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PRODUCTION OF ETHYLENE GLYCOL

Manufacturing process Discrimination


The different processes followed for the production of ethylene glycol includes:
Ethylene carbonate process:
In this method, ethylene oxide is converted to an intermediate, ethylene carbonate, by
reaction with carbon dioxide, which is then hydrolyzed by water to give ethylene glycol.
This process was in use in the 1970s, but this process was replaced later by combined
ethylene oxide-glycol plants.
Halcon Acetoxylatin Process:
Two reaction steps were used in the Oxirane plant. In the first, ethylene glycol
diacatate is obtained by the oxidation of ethylene in an acetic acid solution, catalyzed by
tellurium and a bromine compound.
The reaction complex, which is quite complicated, proceeds via a telluriumbromoethylene complex. The oxidation, which is carried out at 90-200 C and 20-30 atm
pressure, results in a mixture of acetates due to partial hydrolysis of the diacetate.
The reaction liquid effluent is withdrawn and processed to recover glycol acetates and
glycol and provide the recycle streams back to oxidation.
In the second step of the process, the glycol acetates are hydrolyzed to ethylene
glycol and acetic acid.
The process is obviously relatively more complex and will amount to huge capital
cost and Literature also shows that it has operating difficulties. A plant started at Channelview
in United State to produce 800 million lb/yr of ethylene glycol was shut down after
difficulties in start up.

Esterification:
Ethylene glycol can be produced by reaction of formaldehyde with carbon monoxide.
This route first produces glycolic acid which is converted by esterification and
hydrogenolysis to ethylene glycol.

HCHO +CO + H20

HOCH2COOH

HOCH2COOH +ROH

HOCH2COOR + H20

HOCH2COOR + 2H2

HOCH2CH2OH + ROH

Teijin Oxychlorination Process:


This process produces ethylene glycol by the reaction of ethylene with thallium salts
in the presence of water and chloride or bromide ions. 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 Teijin process is still in the works and yet to be
commercialized.
Union Carbide Syngas Process:
The following process developed by Union Carbide, Inc. Uses synthesis gas for the
production of ethylene glycol. Glycerol and propylene oxide are the major byproducts.
Methanol, methyl formate and water are also produced as shown below.
2CO + 3H2 HOCH2CH2OH

An expensive rhodium based catalyst catalyzes the reaction. The process is yet to be
commercialized. Union Carbide has already started work on a modified process in association
with Ube Industries. It plans to set up a commercial scale plant soon.

Oxidation of Ethylene:
This process involves the oxidation of ethylene to ethylene glycol in an aqueous
medium using an iron copper catalyst to produce Ethylene Glycol as represented in the
reaction below.

Fe-Cu
CH2=CH2 + O2 + H20

HOCH2CH2OH

Hydrolysis of Ethylene Oxide:


The reaction chemistry is quite simple; it is either acid or thermally catalyzed. It is
summarized as follows: ethylene oxide reacts with water to form ethylene glycol, and then
further reacts with ethylene glycol and higher homologues in a series of consecutive reactions
as shown in the following equations:

CH2CH2O + H2O HOCH2CH2O


ethylene glycol
2CH2CH2O + H2O HOCH2CH2OCH2CH2OH
diethylene glycol
3CH2CH2O + H2O HOCH2CH2OCH2CH2OCH2CH2O
triethylene glycol

Production Process Description


In the process either a 0.5 to 1.0% sulphuric acid (H2SO4) catalyst is used at 50 to
70oC for 30 minutes or, in the absence of the acid, a temperature of 195oC and 185 psi for 1
hour will form the diol. The formation of higher glycols is inevitable because ethelene oxide
reacts faster with ethylene glycols faster than with water. The most important variable is the
water-to-oxide ration, and the production of diethylene glycol (DEG) and triethylene glycol

(TEG) can be reduced by using a large excess of water. A 90 percent yield is realized when
the ethylene oxide/water molar ratio is 1:5-8.
The advantage of the acid-catalyzed reaction is no high pressure, however the thermal
reaction needs no corrosion resistance and no acid separation step.
The crude glycols are dehydrated and then recovered individually as highly pure
overhead streams from a series of vacuum-operated purification columns. Ethylene glycol
(boiling point: 197.6oC) is readily vacuum distilled and separated from the diethylene glycol
(boiling point: 246oC, density: 1.118, flash point: 124oC) and triethylene glycol (boiling
point: 288oC, density: 1.1274, flash point: 177oC).
Since ethylene glycol is produced in relatively high purity, differences in quality are
not expected. The directly synthesized product meets the high quality demands (polyester
grade glycol).

Other Alternatives:
Other Possible catalyst for this reaction includes quaternary ammonium and
phosphonium salts. A more recently developed catalyst system is based on use of Pd (II)
complexes. A mixture of PdCl2, LiCl and NaNO3 in acetic acid and acetic anhydride has
been shown to give a 95% selectivity
During this process, Pd(II) is reduced to Pd(0). If PdCl 2-CuCl2-CuOCOCH3 is used,
reaction proceeds under mild conditions without formation of a precipitate. A yield of over
90% is obtained.

ETHYLENE GLYCOL PRODUCTION


The production of ethylene glycol by the hydrolysis of ethylene oxide has been
selected in the following Design Thesis because it is by far the most widely used method for
the production of ethylene glycol. It is relatively economical, simple reliable and can be used
in plants that manufacture ethylene oxide and glycol together.
For this Project design there is a modification to the common Flow sheet used for the
Hydrolysis of Ethylene Oxide process that has been shown above. This modified unit
arrangement will still achieve the production of Ethylene Glycol at a lower Capital cost.
As stated above this reaction can be acid or based catalysed but for this work a choice
of a neutral and high pressure and temperature reaction is made because it has the economic
advantage of having no need for corrosion resistance and no acid separation step.
The chemistry of the reaction is summarized as follows: ethylene oxide reacts with
water to form ethylene glycol, and then further reacts with ethylene glycol and higher
homologues in a series of consecutive reactions as shown in the following equations:
Step 1
CH2CH2O + H2O HOCH2CH2O
ethylene glycol
Step 2
2CH2CH2O + H2O HOCH2CH2OCH2CH2OH
diethylene glycol
Step 3
3CH2CH2O + H2O HOCH2CH2OCH2CH2OCH2CH2O
triethylene glycol
The aim of this work is the yield of Ethylene Glycol not those of higher glycol does
this reaction is modified in such a way as to favour reaction step one and disfavour the other
two steps and this is achieved by using excess of water for the reaction to dilute the
concentration of the ethylene glycol produced to discourage the formation of higher glycols.

Production Process Description


Ethylene Oxide and water a passed into a Continous Stirring Tank Reactor which
operates a temperature of 195oC and pressure 185 psi for 1 hour will form the diol. Since the
formation of higher glycols is inevitable because ethelene oxide reacts faster with ethylene
glycols faster than with water then the water-to-oxide ration must be manipulated to reduce if
not eliminate the production of diethylene glycol (DEG) and triethylene glycol (TEG). This is
done by using a large excess of water. In this work, the ethylene oxide/water molar ratio is 1:
7 and the yield of Ethylene glycol is 90%. This Plant is designed to produced 10000kg/yr of
Ethylene Glycol.

The crude Ethylene produced from the reactor is dehydrated and recovered as highly
pure overhead stream from a distillation column with a partial condenser. The Distillate from
the partial condenser is mainly water and is recycled back to the reactor and mixed with
incoming water. The flow sheet for this sequence is shown below

Fig: Shows the Flow sheet for the Production of Ethylene Glycol Simulated on Aspen
Hysis

MATERIAL BALANCE FOR THE REACTOR


Reaction Stoichiometry:
CH2CH2O + H2O HOCH2CH2O
ethylene glycol
Molecular weight of Species:
CH2CH2O = (12x2+1x4+16) = 44kg/kmol
HOCH2CH2O = (12x2+1x6+16x2) =62kg/kmol
Material Balance for Ethylene Oxide:
The target is 10,000kg/yr
10,000kg/yr of HOCH2CH2O = 10,000/62 = 1612.9kmol/yr = 5.33x10-5kmol/sec
HOCH2CH2O
The Ethylene glycol/Water splitter column can only achieve a 99% separation for the
ethylene glycol thus 5.33x10-5/0.99 = 5.38x10-5kmol/sec of ethylene glycol must be produced
from the reactor to be feed into the column.
From Literature, the yield of Ethylene Glycol in the reactor is 90%
Yield of 90% implies
Moles of ethylene oxide used up in the reaction/total moles of ethylene Oxide = 90/100
5.38x10-5kmol/moles of ethylene oxide = 0.9
Therefore, moles of ethylene oxide = 5.38x10-5/0.9 = 5.97x10-5kmol of ethylene Oxide is
used up during the reaction but 5.97x10-5/0.9 = 6.63x10-5kmol/sec of Ethylene is actually feed
into the reactor
Mass of ethylene Oxide required per second = 44kg/kmol x 6.63x10-5kmol = 2.92x10-3kg
Unreacted Ethylene oxide = 6.63x10-5kmol/sec - 5.38x10-5kmol/moles = 6.6x10-6kmol/moles
Material balance for Water:
From Literature,
Since the feed ratio is 1: 7 therefore the moles of water feed = 7 x 6.63x10-5kmols = 4.64x104
kmols
Mass flow rate of water required = 18kg/kmols x 4.64x10-4kmol = 8.35x10-3kg/sec
Taking density of water = 1000kg/m3
The volume of water required per year = 8.35x10-3/1000 = 8.35x10-6m3/sec of water
Unconverted Water
The reacting moles are same for water and ethylene oxide, therefore the amount of water
reacting = amount in moles of ethylene oxide=5.97x10-5kmol.

Therefore
Amount of water left unconverted = Total Water fed Amount that took part in the reaction =
4.64x10-4kmol 5.97x10-5kmol = 4.04x10-4kmol
=4.04x10-4kmol x 18kg/kmols = 7.27x10-3kg/sec of Water
=7.27x10-3/1000 = 7.27x10-6m3/sec of Water
ENERGY BALANCE FOR THE REACTOR
Equation of the reaction
C2H4(g) + H20(g) = C2H6O2(l)
Standard Heat of formation data for this condition
Ethylene Oxide = -52.6kj/mol
Water = -241.8kj/mol
Ethylene glycol = - 460kj/mol
Heat of reaction = Summation of the heat of formation for product summation of the heat of
formation of the reactants
= (1 x -460) ((1 x -52.6) + (1 x -241.8)) = -165.6kj/mol
Therefore DHR (Heat of the reaction) = +165.6kj/mol
The reaction is exothermic so a cooler is incorporated take out the heat produced/mol as the
reaction progresses.
Heat generated by the reaction (Q) = Heat taken by cooling water (Q)
Q = mCPDT of water
Heat generated by the reaction (Q) = 165.6 x 5.38x10-5 (moles of Ethylene oxide produced) =
8.91x10-3kj/s
Where
Where 250c the Temperature of water available
Degree of approach is taken as 100c
CP of water = 4.180kj/kgk
Thus
8.91x10-3kj/s = mCPDT = m x 4.180 x (35-25) +273k
Where 250c the Temperature of water available
Degree of approach is taken as 100c
CP of water = 4.180kj/kgk
m = 8.91x10-3 / 1162.04= 7.67 x 10-6 kg/s
Thus 7.67 x 10-6 kg/s of water must be feed into the cooler system around the reactor to
maintain at operational temperature.

MATERIAL BALANCE FOR THE DISTILLATION COLUNM


Ethylene Glycol has a boiling point of 197.60c while water has a boiling point of
1000c showing that water will boil over first leaving the Ethylene glycol in the bottoms.
From Literature, Relative volatility of Ethylene glycol versus water = 15.1
Specification for the column
Feed rate=F=Amount of water unconverted + Unreacted Ethylene oxide + Ethylene glycol
F=4.04x10-4kmol/s+6.6x10-6kmol/s+5.38x10-6kmol/s=4.64x10-4kmol/s
Which implies that
Water 0.87 moles
Ethylene Glycol 0.12 moles
Ethylene Oxide 0.01 moles
Bottoms (B)
Specification
99% Ethylene Glycol with flow rate of 5.38x10-5x0.99 = 5.33x10-5kmol/s
1% water with flow rate of 4.04x10-4x0.01 = 4.04x10-6kmol/s
Therefore
Bottoms (B) = 5.33x10-5kmol/s + 4.04x10-6kmol/s = 5.734x10-5kmol/s
Distillate (D)
Specification
100% Water
Distillate (D) = F B = 4.64x10-4kmol/s - 5.734x10-5kmol/s = 4.07x10-4kmol/s
L+D=T
Where
L=Flow of Condensate returned to the column
D=Flow of condensate taken out as Distillate
T=Flow of vapour leaving the first stage of the column
Reflux Ration = L/D
At 2.5reflux, L/D=2.5
L=2.5D = 2.5x4.07x10-4kmol/s = 1.02x10-3kmol/s
T=2.5D+D=3.5D=1.4x10-3kmol/s
At total Reflux; the theoretical number of trays can be calculated with relative volatility of
Ethylene glycol versus water = 15.1
Using Fenskes Equation

Nm+1 = log (XD/1-XD 1-XB/XB)/log


=log(0.98/0.12 x 0.99/0.01)/log15.1
Nm= (2.908/1.178) 1 = 2.46 1 =1.46
Using Gillilands rule of thumb, the actual number of tray = 2.5xNm = 2.5x1.46 =3.65trays
Correcting for Tray Efficiencies assuming the efficiency to be 60% = 3.65/0.60 = 6.108= 7
trays

SIMULATION OF THE DISTILLATION COLUNM


The column was simulated using ASPEN HYSIS with the main aim of obtaining the
energy balance of the system and the reboiler and condenser duties. The above calculated
value for the Feed rate and mole composition of the species, reflux ratio, Distillate flow rate,
and number of trays were inputed into the software. Peng Robinson was used as the fluid
package and the specification of the composition of ethylene glycol in the bottoms was
specified as 0.99. It was noted that the HYSIS Estimate of the other Distillate flow, Bottoms
flow etc were very close to the manual calculations made for them. The result of the
simulation is shown below along with the condenser and heater duties.

ETHYLENE GLYCOL/WATER SPLITTER FLOW


SHEET

SPECIFICATION FOR THE REACTOR EFFLUENT


(COLUMN INPUT)

DISTILLATE ESTIMATE

BOTTOMS ESTIMATE