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 tellurium-

bromoethylene 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The reaction liquid effluent is withdrawn and processed to recover glycol acetates and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 + ½ 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 = 4.64x10-
4
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 α = 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 α = 15.1

Using Fenske’s Equation

Nm+1 = log (XD/1-XD 1-XB/XB)/logα

=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