DEPARTMENT OF CHEMICAL ENGINEERING

UNIVERSITY COLLEGE OF TECHNOLOGY (AUTONOMOUS)

OSMANIA UNIVERSITY, HYDERABAD-500007(T.S)

A PROJECT REPORT ON
DESIGN OF ETHYLENE GLYCOL IN PLANT AND
OPTIMISATION
By
MOHAMMED ILIYAS PASHA
ROLL NO: 1008-17-802-025
B.TECH VII - SEMESTER
UNDER THE ESTEEMED GUIDANCE OF
Dr. S.SRINU NAIK
 ABSTRACT
This work deals with the optimization of the process of production of Mono Ethylene
Glycol from Ethylene Oxide by the hydrolysis process. This process also involves an
undesirable reaction between mono ethylene glycol and water to form higher glycols,
mainly Di Ethylene Glycol. Since product distribution depends oxide/water ratio of the
feed stream, excess water is favored to improve the selectivity of the reaction towards
Mono Ethylene Glycol. This results in increase in power consumption during final
isolation stages from dilute aqueous solutions. Costs have to be controlled optimized and
controlled by discovering a suitable method of distillation and designing of the
distillation columns accordingly. All the variations decrease the capital and/or energy
cost but also optimize the purity of final product. Thus, this provides a classic example of
optimization of a process and engineering design. The process present in the design book
by Turton et. Al is alluded to. The aim of this project is to develop an optimum design
for the Mono Ethylene Glycol plant, which aims to save as much power as possible and
also to improve the quality of the final product to a certain extent

I
 INTRODUCTION
The process considered for studying in this report is the production of Mono Ethylene
Glycol, popularly known as MEG from Ethylene Oxide in a MEG production plant. This
process is a classic example to study trade-off in simulation and engineering design as
there is a huge scope for optimization in the reaction section of the plant and the cost in
the separation section.

MEG is produced by the reaction of Ethylene Oxide and water and it also involves an
undesirable reaction between MEG and water to produce higher glycols, mainly Di
Ethylene Glycol(DEG). The raw materials fed to the plant are Ethylene Oxide and water.
The process description of “Chemical Engineering Journal 107(2005), 199-204.” has
been utilized which provides us with valuable and relevant data required for the
simulation and study of the process.

1.1 History
Ethylene Glycol (1, 2 – ethanediol), HOCH2CH2OH usually called MEG is the simplest
Diol. Diethylene glycol and Triethylene glycol are Oligomers of Mono ethylene glycol.
It was first prepared by Wurtz in 1859; by treatment of 1,2 dibromoethane with silver
acetate producing ethylene glycol diacetate via saponification using potassium hydroxide
and later in 1860 from the hydration of ethylene oxide. There was no known commercial
manufacturer or industrial application of ethylene glycol before World War-I. First
commercial use is noted during World War 1 when it was used as substituted for glycerol
in the explosives industry but has since developed into a major industrial product.

In 1917, U.S. patented the use of ethylene glycol as an antifreeze for water in automotive
cooling systems, but this commercial application did not begin until the late 1920s.
National Carbon Co. (Now Union Carbide Corp.) launched the first inhibited glycol
antifreeze in 1930 under the brand name "prestone."

Until the late 1930s, Carbide remained the sole supplier. DuPont launched an ethylene
glycol plant in Belle, West Virginia in 1940, based on its new formaldehyde methanol
process. In 1937, Carbide started the first plant based on Lefort's vapor phase oxidation

1
 process. The worldwide capacity for production of Ethylene Glycol via hydrolysis of
ethylene oxide is estimated to be 7×106 ton/annum [2,3].
CHEMISTRY:
Compound contains more than one –oly group is called Polyhydric Alcohol (Dihydric alcohol) or polyols (Diols).
Diols are commonly known as
Glycols, since they have a
sweet taste (Greek, glycys=
Sweet).
Dihydric alcohols
because compounds
contain two –OH groups
on one carbon are seldom
encountered. This is because they are unstable and undergo spontaneous decomposition to give corresponding
carbonyl compound and water.

Figure-1[10]
According to IUPAC system of nomenclature, IUPAC name of glycol is obtained by adding suffix Diol to the name
of parent alkanes.

HO OH H H H H
H--C---C--H HO--C---C--OH H--C---C--H
H H H H HO OH
1, 2 Glycol 1, 3 Glycol 1, 4 Glycol
(α- Glycol) (β- Glycol) (γ- Glycol)

Glycols are Diols. Compounds containing two hydroxyl groups attached to separate carbon in an aliphatic chain.
Although glycols may contain heteroatom can be represented by the general formula C 2nH4nOn-1(OH) 2. [3, 4]
Formula Common name IUPAC name
CH2OHCH2OH Ethylene Glycol Ethane-1, 2-Diol

1.2 Industrial Uses of MEG

Around 50% of MEG is used to produce anti-freeze for internal combustion engines and
around 40% of it is used as a raw material for polyesters such as Polyethylene
Terephthalate popularly known as PET. It is also used as a substitute for glycerol in
 explosives as it allows detonation even at low temperatures where ordinary dynamites
freeze. In terms of consumer market, MEG is widely used as a precursor for production
of numerous fibres such as Dacron, Terylene, Fortel etc. These fibres are made by
polymerisation of MEG with BisHydroxyEthyl Terephthalate also known as BHET.

We can also discover usage of MEG in minor amounts as a hydraulic fluid, production of
resins, solvent in capacitors and a moisture retaining agent.
USES:
The following is a summary of the major uses of ethylene glycol:
1.3.1 Antifreeze
 A major use of ethylene glycol is as antifreeze for internal combustion engines. Solutions containing
ethylene glycol have excellent heat transfer properties and higher boiling points than pure water. Accordingly, there
is an increasing tendency to use glycol solutions as a year-round coolant. Ethylene glycol solutions are also used as
industrial heat transfer agents.
 Mixtures of ethylene glycol and propylene glycol are used for defrosting and de-icing aircraft and
preventing the formation of frost and ice on wings and fuselages of aircraft while on the ground. Ethylene glycol-
based formulations are also used to de-ice airport runways and taxiways as de-icing agent.
 Asphalt-emulsion paints are protected by the addition of ethylene glycol against freezing, which would
break the emulsion. Carbon dioxide pressurized fire extinguishers and sprinkler systems often contain ethylene
glycol to prevent freezing.
1.3.2 Explosives

 Ordinary dynamite will freeze at low temperatures and cannot then be detonated. Ethylene glycol dinitrate,
which is an explosive itself, is mixed with dynamite to depress its freezing point and make it safer to handle in
cold weather.
 Mixtures of glycerol and ethylene glycol are nitrated in the presence of sulfuric acid to form solutions of
nitroglycerin in ethylene glycol dinitrate, which are added to dynamite in amounts ranging from 25 to 50%.
1.3.3 Polyester Fibers

 The use of ethylene glycol for fibers is becoming the most important consumer of glycol worldwide. These
fibers, marketed commercially under various trade names like Dacron, Fortel, Kodel, Terylene etc are made by the
polymerization of ethylene glycol with BisHydroxyEthyl Terephthalate (BHET).
 These Polyester fibers are used for recyclable bottles.
1.3.4 Resins

 Polyester resins made from maleic and phthalic anhydrides, ethylene glycol, and vinyl-type monomers have
important applications in the low-pressure lamination of glass fibers, asbestos, cloth and paper.
 Polyester-fiberglass laminates are used in the manufacture of furniture, automobile bodies, boat hulls,
suitcases and aircraft parts. Alkyd-type resins are produced by the reaction of ethylene glycol with a dibasic acid
 such as o-phthalic, maleic or fumaric acid. These resins are used to modify synthetic rubbers, in adhesives, and for
other applications.

PROPERTIES

2.1 PHYSICAL PROPERTIES:

 Monoethylene glycol and its lower polyglycols are clear, odorless, colorless, syrupy liquid with a sweet
taste.
 It is a hygroscopic liquid completely miscible with many polar solvents, such as water, alcohols, glycol
ethers, and acetone.
 Its solubility is low however in non polar solvents, such as benzene, toluene, dichloroethane, and
chloroform. It is miscible in ethanol in all proportion but insoluble in ether, completely miscible with many polar
solvents, water, alcohols, glycol ethers and acetone. Its solubility is low, however in nonpolar solvents, such as
benzene, toluene, dichloromethane and chloroform.
 It is a toxic as methyl alcohol when taken orally.
 Ethylene glycol is difficult to crystallize, when cooled; it forms a highly viscous, super-cooled
mass that finally solidifies to produce a glasslike substance.
 The widespread use of ethylene glycol as an antifreeze is based on its ability to lower freezing
point when mixed with water. [3, 4]

Table 2.1 Physical Properties. [1, 2]

Sr. no. Physical Properties
1. Molecular formula C2H6O2
2. Molecular weight 62
3. Specific gravity at 20/20oC 1.1135
4. Boiling point oC at 101.3 KPa 197.60
5. Freezing point oC -13
6. Heat of vaporization at 101.3 KPa; KJ/mol 52.24
7. Heat of combustion (25oC) MJ/mol 19.07
8. Critical Temp. oC 372
9. Critical pressure, KPa 6513.73
10. Critical volume, L/mol 0.1861
11. Refractive index, ŋ 1.4318
12. Cubic expansion coefficient at 20 oC, K-1 0.62 × 10-3
13. Viscosity at 20oC; mPa S 19.83
14. Liquid density (20oC) gm/cm3 1.1135
15. Flash point, oC 111

16. Auto-ignition temp in air oC 410

17. Flammability limits in air; vol%
Upper 53
Lower 3.2
2.2 CHEMICAL PROPERTIES:
Ethylene Glycol contains two primaries –OH groups. Its chemical reactions are therefore, those of primary alcohols
twice over. Generally, one –OH group is attacked completely before other reacts.
2.1.1 Dehydration
 With Zinc chloride, it gives Acetaldehyde
HOCH2CH2OH CH3CHO + H2O
(Ethylene Glycol) (Acetaldehydes)
o
 On heating alone at 500 C, it gives Ethylene oxide.
 With H2SO4 it gives dioxane which is important industrial solvent.
2.1.2 Oxidation
Ethylene glycol is easily oxidized to form a number of aldehydes and carboxylic acids by oxygen, Nitric acid and
other oxidizing agents.
The typical products derived from alcoholic functions are Glycolaldehyde (HOCH 2CHO), Glycolic acid
(HOCH2COOH), Glyoxylic acid (HCO-COOH), Oxalic Acid (HOOCCOOH), formaldehyde & formic acid.
 With HNO3 oxidation it yields nos. of substance as one or both primary –OH groups may be oxidized to
aldehydes and these carboxylic groups.
HNO3 [O] [O]
HOCH2CH2OH HOCH2CHO HOCH2CH2COOH CHOCOOH
(Ethylene Glycol) (Glycol aldehydes) (Glycolic acid) (Glyoxylic acid)

[O]
HOOC-COOH
(Oxylic acid)
[O]
HNO3 [O] [O]
HOCH2CH2OH HOCH2CHO CHOCHO CHOCOOH
(Ethylene Glycol) (Glycol aldehydes) (Glyoxal) (Glyoxylic acid)
2.1.3 Other reactions
The hydroxyl groups on glycols undergo the usual alcohol chemistry giving a wide variety of possible derivatives.
Hydroxyls can be converted to aldehydes, alkyl halides, amides, amines, azides, carboxylic acids, ethers,
mercaptans, nitrate esters, nitriles, nitrite esters, organic esters, peroxides, phosphate esters, and sulfate esters.
 Reaction with sodium at 50 oC to form monoalkoxide and dialkoxide when temperature is raised.
Na at 50 oC Na at 160 oC
HOCH2CH2OH HOCH2CH2ONa NaOCH2CH2ONa
(Ethylene Glycol) (Mono Alkoxide) (Di Alkoxide)
 Reaction with Phosphorus pentahalide (PCl5) it first gives Ethylene chlorohydrins and then 1, 2
dichloroethane. PBr5 reacts in same way.
PCl5 PCl5
HOCH2CH2OH HOCH2CH2Cl ClCH2CH2Cl
(Ethylene Glycol) (Ethylene chlorohydrins) (1, 2-Dicholorochlorohydrins)
 With Phosphorus trihalide (PBr3) to form responding dihalide
PBr3 PBr3
HOCH2CH2OH HOCH2CH2Br BrCH2CH2Br
(Ethylene Glycol) (Ethylene Bromohydrins) (1, 2-Dibromohydrins)
 With HCl in two step reaction, form ethylene chlorohydrins at 160 oC and second forms 1, 2 dichloroethane
at 200oC.
160 oC 200 oC
HOCH2CH2OH HOCH2CH2Cl ClCH2CH2Cl
(Ethylene Glycol) (Ethylene chlorohydrins) (1, 2-Dicholorochlorohydrins)
 The largest commercial use of ethylene glycol is its reaction with dicarboxylic acids (1) to form linear
polyesters. Poly (Ethylene Terephthalate) (PET) (2) is produced by esterification of teraphthalic acid to form
BisHydroxyEthyl Terephthalate (BHET) (3). BHET polymerizes in a transesterification reaction catalyzed by
antimony oxide to form PET.
2HOCH2CH2OH
+

HOOC COOH + HOCH2CH2OOC COOCH2CH2OH

(1) (2)

Sb2O3
H* OOC COOCH2CH2 *H
+ HOCH2CH2OH
n
(3)

Ethylene glycol esterification of BHET is driven to completion by heating and removal of the water
formed. PET is also formed using the same chemistry starting with dimethyl Terephthalate and ethylene
glycol to form BHET also using an antimony oxide catalyst.

 Ethylene glycol also produces 1, 4-dioxane by acid-catalyzed dehydration to Diethylene glycol followed by
cyclization. Cleavage of Triethylene and higher glycols with strong acids also produces 1, 4-dioxane by catalyzed
ether hydrolysis with subsequent cyclization of the Diethylene of the Diethylene glycol fragment. Diethylene glycol
condenses with primary amines of form cyclic structures, e.g., methylamine reacts with Diethylene glycol to
produce N-methylmorpholine.
HOCH2CH2OCH2CH2OH + CH3NH2 O N CH3 + 2H2O (6)

 Ketones and aldehydes react with ethylene glycol under acidic conditions to
Form 1, 3-dioxolanes cyclic ketals and acetals.
O
+ R'
H
HOCH2CH2OH + RCOR+ + H 2O (7)
R
O
 Ethylene glycol reacts with ethylene oxide to form di, tri, tetra and polyethylene glycols.

Ethylene glycols is stable compound, but special care is required when ethylene glycol is
heated at a higher temperature in presence of NaOH, which is exothermic reaction at
temperature above 250 oC of evolution of H2 (-90 to -160 KJ/Kg).[

1.3 Objective of This Project

The task of assessing the extent of design possible in this process was to design the econ
omically optimal design taking into account reactor design, capital costs, production rate,
energy costs and raw material procurement costs. The current project's objectives are as
follows:

1) To utilize the MEG process to demonstrate the design optimization for the process by
using the optimization variables such as reactor size and water recycle ratio.

2) To create an optimum design to achieve a low operating cost, low capital cost and a
commendable conversion rate of reactants to desired products.
 1. Literature Survey
This literature survey was undertaken with the aim to gather information related to Mono
Ethylene Glycol and its production from a number of varied sources. Such sources
include chemical engineering abstracts, periodicals, books on chemical technology,
encyclopedias and websites. The survey gathered plenty of information on Ethylene
Glycol. A brief review of information gathered from the literature survey is presented
below. Many Journals, Manuals and Hand book have been sited during the project work.
The manufacturing process have been taken from “Chemical Engineering Journal
107(2005), 199-204.” And Turton et. al. and selectivity and other process parameters
have been taken from “Chemical Engineering Journal 107(2005), 199-204.” Price of
various equipment and raw material have been taken from the internet.
DERIVATIVES OF MONO ETHYLENE GLYCOL:
In addition to Oligomers ethylene glycol dervative classes include monoethers, diethers, esters, acetals, and ketals
as well as numerous other organic and organometalic molecules. These derivatives can be of ethylene glycol,
Diethylene glycol, or higher glycols and are commonly made with either the parent glycol or with sequential
addition of ethylene oxide to a glycol alcohol, or carboxylic acid forming the required number of ethylene glycol
submits.

3.1.1 Diethylene Glycol:

Physical properties of Diethylene glycol are listed in Table. Diethylene glycol is similar in many respects to
ethylene glycol, but contains an ether group. It was originally synthesized at about the same time by both Lourenco
and Wurtz in 1859, and was first marketed, by Union Carbide in 1928. It is a co product (9 - 10%) of ethylene
glycol produced by ethylene oxide hydrolysis. It can be made directly by the reaction of ethylene glycol with
ethylene oxide, but this route is rarely used because more than an adequate supply is available from the hydrolysis
reaction.
Triethylene Glycol:
Triethylene glycol is a colorless, water-soluble liquid with chemical properties essentially identical to
those of Diethylene glycol. It is a co product of ethylene glycol produced via ethylene oxide hydrolysis.
Significant commercial quantities are also produced directly by the reaction of ethylene oxide with the
lower glycols.

Triethylene glycol is an efficient hygroscopicity agent with low volatility, and about 45%
is used as a liquid drying agent for natural gas. Its use in small packaged plants located at
the gas wellhead eliminates the need for line heaters in field gathering systems as a
solvent (11 %) Triethylene glycol is used in resin impregnants and other additives,
 steam-set printing inks, aromatic and paraffinic hydrocarbon separations, cleaning
compounds, and cleaning poly (ethylene Terephthalate) production equipment. The
freezing point depression property of Triethylene glycol is the basis for its use in heat-
transfer fluids
Tetra ethylene Glycol:
Tetra ethylene glycol has properties similar to Diethylene and Triethylene glycols and may be used preferentially in
applications requiring a higher boiling point, higher molecular weight, or lower hygroscopicity.
Tetra ethylene glycol is miscible with water and many organic solvents. It is a humectants that, although
less hygroscopic than the lower members of the glycol series, may find limited application in the
dehydration of natural gases. Other possibilities are in moisturizing and plasticizing cork, adhesives, and
other substances.

2.1 Process
Many laboratory and industrial based methods have been employed for the production of
MEG, though the most industrially viable method since 1981 has been the hydration of
Ethylene Oxide with and without the presence of a catalyst
2 Industrial methods:
 The production of ethylene glycol by the hydration of ethylene oxide is simple, and can be
summarized as follows: ethylene oxide reacts with water to form glycol, and then further reacts with
ethylene glycol and higher homologues in a series of consecutive reactions as shown in the following
equations.
 H2C CH2 + H2O H2C CH2

O O O
Ethylene Oxide H H
Ethylene Glycol
H2C CH2 + H2C CH2 H2C CH2 O CH2 CH2

O O O O O
H H H H
Diethylene Glycol

H2C CH2 + H2C CH2 O CH2 CH2

O O O
H H
H2C CH2 O CH2 CH2 O CH2 CH2

O O
H H
Triethylene Glycol
Ethylene oxide hydrolysis proceeds with either acid or base catalysis or uncatalyzed in neutral medium.
Acid-catalyzed hydrolysis activates the ethylene oxide by protonation for the reaction with water. Base-
catalyzed hydrolysis results in considerably lower selectivity to ethylene glycol. The yield of higher
glycol products is substantially increased since anions of the first reaction products effectively compete
with hydroxide ion for ethylene oxide. Neutral hydrolysis (pH 6-10), conducted in the presence of a large
excess of water at high temperatures and pressures, increases the selectivity of ethylene glycol to 89-91%.
In all these ethylene oxide hydrolysis processes the principal byproduct is Diethylene glycol. The higher
glycols, i.e., Triethylene and Triethylene glycols, account for the remainder.

Although catalytic hydration of ethylene oxide to maximize ethylene glycol production has been studied
by a number of companies with numerous materials patented as catalysts, there has been no reported
industrial manufacture of ethylene glycol via catalytic ethylene oxide hydrolysis. Studied catalyst include
sulfonic acids, carboxylic acids and salts, cation-exchange resins, acidic zeolites, halides, anion-exchange
resins, metals, metal oxide and metal salts. Carbon dioxide as a co catalyst with many of the same
materials has also received extensive study.

 Ethylene glycol was commercially produced in the United States from ethylene chlorohydrins
which was manufactured from ethylene and hypochlorous acid. Chlorohydrins can be converted directly
to ethylene glycol by hydrolysis with a base, generally caustic or caustic/bicarbonate mix. An alternative
production method is converting chlorohydrins to ethylene oxide with subsequent hydrolysis.
 CH2 CH2 + HOCl HOCH2CH2Cl (8)

HOCH2CH2Cl + NaOH HOCH2CH2OH + NaCl (9)

O

HOCH2CH2Cl + Ca(OH)2 CH2 CH2 + NaCl (10)

O

CH2 CH2 + H2O HOCH2CH2OH (11)

 Du Pont commercially produced ethylene glycol from carbon monoxide, methanol, hydrogen, and
formaldehyde until 1968 at Belle, West Virginia. The process consisted of the reaction of formaldehyde,
water, and carbon monoxide with an acid catalyst to form glycolic acid. The acid is esterified with
methanol to produce methyl glycolate. Subsequent reduction with hydrogen over a chromate catalyst
yields ethylene glycol and methanol. Methanol and formaldehyde were manufactured on site from syngas.

+ H+
CO CH2O + H2O HOOCCH2OH + NaCl (12)

HOOCCH2OH + CH3OH CH3OOCCH2OH + H2O (13)

Cr2O3
CH3OOCCH2OH + H2 HOCH2CH2OH + CH3OH (14)

Coal was the original feedstock for syngas at Belle; thus ethylene glycol was commercially manufactured from coal
at one time. Ethylene glycol manufacture from syngas continues to be pursued by a number of researchers.
 Ethylene glycol can be produced from acetoxylation of ethylene. Acetic acid, oxygen, and
ethylene react with a catalyst to form the glycol mono and diacetate. Catalysts can be based on palladium,
selenium, tellurium, or thallium. The esters are hydrolyzed to ethylene glycol and acetic acid. The net
reaction is ethylene plus water plus oxygen to give ethylene glycol. This technology has several issues
which have limited its commercial use.

Te2Br2
CH3COOH + CH2 CH2 + O2 CH3COOCH2OOCCH3 (15)

3 H2O
CH3COOCH2CH2OH + CH3COOCH2CH2OOCCH3 2 HOCH2CH2OH + 3 CH3COOH (16)
The catalysts and acetic are highly corrosive, requiring expensive construction materials. Trace amounts of ethylene
glycol mono-and diacetates are difficult to separate from ethylene glycol limiting the glycol’s value for polyester
manufacturing. This technology (Halcon license) was practiced by Oxirane in 1978 and j1979 but was discontinued
due to corrosion problems.
 Ethylene glycol can be manufactured by the transesterification of ethylene carbonate. A process
based on the reaction of ethylene carbonate with methanol to give dimethyl carbonate and ethylene glycol
is described in a Texaco patent; a general description of the chemistry has also been published.

Zr2Cl4
C + 2 CH3OH HOCH2CH2OH + CO(CH3O)2 (18)

O O

Selectivity to
ethylene glycol are excellent with little Diethylene glycol or higher glycols produced. A wide range of
catalysts may be employed including ion exchange resins, zirconium and titanium compounds, tin
compounds, phosphines, acids and bases. The process produces a large quantity of dimethyl carbonate
which would require a commercial outlet.

 Oxalic acid produced from syngas can be esterified and reduced with hydrogen to form ethylene glycol
with recovery of the esterification alcohol. Hydrogenation requires a copper catalyst giving 100% conversion with
selectivity to ethylene glycol of 95%.

HOOCCOOH + 2 ROH ROOCCOOR + 2 H2O (20)

Cu
ROOCCOOR + 4 H2 HOCH2CH2OH + 2 ROH (21)

 The Teijin process, which has not been commercialized to date, produces ethylene glycol by the
reaction of ethylene with thallium salts in the presence of water and chloride or bromide ions. The major
by-product in the reaction is acetaldehyde. A redox metal compound (such as copper) oxidizable with
molecular oxygen is added to the reaction medium to permit the regeneration of the thallium salt.
The DuPont process, based on feeds derived from synthesis gas (CO and formaldehyde),
became economically obsolete because of low-priced ethylene. With the high price of oil
and natural gas, there has been increasing interest in coal gasification to produce fuel and
also synthesis gas for petrochemical manufacture. In 1976, Union Carbide announced
that a process for the production of ethylene glycol from synthesis gas was being
developed for commercialization in the early 1980.The proposed reaction was based on
using a rhodium-based catalyst in tetrahydrofuran solvent at 190-230C and high
pressure (3400 atm). The equi molar mixture of CO and H 2 would be converted mainly
to ethylene glycol and by-product glycerol and propylene oxide. Methanol, methyl
formate, and water would also be produced.[
Yield achieved in this method is often as high as 99% and above, though the actual
trouble begins when we discuss selectivity of this reaction. High molar ratio of water
compared to Ethylene Oxide is used to drive reaction towards high selectivity. This
causes significant increase in operating costs due to power consumption during isolation
of MEG from dilute aqueous solution, this ratio can be further decreased by using a
suitable catalyst such as a cross linked styrene divinylbenzene anion exchange resin
activated by exchanging anion with sodium bicarbonate solution.

𝐾1
H2O + C2H4O → HOCH2CH2O

(Mono Ethylene Glycol)

𝐾2
C2H4O + HOCH2CH2OH → HO (CH2CH2O)2 H

(Di Ethylene Glycol)

Figure 1: Process Flowsheet for Production of Ethylene Glycol

2.2 Economic Scenario

Ethylene Glycol is extensively used in the chemical industry and is of utmost importance.
Around 50% of the world’s produce of Ethylene Glycol is used as an anti-freeze solution
for internal combustion engines while as much as 40% of the produce is used as a pre-
cursor to many industrially important fibres. Some of the major producers of MEG are: -

1) BASF (America)
2) OXYPETROCHEMICALS (America)
3) INDIA GLYCOL ( NORTH INDIA)
4) Reliance Industries Ltd. (Gujarat)
5) NOCIL (Thane, near Mumbai)

The demand for MEG has been steadily witnessing a CAGR of 9.7% since fiscal year
2007 to 2017. Due to heavy requirement of PET bottles and fibres, demand for MEG has
surged in countries like China and India.

2.3 Storage and Transportation

Pure anhydrous ethylene glycol is mostly non-reactive towards most of the metals and
plastics. Since ethylene glycol is non caustic and has a very low vapour pressure, it can
be handled with ease. It is transported via rail, trucks, and ships. Tanks used for carrying
ethylene glycol are normally made up of steel. High grade materials are only required in case
of special quality requirements. To protect ethylene glycol from oxidation, nitrogen
blanketing is used. Aluminium is resistant to pure glycol at ambient temperatures,
however corrosion does occur at 100 and hydrogen is evolved in the process. If
impurities like water, air and aldehydes are present, reaction gets accelerated. Whenever
phenolic resins are involved, great care should be taken as they are not resistant to
glycols.

PROCESS DESCRIPTION:
This process produced mono ethylene glycol by the catalytic hydrolysis of ethylene oxide in the presence of less
excess of water. After the hydrolysis reaction is completed the glycol is separated from the excess water and then
refined to produce mono ethylene glycol (MEG). The process is devided in to five different sections.
5.3.1 MEG reaction unit:
Ethylene oxides mixed with recycle water and pumped to glycol reactor where it is reacted with water at 105 0C
&1.5 MPa in the presence of catalyst. The Reactor is Catalytic Plug flow Fixed bed type. The reaction volume
consists of two phase, the liquid phase and ionite (catalyst) phase. The liquid streams through catalyst bed in a plug
flow regime. The catalytic and non catalytic ethylene oxide hydration takes place in the ionite phase, and only non
catalytic reaction takes place in the liquid phase. The distribution of the components of the reaction mixture
between liquid and ionite phases is result of the rapid equilibrium. The glycol reactor operate at approximately
1.5MPa.pressure which is supplied by the reactor feed pump. The reactor effluent goes to the evaporation unit for
the evaporation of excess water.
5.3.2 MEG evaporation unit:
The glycol evaporation system consists of multiple effect evaporation system(three effects). The reactor
effluent flows by difference in pressure from one evaporator to the next the water content of glycol is
reduced to about 15% in the evaporators. The remaining water is removed in drying column, the pressure
of the system is such that the reactor effluent is maintained as a liquid and is fed as such in to the vapor
portion of the first effect evaporator.
Evaporation in the first effect is accomplished by 12Kg/cm 2 (g) pressure steam. The overhead vapor from the first
effect is used as heating media in the second effect. The steam condensate from the first effect is goes to the
medium pressure condensate header.
The overhead vapor from the second effect is used as heating media in the third effect. The third effect operated
under vacuum. The vacuum is maintained by using steam jet ejector. The bottom of the third effect containing 15%
water is fed to crude glycol tank via glycol pump, which is then fed to the drying unit. The condensate from first
two effects and the vapor from third effect containing water and some amount of glycol are fed to the glycol
recovery unit.
5.3.3 MEG drying unit:
The concentrated glycol from the third effect is containing approximately 15% water. Essentially all the water is
removed from the aqueous ethylene glycol solution in the drying column. Normally the drying column is fed from
the crude glycol tank. The drying column operated under vacuum which is maintained by steam jet ejector. Drying
column bottom which are free from water are transferred by column bottom pump to MEG refining column. Where
the MEG is separated from the higher glycol, Water vapors leaving the top of the drying column are fed to MEG
recovery unit for glycol recovery. (An inert gas line is provided at the base of the drying column for breaking the
vacuum).
5.3.4 MEG refining unit:
Drying column bottoms essentially free of water are fed to the MEG refining column. (PACKED COLUMN).
About 15% of the feed to the MEG column enters as vapor due to flashing. MEG product is withdrawn from the top
of the column. Some MEG is purged in the overhead to the vacuum jets to reduce the aldehydes in the product. The
MEG column bottoms primarily di-ethylene glycols are pumped from the column bottom to the storage tank. The
MEG column operates at a pressure of 10mmHg (A). The vacuum is maintained by MEG column ejector system.
The MEG column condenser is mounted directly on the top of the MEG column.
5.3.5 MEG recovery unit:
The MEG leaving along with water from the Top of the multiple effect evaporator & drying column are recovered
in the MEG Recovery Column (PLATE COLUMN). The column is operated under Atmospheric pressure.MEG
leaving from the bottom of the column and the water leaving from the top of the column are Recycle to reactor.
 CHAPTER 4

2. MATERIAL BALANCE
We can write a general conservation equation for any process as follows: -

Material out = Material In + Accumulation

As we are considering a steady state process, we will assume the accumulation term to be
zero. Assuming no chemical reaction is taking place, no chemical species is assumed to
be formed or consumed.

Material out = Material In

We will now write a balanced equation for each equipment separately.

Basis: 100000 Tons Per Annum

We will plan this process with the assumption that it is continuous and is operated for 24
hours a day for 333 days in a year.

Hence, number of working days = 333

100000
Capacity =
333

= 300.3 T/day

= 201.47 kmol/hr
6.2 MOLECULAR WEIGHT (KG / KMOL):
Ethylene Glycol : 62
Water : 18
Carbon Dioxide [CO2] : 44.01
Water [H2O] : 18
Nitrogen [N2] : 28

2.1 Material Balance on individual equipment

Assuming that 99% of the MEG in feed to the distillation column is received in the
distillate and 95% of MEG in feed to the recovery column is obtained at last.

Therefore, Kmol of MEG in the feed stream to the column = 204.6 Kmol/hr

2.1.1 Reactor
 The following reaction takes place in the reactor: -

6.3.1 Reactor:

Ethylene Oxide = 9190.54 Kg Mono Ethylene Glycol = 204.7Kmols

= 208.876 Kmols REACTOR = 12691.4 Kg
Temp. = 100 0C
Water = 1881.972 Kmols
Conversion = 100 % = 33875.496Kg
Water = 37597.68 Kg Pressure = 1.5-2MPa
= 2088.76 Kmol
Higher glycol = 2.088 Kmol
= 221.328Kg

𝐾1
H2O + C2H4O → HOCH2CH2O (1)

(mono ethylene glycol)

𝐾2
C2H4O + HOCH2CH2OH → HO (CH2CH2O)2 H (2)

(Di Ethylene Glycol)

Selectivity is 99%

Moles of side product (undesired) formed = 204.6

99

= 2.068 Kmol

Moles of MEG required from reactor =206.68 Kmol

Moles of EO consumed by reaction (1) = 206.68 Kmol

Moles of EO reacted by reaction (2) = 206.68 + 2.068

= 208.74 Kmol considering conversion to be 100%

Moles of EO required to be charged = 208.74 Kmol

From literature, water to ethylene oxide ratio required for 99% selectivity is 10

Therefore, amount of needed for reaction = 2087.4 Kmol

From reaction, moles of water reacted = 206.68 Kmol

Therefore, moles of water un-reacted = 2087.4 – 206.68

= 1880.72 Kmol

Table 5: Material Balance Summary for Reactor

Component In (Kg) Out (Kg)

Ethylene Oxide 9184.56 -

Water 37573.2 33852.96

MEG - 12814.16

Higher Glycol - 220.31

 2.1.2 Triple Effect Evaporator
We want to remove water content of MEG to 15%. That is, 85% of water is to be
removed.

Considering the three evaporators to be a single unit,

Quantity of water evaporated = 0.85*1880.72

= 1598.61 Kmol
= 28775 Kg
We still have 15% water remaining in the bottom product along with MEG and
Higher glycols, mainly DEG.
Therefore, quantity of water in the bottom product = 1880.72 – 1598.61
= 292.11 Kmol
= 5077.98 Kg
There is some quantity of glycol carry over along with water from the top of evaporator.
Amount of glycol carry over along with water from 1st effect = 165.58 kg

F = 2088.76 Kmol
= (46788.224 kg) 1st effect evaporator
M.E.G = 204.7Kmol To 2nd effect evaporator
Pressure = 7 kg/cm2
= 12691.4 Kg
Temp = 159 oC
Water =1881.972 Kmol
= 33875.496Kg

Amount of glycol carry over along with water from II st effect = 189.139kg

W2= 9689.31kg
MEG = 189.139kg
H2O = 9500.171kg

2nd effect evaporator

Pressure = 3.5 kg/cm2

From 2nd effect To 3rd effect evaporator
evaporator Temp = 141 oC

To MEG Recovery column

Y= 1610.8012kmol
 Amount of glycol carry over along with water from II st effect = 335.064 kg

W3= 11508.96kg
MEG = 335.064kg
H2O = 11173.89kg

To MEG Refining
From 3rd effect 3rd effect evaporator column
evaporator X = 477.9588
Kmol
Pressure = 0.25 kg/cm2
Temp = 118 oC

To MEG Recovery column

Y= 1610.8012kmol

(Finding using VLE calculation)

Total amount of glycol carry over along with water = 689.783 Kgm.
=11.125 Kmol
Total quantity (water +MEG) leaving from the top of 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.
(Total quantity leaving from the bottom of last effect)

Total Quantity of water+ MEG leaving from the top of triple effect =1600.8012
Kmol
Therefore, total quantity leaving from bottom = 476.96 Kmol
Table 6: Material Balance Summary for Triple Effect Evaporator
Component In (Kg) Out (Kg)

Liquid Phase Vapour Phase

Water 33852.96 5077.98 28774.98

MEG 12814.16 11999.62 814.54

 HG 220.31 220.31 -

2.1.3 Drying Column

F = 477.9588 kmol
= 17304.2585 kg Drying column
MEG = 12001.606kg Pressure = 0.21 kg/cm2
Temp = 87 oC
H2O = 5081.324 kg.
X = 188.306 Kmol
HG = 221.328kg. = 11766.873 kg
MEG = 186.218kmol
= 115453545kg

HG = 2.088 Kmol
= 221.328kg

At this point we will consider that all the water is removed after this process.
Therefore, Quantity of water removed = 5077.98 Kg
= 282.11 Kmol
Some quantity of MEG will also get carried along with water at the top of drying
column,
This quantity = 456 Kg (VLE Calculations)
 Hence, total quantity leaving from the top of column = Quantity of water +
Quantity of MEG = 282.11 + 7.35
= 289.46 Kmol
Overall Material Balance will now give,
F=X+Y
476.96 = X + 289.46
Therefore, X = 187.5 Kmol (Total Quantity leaving from bottom of drying
column)
Also,
Total quantity of MEG leaving with water during evaporation = 1145.844 Kg
= 18.49Kmol
And,
Quantity of feed to the MEG recovery column = 1900.5 Kmol

Table 7: Material Balance Summary for Drying Column

Component In (Kg) Out (Kg)

Water 5077.98 - 5077.98

MEG 11999.62 10853.24 1146.38

HG 220.31 220.31 -

1.1.1 MEG Refining Column (Packed)

F = 188.306 Kmol
= 11766.873 kg MEG refining column
Pressure = 10 mmHg
MEG = 186.218kmol Temp = 93.2 oC
=11545.545kg

HG =2.088kmol
= 221.328kg

W = 3.766 Kmol
= 317.664 kg

MEG = 1.8523kmol

HG = 1.9136kmol
Here we assume a recovery of 99% of MEG of total incoming feed

Therefore, Kmol of MEG in distillate = 181.81*0.99*0.98891

= 177.998 kmol/hr
= 11747.87 Kg/hr
Kmol of Distillate (D) = 177.998/0.99
= 179.79 Kmol/hr
Average molecular weight of distillate = 0.999*62 + 0.001*106

= 62.044 Kg/Kmol
Therefore, quantity of distillate (D) = 179.79*62.04
= 11154.54 Kg/hr
Quantity of Higher Glycols in Distillate = 179.79*0.001
= 0.179 Kmol/hr
= 18.974 Kg/hr
Kmol of feed (F) = 184.206 Kmol/hr
= 11766.874 Kg/hr
Taking overall Mass Balance;
F=D+W
184.206 = 179.79 + W
W=4.416 Kmol/hr

Material Balance for MEG gives,

F*(XfMEG) = D*(XdMEG) + W*(XbMEG)

184.206*0.9889=179.79*0.999+4.416*(XbMEG)
Therefore, XbMEG = 0.577 (mole fraction of MEG in the bottom)
And, XbHG = 1-0.577 = 0.423 (Mole fraction of HG in the bottom)

Table 8: Material Balance Summary for Refining Column

Component In (kg) Out (Kg)

Liquid Phase Vapor Phase

 MEG 11999.62 114.83 11884.79

HG 220.31 201.84 18.47

MEG recovery column (Plate column):

F = 1900.451kmol
= 35021.339 kg MEG recovery column

MEG = 18.481kmol Plate column

=1145.844kg

H2O =1881.97kmol
= 33875.496kg.
W = 18.481kmol
=1205.55 kg

MEG = 17.122kmol

H2O = 1.3584kmol

Assuming 99.9 % of total water in feed to distillation column is obtained in the distillate.
 Kmol of Water in Distillate = 1881.97 x 0.999
= 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.
TAKING OVERALL M.B.
F = D+ W
1900.451 = 1881.47 + W
W = 18.481kmol / hr
M.B. ON 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)
 Amount of MEG in Bottoms = 18.481 x 0.9264
= 17.122 Kmol / hr
= 17.122 x 62
= 1061.56 kg/hr.
 Kmol of Water in Bottoms = 18.481 – 17.130
= 1.3584 Kmol / hr
= 1.3584 x 18
= 143.99 kg/ hr.
Table 6.5 Material balance over Recovery plate column
Component In, Kg Out, Kg
Liquid phase Vapor phase
Water 33875.496 24.4512 33841.44
MEG 1145.844 1061.546 116.56
Table 9: Overall Material Balance Summary

Equipment Component In (Kg) Out (Kg)

Liquid Phase Vapor Phase

Reactor Ethylene 9184.56 - -

Oxide

Water 37573.2 33852.96 -

MEG - 12814.16 -

HG - 220.31 -

Triple Effect Water 33852.96 5077.98 28774.98

Evaporator
MEG 12814.16 11999.62 814.54

HG 220.31 220.31 -

Drying Colum Water 5077.98 - 5077.98

MEG 11999.62 10853.24 1146.38

HG 220.31 220.31 -

MEG MEG 11999.62 114.83 11884.79

Refining
HG 220.31 201.84 18.47

MEG Water 33875.5 24.46 33841.4

Recovery
MEG 1145.85 1061.55 116.57
 REFERENCES

1. “Chemical Engineering Journal 107(2005), 199-204.”

2. Ullmann, “Ullmann’s Encyclopedia of Industrial Chemistry”,Wiley-VCH-Verlag
GMBU & Co. Weinheim, 2003, sixth edition, vol-12 (p-593-608).
3. Kirk & Othmer, “Encyclopedia of Chemical Technology”, John Wiley &
Sons, New York, Toronto; fourth Edition; 1996; vol-12 (p-696 - 714).
4. https://www.indiamart.com/proddetail/mono-ethylene-glycol-meg-3846020412.h
tml
5. https://dowac.custhelp.com/app/answers/detail/a_id/7449