant "ethylene
diacetate" with potassium hydroxide. Wurtz named his new compound "glycol"
because it shared qualities with both ethyl alcohol (with one hydroxyl group) and
glycerin (with three hydroxyl groups) [1]. In 1859, Wurtz prepared ethylene
glycol via the hydration of ethylene oxide [2]. There appears to have been no
commercial manufacture or application of ethylene glycol prior to World War I,
when it was synthesized from ethylene dichloride in Germany and used as a
substitute for glycerol in the explosives industry. In the United States,
semicommercial production of ethylene glycol via ethylene chlorohydrin started
in 1917. The first large-scale commercial glycol plant was erected in 1925 at
South Charleston, West Virginia, by Carbide and Carbon Chemicals Co. (now
Union Carbide Corp.). By 1929, ethylene glycol was being used by almost all
dynamite manufacturers. In 1937, Carbide started up the first plant based on
Lefort's process for vapor-phase oxidation of ethylene to ethylene oxide. Carbide
maintained a monopoly on the direct oxidation process until 1953, when the
Scientific Design process was commercialized and offered for licensing [3].

1.2. Chemistry

Ethylene glycol is metabolized in the liver through a series of enzymes. The

intermediate metabolites of the pathway (in order) are: glycoalde-hyde, glycolic
acid, and glyoxylic acid. Ultimately, glyoxylic acid is converted to oxalic acid,
which pre-cipitates in the presence of calcium as calcium oxalate crystals. The
most clinically significant metabolite in the pathway is glycolic acid which is
primarily responsible for the meta-bolic acidosis. The pathway is assists in
explaining our patient’s laboratory and urine microscopy findings [4].

1.3. Physical properties

Ethylene glycol is the simplest diol and possesses several unique properties
owing to its characteristic structure (i.e., two hydroxyl (OH) groups at adjacent
positions along a hydrocarbon chain).1 Ethylene glycol is a colorless, odorless,
relatively non-volatile, and hygroscopic liquid with low viscosity (detailed
physical properties are listed in Table 1). It tastes sweet and imparts a warming
sensation to the tongue upon swallowing. It is completely miscible with many
 polar solvents (e.g., water, alcohols, glycol ethers, and acetone) and only slightly
soluble in non-polar solvents such as benzene, toluene, dichloroethane, and
chloroform. It is difficult to crystallize, When it is cooled, it forms a highly
viscous, super-cooled mass that eventually solidifies to produce a glass-like
substance [5].

Table (1.1): Physical properties of ethylene glycol [5].

Physical Properties

Boiling point: 198°C

Melting point: -13°C
Flash point: 111°C closed cup
119°C open cup
Explosive limits: 3.2 – 15.3 volume % in air
Autoignition 398°C
temperature:
Relative density of 1.00
vapour/air mixture at
20°C (air = 1):
Conversion factors: 1 mg/m3 = 0.37 ppm (Atm 25°C)
1 ppm = 2.54 mg/m3 (Atm 25°C)
Solubility: Soluble in water, ethanol, acetone, acetic acid,
glycerine, pyridine, aldehydes;
Little soluble in ether;
Insoluble in oil, fat, hydrocarbures halogènes.
1.4 Chemical Properties and Reactions

The presence of two hydroxyl groups in the glycol molecule determines its
chemistry and permits reactions such as esterification, dehydration, oxidation,
halogenation and formation of alcoholates and acetals to take place. In the
following examples, ethylene glycol is used to illustrate some of its reaction
characteristics[6], [7].

• Ethylene glycol reacts with metals like sodium mono and disodium
derivatives.

𝑵𝒂 𝟏
𝑪𝑯𝟐 𝑶𝑯 − 𝑪𝑯𝟐 𝑶𝑯 → 𝑪𝑯𝟐 𝑶𝑯 − 𝑪𝑯𝟐 𝑶𝑵𝒂 + 𝑯𝟐
𝟐
Monosoduim glycolate
• Reaction with halogen acids.

𝟒𝟑𝟑𝑲
𝑪𝑯𝟐 𝑶𝑯 − 𝑪𝑯𝟐 𝑶𝑯 + 𝑯𝑪𝒍 → 𝑪𝑯𝟐 𝑶𝑯 − 𝑪𝑯𝟐 𝑪𝒍 + 𝑯𝟐 𝑶
Ethylene clorohydrine
• Reaction with phosphorous trihalides

𝟑𝑪𝑯𝟐 𝑶𝑯 − 𝑪𝑯𝟐 𝑶𝑯 + 𝟐𝑷𝑪𝒍𝟑 → 𝟑𝑪𝑯𝟐 𝑪𝒍 − 𝑪𝑯𝟐 𝑪𝒍 + 𝟑𝑯𝟑 𝑷𝑶𝟒

• Reaction with phosphorous pantahalide and thionyl chloride

𝑪𝑯𝟐 𝑶𝑯 − 𝑪𝑯𝟐 𝑶𝑯 + 𝟐𝑷𝑪𝒍𝟓 → 𝟑𝑪𝑯𝟐 𝑪𝒍 − 𝑪𝑯𝟐 𝑪𝒍 + 𝑷𝑶𝑪𝒍𝟑 + 𝟐𝑯𝑪𝒍

𝑪𝑯𝟐 𝑶𝑯 − 𝑪𝑯𝟐 𝑶𝑯 + 𝟐𝑺𝑶𝑪𝒍𝟐 → 𝑪𝑯𝟐 𝑪𝒍 − 𝑪𝑯𝟐 𝑪𝒍 + 𝟐𝑺𝑶𝟐 + 𝟐𝑯𝑪𝒍

• Reaction with aldehyde and ketone

 𝑶𝑪𝑯
𝑨𝒍𝒅𝒆𝒉𝒊𝒅𝒆 + 𝑪𝑯𝟐 𝑶𝑯 − 𝑪𝑯𝟐 𝑶𝑯 → 𝑹 − 𝑪𝑯 <𝑶𝑪𝑯𝟐𝟐
Cyclic acetal
𝑶𝑪𝑯
𝑲𝒆𝒕𝒐𝒏𝒆 + 𝑪𝑯𝟐 𝑶𝑯 − 𝑪𝑯𝟐 𝑶𝑯 → 𝑹𝑹> 𝑪 <𝑶𝑪𝑯𝟐𝟐
Cyclic ketal

1.5. Production

Ethylene glycol is produced from ethylene (ethene), via the intermediate ethylene
oxide. Ethylene oxide reacts with water to produce ethylene glycol according to
the chemical equation:

C2H4O + H2O → HO−CH2CH2−OH

This reaction can be catalyzed by either acids or bases, or can occur at

neutral pH under elevated temperatures. The highest yields of ethylene glycol
occur at acidic or neutral pH with a large excess of water. Under these conditions,
ethylene glycol yields of 90% can be achieved. The major byproducts are the
oligomers diethylene glycol, triethylene glycol, and tetraethylene glycol. The
separation of these oligomers and water is energy-intensive. About 6.7 million
tonnes are produced annually [8]. A higher selectivity is achieved by use of
Shell's OMEGA process. In the OMEGA process, the ethylene oxide is first
converted with carbon dioxide (CO2) to ethylene carbonate. This ring is then
hydrolyzed with a base catalyst in a second step to produce mono-ethylene glycol
in 98% selectivity [9]. The carbon dioxide is released in this step again and can
be fed back into the process circuit. The carbon dioxide comes in part from the
 ethylene oxide production, where a part of the ethylene is completely oxidized.
Ethylene glycol is produced from carbon monoxide in countries with large coal
reserves and less stringent environmental regulations. The oxidative
carbonylation of methanol to dimethyl oxalate provides a promising approach to
the production of C1-based ethylene glycol [10]. Dimethyl oxalate can be
converted into ethylene glycol in high yields (94.7% [11]) by hydrogenation with
a copper catalyst [12]:

Figure (1.1): Pathway of synthesis of Ethylene glycol.

Because the methanol is recycled, only carbon monoxide, hydrogen, and oxygen are
consumed. One plant with a production capacity of 200 000 tons of ethylene glycol
per year is in Inner Mongolia, and a second plant in the Chinese province of Henan
with a capacity of 250 000 tons per year was scheduled for 2012. As of 2015, four
plants in China with a capacity of 200 000 t/a each were operating with at least 17
more to follow [12].

1.6. Application of ethylene glycol

Minor uses of ethylene glycol include the manufacture of capacitors, as a chemical

intermediate in the manufacture of 1,4-dioxane, as an additive to
prevent corrosion in liquid cooling systems for personal computers, and inside the
lens devices of cathode-ray tube type of rear projection televisions. Ethylene glycol
is also used in the manufacture of some vaccines, but it is not itself present in these
injections. It is used as a minor (1–2%) ingredient in shoe polish and also in some
inks and dyes. Ethylene glycol has seen some use as a rot and fungal treatment for
wood, both as a preventative and a treatment after the fact. It has been used in a few
cases to treat partially rotted wooden objects to be displayed in museums. It is one
of only a few treatments that are successful in dealing with rot in wooden boats, and
is relatively cheap. Ethylene glycol may also be one of the minor ingredients in
screen cleaning solutions, along with the main ingredient isopropyl alcohol.
Ethylene glycol is commonly used as a preservative for biological specimens,
especially in secondary schools during dissection as a safer alternative
to formaldehyde. It is also used as part of the water-based hydraulic fluid used to
control subsea oil and gas production equipment. Ethylene glycol is used as
a protecting group in organic synthesis to protect carbonyl compounds such as
ketones and aldehydes. Silicon dioxide reacts in heated reflux under dinitrogen with
ethylene glycol and an alkali metal base to produce highly
reactive, pentacoordinate silicates which provide access to a wide variety of new
silicon compounds.[20] The silicates are essentially insoluble in all polar solvent
except methanol. It also can be used in vaccine manufacture or as a formaldehyde
substitute when preserving biological specimens, see Figure (1.2) [13], [5].
 Figure (1.2): Synthetic methodologies and applications of EG covered in
this review.

1.7. Derivatives of mono Ethylene glycol

India Glycols has set up its ethylene glycol plant in technical collaboration
with Scientific Design Inc, USA. The plant produces three derivatives of ethylene
glycols are monoethylene glycol (MEG), diethylene glycol (DEG) and
triethylene glycol (TEG). IGL has been manufacturing bio-MEG derived from
bio-ethanol since 1989, and meeting stringent international specifications as
required by the polyester fibre, yarn, film and PET resin industries. MEG is a
colourless, odourless, non-volatile liquid. It is completely miscible in water and
many organic solvents. The MEG manufactured is of minimum 99.5 per cent
purity and meets the required UV transmittance values specified by polyester
manufacturers. DEG is a stable, high-boiling, odourless and hygroscopic liquid,
which is completely miscible in water. TEG is a colourless, odourless and stable
liquid with low viscosity and a high boiling point. It is miscible in water and
hygroscopic in nature see figure (1.2) [14].

(a)
(b)

(c)

Figure (1.2): structures of derivatives of EG, (a): MEG, (b): DEG, (c): TEG.

1.8. Storage and distribution

Mono Ethylene Glycol can be stored in stainless steel, aluminium, or lined

drums, tank cars, or tank trucks. It has a specific gravity of 1.115 and a flash point
of 110 °C (closed cup). It is not regulated for transport on road, rail, air, or sea
but it is classified as harmful, and is harmful if swallowed [15].

1.9. Market survey

 The U.S. Market is Estimated at $8.3 Billion, While China is Forecast to Grow
at 5.8% CAGR. The Ethylene Glycol market in the U.S. is estimated at US$8.3
Billion in the year 2020. China, the world`s second largest economy, is forecast
to reach a projected market 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 markets are Japan and Canada, each forecast to grow at
0.8% and 2.3% respectively over the 2020-2027 period. Within Europe, Germany
is forecast to grow at approximately 1.5% CAGR. Triethylene Glycol (TEG)
Segment to Record 1.7% CAGR. In the global Triethylene Glycol (TEG)
segment, USA, Canada, Japan, China and Europe will drive the 1.4% CAGR
estimated for this segment. These regional markets accounting for a combined
market 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 markets. Led by countries such as
Australia, India, and South Korea, the market in Asia-Pacific is forecast to reach
US$5.3 Billion by the year 2027, while Latin America will expand at a 2.5%
CAGR through the analysis period. We bring years of research experience to this
6th edition of our report. The 271-page report presents concise insights into how
the pandemic has impacted production and the buy side for 2020 and 2021. A
short-term phased recovery by key geography is also addressed [16].

1.10. Quality specification

Mono-, di- and triethylene glycols are colorless, essentially odorless stable
liquids with high boiling points. The three have many similar chemical
properties. Differences in their applications are due chiefly to variations in
physical properties such as viscosity, hygroscopicity and boiling points.
Monoethylene Glycol (MEG) is by far the largest volume of the glycol products
sold by the industry and is normally sold in three grades: fiber grade, industrial
grade, and antifreeze grade. Each of these grades can be distinguished by their
glycol and water contents. Fiber grade MEG is typically 99.9% (w) minimum
MEG. Industrial grade is 99.0% (w) minimum MEG, and antifreeze grade is 95.0%
(w) minimum MEG. We directed attention in an earlier paragraph to the
important role ethylene glycol plays as an intermediate in the manufacture of
polyester products. Fiber grade MEG is the principal raw material sought by
processors to assure production of the highest quality polyester products for
sale in the marketplace. Some illustrative manufacturing specifications for fiber
grade MEG are given in Table (1.2). For a number of users, fiber grade MEG must
also meet specific ultra violet (UV) light transmittance requirements. For
example, a 98% minimum UV transmittance at 350 nanometers is set forth in
some sales contracts [17].

Table (1.2):. Manufacturing composition limits for fiber grade MEG

Reference

[1] Adolphe Wurtz (1856). "Sur le glycol ou alcool diatomique" [On glycol or
dibasic alcohol]. Comptes Rendus. 43: 199–204.
[2] Wurtz (1856), page 200: "… je propose de le nommer glycol, parce qu'il se
rapproche à la fois, par ses propriétés, de l'alcool proprement dit et de la
glycérin, entre lesquels il se trouve placé." ( … I propose to call it glycol because,
by its properties, it is simultaneously close to [ethyl] alcohol properly called and
glycerin, between which it is placed)

[3] Ad. Wurtz (1859) "Synthèse du glycol avec l'oxyde d'éthylène et l'eau"
(Synthesis of glycol from ethylene oxide and water), Comptes rendus, 49 : 813–
815.

[4] Harris, J. M. (Ed.). (2013). Poly (ethylene glycol) chemistry: biotechnical and
biomedical applications. Springer Science & Business Media.

[5] Yue, H., Zhao, Y., Ma, X., & Gong, J. (2012). Ethylene glycol: properties,
synthesis, and applications. Chemical Society Reviews, 41(11), 4218-4244.

[6] Möbius, D., Miller, R., & Fainerman, V. B. (2001). Surfactants: chemistry,
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[7] Dobson, S., & World Health Organization. (2000). Ethylene glycol:
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[8] Siegfried Rebsdat; Dieter Mayer. "Ethylene Glycol". Ullmann's Encyclopedia

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[9] Scott D. Barnicki "Synthetic Organic Chemicals" in Handbook of Industrial

Chemistry and Biotechnology edited by James A. Kent, New York : Springer,
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[10] Nexant/Chemsystems, "Coal to MEG, Changing the Rules of the Game"
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(PDF; 5,4 MB), 2011 Prospectus.

[11] 983 EP 046 983, S. Tahara et al., "Process for continuously preparing
ethylene glycol", assigned to Ube Industries and H. T. Teunissen and C. J.
Elsevier, Ruthenium catalyzed hydrogenation of dimethyl oxalate to ethylene
glycol, J. Chem. Soc., Chem. Commun., 1997, 667–668),
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[12] S. Zhang et al., Highly-Dispersed Copper-Based Catalysts from Cu–Zn–Al

Layered Double Hydroxide Precursor for Gas-Phase Hydrogenation of Dimethyl
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DOI:10.1007/s10562-012-0871-8. "China's coal-based chemicals are a trade-
off".

[13] "Monoethylene Glycol". Berryman Chemical. 2020-07-20. Retrieved 2020-

08-05. Theodora W. Greene; Peter G. M. Wuts (1999). Protective Groups in
Organic Synthesis (Third ed.). John Wiley & Sons. pp. 312–322. ISBN 978-0-
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[15] Sundararajan, S., Kumar, A., Chakraborty, B. C., Samui, A. B., & Kulkarni,
P. S. (2018). Poly (ethylene glycol)(PEG)-modified epoxy phase-change polymer
with dual properties of thermal storage and vibration damping. Sustainable
Energy & Fuels, 2(3), 688-697.

[16] Trmcic-Cvitas, J., Hasan, E., Ramstedt, M., Li, X., Cooper, M. A., Abell,
C., ... & Gautrot, J. E. (2009). Biofunctionalized protein resistant oligo (ethylene
glycol)-derived polymer brushes as selective immobilization and sensing
platforms. Biomacromolecules, 10(10), 2885-2894.
[17] Dye, R. F. (2001). Ethylene glycols technology. Korean Journal of Chemical
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