Ministry of Higher

Education and Scientific

Research
Al-Muthanna University
Engineering College
Chemical Engineering
Department

Production of mono
ethylene glycol Energy
Balance
By
Sadiq salem mohammed
Class:
Third stage
Subject:
Chemical industry
Supervised by:
Dr. Ahmed Hassan

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.

Production
Industrial routes
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.
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 (CO
2) to ethylene carbonate. This ring is then hydrolyzed with a base catalyst in a second
step to produce mono-ethylene glycol in 98% selectivity. The carbon dioxide is

2
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.[6] Dimethyl oxalate can be converted into ethylene glycol
in high yields (94.7%) by hydrogenation with a copper catalyst:

3
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.[9] 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.

Historical routes
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). In 1859, Wurtz prepared ethylene glycol
via the hydration of ethylene oxide.[16] 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.

4
Uses
Ethylene glycol is primarily used in antifreeze formulations (50%) and as a raw
material in the manufacture of polyesters such as polyethylene terephthalate (PET)
(40%).
Coolant and heat-transfer agent
The major use of ethylene glycol is as a medium for convective heat transfer in, for
example, automobiles and liquid-cooled computers. Ethylene glycol is also
commonly used in chilled-water air-conditioning systems that either place the
chiller or air handlers outside or must cool below the freezing temperature of water.
In geothermal heating/cooling systems, ethylene glycol is the fluid that transports
heat through the use of a geothermal heat pump. The ethylene glycol either gains
energy from the source (lake, ocean, water well) or dissipates heat to the sink,
depending on whether the system is being used for heating or cooling.
Pure ethylene glycol has a specific heat capacity about one half that of water. So,
while providing freeze protection and an increased boiling point, ethylene glycol
lowers the specific heat capacity of water mixtures relative to pure water. A 1:1 mix
by mass has a specific heat capacity of about 3140 J/(kg·°C) (0.75 BTU/(lb·°F)),
three quarters that of pure water, thus requiring increased flow rates in same-system
comparisons with water. The formation of large bubbles in cooling passages of
internal combustion engines will severely inhibit heat flow (flux) from the area, so
that allowing nucleation (tiny bubbles) to occur is not advisable. Large bubbles in
cooling passages will be self-sustaining or grow larger, with a virtually complete
loss of cooling in the area. With pure MEG (mono-ethylene glycol) the hot spot will
reach 200 °C (392 °F). Cooling by other effects such as air draft from fans (not
considered in pure nucleation analysis) will assist in preventing large-bubble
formation.

5
The mixture of ethylene glycol with water provides additional benefits to coolant
and antifreeze solutions, such as preventing corrosion and acid degradation, as well
as inhibiting the growth of most microbes and fungi.
Antifreeze
Pure ethylene glycol freezes at about −12 °C (10.4 °F) but, when mixed with water,
the mixture freezes at a lower temperature. For example, a mixture of 60% ethylene
glycol and 40% water freezes at −45 °C (−49 °F). Diethylene glycol behaves
similarly. The freezing point depression of some mixtures can be explained as
a colligative property of solutions but, in highly-concentrated mixtures such as the
example, deviations from ideal solution behavior are expected due to the influence
of intermolecular forces.
There is a difference in the mixing ratio, depending on whether it is ethylene glycol
or propylene glycol. For ethylene glycol, the mixing ratios are typically 30/70 and
35/65, whereas the propylene glycol mixing ratios are typically 35/65 and 40/60. It
is important that the mixture is frost-proof at the lowest operating temperature. (in
Danish)
Because of the depressed freezing temperatures, ethylene glycol is used as a de-
icing fluid for windshields and aircraft, as an antifreeze in automobile engines, and
as a component of vitrification (anticrystallization) mixtures for low-temperature
preservation of biological tissues and organs. Mixture of ethylene glycol and water
can also be chemically termed as glycol concentrate/compound/mixture/solution.
The use of ethylene glycol not only depresses the freezing point of aqueous mixtures,
but also elevates their boiling point. This results in the operating temperature range
for heat-transfer fluids being broadened on both ends of the temperature scale. The
increase in boiling temperature is due to pure ethylene glycol having a much higher

6
boiling point and lower vapor pressure than pure water, as is typical with
most binary mixtures of volatile liquids.

Production of mono ethylene glycol flow sheet

7
 Energy Balance

Introduction
The calculations will be based on the first law of thermodynamic (The total quantity

of energy is constant. When energy disappear in one form, it appears in other forms).

Δ [(H + (1/2* U2) + Z*g) m] = Q - Ws (for open system)

Where:

Q = heat gained by system (positive)

Ws = work done by system

Assumptions:

1. Neglect kinetic and potential energy.

ΔH = Q -Ws

2. For open system shaft work (Ws) =0

3. For open system with physical operation

ΔH = Q

4. For open system with chemical reaction

ΔH + ΔH reaction = Q

ΔH = H out – H in

H = m Cp mean ΔT

8
Cp mean = Σ (Xi * Cpi) or Cp mean = Σ ( yi * Cpi )

ΔT = T – T reference

T reference = 25ₒC=298 K

1. Energy Balance on Packed Column Reactor

3 4

65ₒC 60ₒC

ΔH3 = 1114935.832kJ
Hbiodiesel = 1304.43kg* 0.123kJ/kg.C*(60 - 25)C = 5615.571kJ
HGlycerol = 158.27 kg * 0.266 kJ/kg.C*(60 - 25)C = 1473.494 kJ
HMethanol = 221969.364 kg * 0.083 kJ/kg.C*(60 - 25)C = 644821.002kJ
HHexane = 33295.404 kg * 0.1962 kJ/kg.C*(60 - 25)C = 228639.539kJ
HH2SO4 = 73.131 kg * 0.1447 kJ/kg.C* (60 - 25)C = 370.372kJ
ΔH4 = Hbiodiesel+ HGlycerol+ HMethanol+ HHexane+ HH2SO4
ΔH4 = 5615.571+1473.494 +644821.002 +228639.539 +370.372
ΔH4 =880919.978kJ
Q = ΔH4 – ΔH3
Q=880919.978-1114935.832
Q=-234015.854kJ
Oil + 3methanol = 3ester + glycerol
Hfmethanol = -238.42 KJ/mol , Hfglycerol= - 669.6 KJ/mol
Hfoil = 9767.52 KJ/ mol
ΔHreaction = ΣHfₒ (product) - ΣHfₒ (reaction)

9
ΔHreaction=[3* Hfₒ easter + Hfₒ glycerol] – [Hfₒ oil +3* Hfₒmethanol]
ΔHreaction = [3*-22430.895+(-669.6)] – [9767.52 + (-3*238.42)]
ΔHreaction = -77014.545 KJ
Q = ΔH +ΔH reaction
Q= -234015.854kJ +(-77014.454) = -311030.308kJ
2. Energy Balance on Decanter (Separator)
ΔH4 =880919.978kJ
ΔH6+ ΔH5 = ΔH4 =880919.978kJ
Q = (ΔH6+ ΔH5) - ΔH4 = 0

3. Energy Balance on Washing

25ₒC Water

60ₒC
washing
35ₒCWater 40ₒC

H8 = 7300kg* 4.18kJ/kg.C *(25 - 25)C= 0

HBiodiesel = 1304.43 kg * 0.123 kJ/kg.C * (60 - 25) C = 5615.571kJ
Hmethanol= 1109.85 kg * 0.0832 kJ/kg.C * (60 - 25) C = 3231.883 kJ
H Hexane =166.48 kg* 0.196 kJ/kg.C * (60 - 25) C = 1142.053 kJ
HGlycerol = 0.791 kg * 0.26631 kJ/kg.C * (60 - 25) C = 7.373 kJ
ΔH5=HBiodiesel +Hmethanol +H Hexane +H Glycerol
ΔH5=5615.571+3231.883 +1142.053 +7.373
ΔH5= 9996.88kJ

10
H9= 7300kg* 4.18 kJ/kg.C * (35 - 25)C = 305140kJ
HBiodiesel = 1304.43kg * 0.1318 kJ/kg.C *(40 - 25)C = 2578.858kJ
34
Hmethanol= 1109.85kg* 0.0812 kJ/kg.C * (40 – 25)C= 1351.797kJ
HHexan=166.48kg* 0.1906 kJ/kg.C * (40 - 25)C = 475.966kJ
HGlycerol = 0.791kg * 0.2633 kJ/kg.C * (40 - 25)C = 3.124kJ
ΔH7= HBiodiesel+ Hmethanol+ HHexan+ HGlycerol
ΔH7= 305140+2578.858+1351.797+475.966+3.124
ΔH7=4409.745kJ
Q = (ΔH7+H9) – (ΔH5 +H8)
Q=(4409.745+ 305140)-( 9996.88+0) =
Q=299552.865kJ
Q = (ΔH10+ ΔH11)- ΔH8
Q= (18099.056+22242.825)- 4409.745kJ
Q=35932.136KJ

4. Energy Balance on Distillation 1

QL
Q] 60ₒC=333k
q

Dist.1 QV QD
QF Q] Q]
Q] q q 60ₒC=333k
q
13
QW
Q]
333k=60ₒC q

Qf=ΔH13 =887478.029kJ

11
At Bottom
Xmethanol =0.01 mmethanol = 221969.364kg*0.01=2219.694kg
mtotal=mmetanol+mHexane+mH2O+mglycerol+mNa2SO4
mtotal=2219.693 + 33295.404 + 26.58744 + 158.27 + 105.932
mtotal=35805.886kg
mmethanol 2219.69.3kg
Xmethanol = = = 0.062
mtotal 35805.886kg
mHexane 33295.404kg
XHexane = = = 0.93
mtotal 35805.886kg
mGlycerol 158.27kg
XGlycerol = = = 0.004
mtotal 35805.886kg
mNa2SO4 105.932kg
XNa2SO4 = = = 0.003
mtotal 35805.886kg
mH2O 26.587kg
X H2O = = = 0.0007
mtotal 35805.886kg
37
Cpmean = (Xmethanol*Cp) + (X Na2SO4*Cp) + (XHexane*Cp) + (X glycerol * Cp) +
(Xwater*Cp)
Cpmean = (0.062* 2. 658) + (0.003 *1.596) + (0.93* 2.413) + (0.004* 1.263) +
(0.0007*4.174)
Cpmean = 2.422kJ/kg .k
Qw = m cpmean ΔT
Qw = 35805.886kg*2.422kJ/kg .k * (338 - 298)k= 3468874.236kJ
At top
Xmethanol=0.99 XH2O=0.01
Cpmean = (Xmethanol * Cp ) + ( Xwater * Cp )
Cpmean =(0.99* 2.693)+(0.01* 4.172)
Cpmean =2.70779 kJ / kg .k
mmethanol= minput xmethanol

12
mmethanol=221969.364*0.99=219749.67kg
mH2O= minput* xH2O
mH2O =26.856*0.01=0.26856kg
QD= m CPmean ∆T
QD=219749.67kg *2.693kJ/ kg .k *(343 – 298) K =26630363.76KJ
Qv = QD + QL + QC
R= L/ D → L=R*D ( R=2)
L=2D…………….(1)
V= L+D………….(2) substitute equation (1) in equation (2)
V=2D +D → V = 3D
D=219749.67kg
V= 3 * 219749.67kg
V= 6591749.01 Kg ………. substitute equation (1)
38
L = 2 D= 2 * 219749.67kg= 4394499.34Kg
Amount of methanol in V=0.99* 6591749.01 Kg = 6525831.52kg
Amount of water in V= 0.01*6591749.13 Kg= 65917.4901Kg
Cpmean = (Xmethanol * Cp ) + ( Xwater * Cp )
Cpmean =(0.99* 1.495)+(0.01* 4.883)=1.529kJ/kg .k
QV= m CPmean ΔT
QV=6591749.01Kg *1. 529kJ / kg .k *(343 – 298)k=453545290.6kJ
λmethanol = 1085 kJ/kg mmethanol=6525831.52kg
ʎ H2O= 2257 KJ/Kg mH2O =65917.4901Kg
Ʃ mʎ =(mʎ)H2O+(mʎ)methanol
Ʃ mʎ =2257KJ/kg*65917.4901Kg +1085KJ/Kg*6525831.52kg
Ʃ mʎ =7229302974kJ
QV=m CPmean ΔT + Ʃ mʎ

13
QV=453545290.6kJ +7229302974kJ=7682848265KJ
Amount of methanol in L = 0.99 * 4394499.34Kg=4350554.347kg
Amount of H2O in L = 0.01 *4394499.34Kg=43944.993kg
Cpmean = (Xmethanol * Cp ) + ( Xwater * Cp )
Cpmean =(0.99* 2.639)+(0.01* 4.172) =2.654kJ / kg .k
QL = m Cpmean ΔT
QL = 4394499.34Kg * 2.654kJ/kg.k * ( 343 - 298 )k=524835056.2kJ
QC = QV - QD – QL
QC =7682848265-26630363.76-524835056.2
QC =7131382845.04kJ
QV =Qf +QR
QR = Qv- Qf
QR =7131382845.04-887478.029 =7130495367.011kJ
5. Energy Balance on Distillation 2
QL
Q] 60ₒC=333k
60ₒC=333k q
QF
Dist.2 QV QD
Q]
Q] Q]
q ₒ
q q60 C=333k

QW
Q]
q

QW from Dist.1=Qf for Dist.2=3468874.236kJ

At Bottom
Hexane (out) from bottom 1%=33295.404*0.01=332.954kg
Qw = m cp mean ΔT

14
mtotal=mmetanol+mHexane+mH2O+mglycerol+mNa2SO4
mtotal=2219.693 + 332.954 + 26.58744 + 158.27 + 105.932
mtotal=2843.43644kg
mmethanol 2219.693kg
Xmethanol = = = 0.78
mtotal 2843.43644kg
mHexane 332.954kg
XHexane = = = 0.12
mtotal 2843.43644kg
mGlycerol 158.27kg
XGlycerol = = = 0.06
mtotal 2843.43644kg
mNa2SO4 105.932kg
XNa2SO4 = = = 0.04
mtotal 2843.43644kg
mH2O 26.587kg
X H2O = = = 0.01
mtotal 2843.43644kg

Cp mean = (Xmethanol* Cp) + (XNa2SO4 *Cp) + (XHexane * Cp) + (Xglycerol *Cp) + (Xwater
*Cp)
Cpmean = (0.78* 2.658) + (0.04* 1.596) +(0.12*2.413)
40 +(0.06*1.263 ) + (0.01*
4.174)
Cpmean = 2.544kJ/kg.k
Qw = 2843.43644kg * 2.544kJ/kg.k * (343 - 298 )k= 325516.599kJ
At top
Hexane (out) from top 99% =input *99%
Hexane (out) from top 99% =33295.404*0.99=32962.45kg
water (out) from top 1% =input*0.01=26.58744 ∗ 0.01
water (out) from top 1% =0.2658744kg
XHexane=0.99 XH2O=0.01
Cpmean = (XHexane* Cp ) + ( Xwater * Cp )
Cpmean =(0.99* 2.45)+(0.01* 4.172) =2.46722kJ / kg .k
QD = m Cpmean ΔT

15
QD= 32962.45kg*2.46722kJ/kg.k*(343 - 298)k= 3659652.715kJ
QV = QD + QL + QC
R= L/ D → L=R*D ( R=2)
V= L+D
V=2D +D → V = 3D
V= 3* 32962.45= 98887.35kg
L=2D
L= 2 * 32962.45kg=65924.9kg
Amount of hexane in V=0.99* 98887.35kg=97898.48kg
Amount of water in V= 0.01* 98887.35kg=988.874kg
Cpmean = (XHexane * Cp ) + ( Xwater * Cp )
Cpmean =(0.99*1.891)+(0.01* 1.893)
Cpmean =1.891kJ/kg.k
QV= m CPmean ΔT
QV=98887.35kg*1.891kJ/kg.k *(343 – 298)
41 k=8414819.048KJ
λ H2O = 2257 kJ/kg mHexane=97898.48kg
λ Hexane = 365 kj/kg mHexane =988.874kg
Ʃ mʎ =(mʎ)Hexane+(mʎ)H2O
Ʃ mʎ =365KJ/kg*97898.48kg +2257KJ/Kg*988.874kg
Ʃ mʎ =37964833.82kJ
QV=m CPmean ΔT + Ʃ mʎ
QV=8414819.048+37964833.82=46379652.868kJ
L =65924.9kg
Amount of hexane in L = 0.99*65924.9= 65265.65kg
Amount of H2o in L = 0.01*65924.9=659.249kg
Cpmean = (XHexane*Cp) + ( Xwater * Cp)

16
Cpmean =(0.99* 2.393)+(0.01* 4.172)
Cpmean =2.411kJ / kg .k
QL = m Cpmean ΔT
QL = 65924.9kg* 2.411kJ/kg.k*( 343 - 298 )k=7152522.026kJ
QC = QV - QD - QL
QC =46379652.868kJ - 3659652.715kJ -7152522.026kJ
QC=35567478.127 kJ
QV =Qf +QR
QR = QV-Qf
QR=46379652.868kJ -3468874.236kJ
QR=42910778.632KJ

17
References
1. ^ Jump up to:a b c d e f NIOSH Pocket Guide to Chemical
Hazards. "#0272". National Institute for Occupational Safety and
Health (NIOSH).
2. ^ "Ethylene glycol". www.chemsrc.com.
3. ^ Elert, Glenn. "Viscosity". The Physics Hypertextbook. Retrieved 2007-10-
02.
4. ^ Jump up to:a b c Siegfried Rebsdat; Dieter Mayer. "Ethylene
Glycol". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-
VCH. doi:10.1002/14356007.a10_101.
5. ^ Scott D. Barnicki "Synthetic Organic Chemicals" in Handbook of Industrial
Chemistry and Biotechnology edited by James A. Kent, New York : Springer,
2012. 12th ed. ISBN 978-1-4614-4259-2.
6. ^ Nexant/Chemsystems, "Coal to MEG, Changing the Rules of the
Game" (PDF). Archived from the original on July 14, 2011. Retrieved 2016-
08-08. (PDF; 5,4 MB), 2011 Prospectus.

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