Industrial production of ethylene oxide

How is ethylene oxide produced on an industrial

scale and how does the ethylene oxide process
qualitatively compare to the production of propylene
oxide?

Hans David Wendt, Lars Heuvels, Eline van Daatselaar and Tim van Schagen
(Group B)

April 3, 2014

Contents
1
2

Introduction . . . . . . . . . . . . . . . . . . . . . .
Ethylene oxide production . . . . . . . . . . . . . .
2.1
Reaction . . . . . . . . . . . . . . . . . . . .
2.2
Chlorohydrin process . . . . . . . . . . . . .
Distillation . . . . . . . . . . . . . . . . . . . . . .
3.1
Determination of the adiabatic temperature
3.2
Temperature rise in the reactor . . . . . . .
3.3
Constant reactor temperature . . . . . . . .

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Introduction

In this project we researched the production process of ethylene oxide (abbreviated EtO, C2 H4 O). Ethylene oxide is a frequently used intermediate in
the chemical industry. The reason for this is the easily broken ring (Figure
1), because the breaking of these bonds releases a lot of energy. So ethylene
oxide is a very reactive and much used compound. Because of this, very
much ethylene oxide is produced on a yearly basis. In earlier times, the
production process involved a chlorohydrin process, which was less efficient
then the oxidation process that is used presently. We focussed on the direct
oxidation process, with pure oxygen and not with air. We made this choice,
since the process with pure oxygen is more often used and has a higher production rate. For this process we evaluated mass balances, where different
variables are discussed, like the influence of the conversion, selectivity and
feed rate. We also had a look at the separator units, mainly the distillation
column. Those columns are important for these kind of processes, because
these units improve the purity of the final product. At the end, the energy balance is computed. To evaluate these three processes, we have used
calculation programs like Matlab and Microsoft Excel.
Our research questions are:
How is the mass balance of the production of EtO arranged?
How does the distillation column work for this process?
How are the energy flows in the system set up?
Besides the production process of ethylene oxide, the production of propylene oxide (abbreviated PO, C3 H6 O) also is evaluated. We qualitatively
compare this process to the production process of EtO. The differences and
similarities will be discussed with the following question:
How much differs the production of PO from that of EtO?

Figure 1: The molecular structure of ethylene oxide

Ethylene oxide production

We will start with discussing the production of ethylene oxide in a chemical

factory.

2.1

Reaction

The reaction we are evaluating is the production of ethylene oxide from

ethylene and oxygen. The reactions that occur in the reactor are depicted
in Figure 2, Figure 3 and Figure 4. The reaction in Figure 2 is the desired
reaction to produce ethylene oxide. Unfortunately, there is a side reaction.
Ethylene oxide reacts further to carbon dioxide and water (Figure 3). The
reaction in Figure 4 is the sum of 2 and 3 and so the total reaction equation
for the byproducts.
2 H2 C

CH2 +

O2

Ag

O
2

Figure 2: The formation of ethylene oxide out of ethylene and oxygen catalyzed by a silver catalyst
O
2

+ 5 O2

4 CO2 + 4 H2 O

Figure 3: Combustion reaction of ethylene oxide.

H2 C

CH2 +

3 O2

2 CO2 + 2 H2 O

Figure 4: Combustion reaction of ethylene.

The process in which ethylene oxide is produced, is schematically represented
in Figure 5. In this figure, all mass flows and separators are pointed out and
will be computed in following paragraphs.[1]

2.2

Chlorohydrin process

The process to make propylene oxide by using chlorohydrins consists basically of three steps: chlorohydration, epoxidation and purification. In the
chlorohydration step, propylene gas and chlorine gas are mixed stoichiometric, while reacting as following to a chloronium ion intermediate (Figure
6):
This intermediate can react in three ways to different products. The desired products are two isomers of propylene chlorohydrin, namely 1-chloro2-propanol (Figure 7) and 2-chloro-1-propanol (Figure 8), which arise from
a reaction with water:
3

Figure 5: Schematic representatation of the ethylene oxide process.

Cl

CH2
CH3

Cl

CH3

Cl

Cl

Figure 6: The reaction of propylene with chorine to form the chloronium

ion.
OH

Cl
CH3

H3 C

O
+ H

+ HCl

H + Cl
Cl

Figure 7: Reaction of the chloronium ion with water to form 1-chloro-2propanol.

Cl
CH3

Cl

H3 C
O
+ H

+ HCl

H + Cl
HO

Figure 8: Reaction of the chloronium ion with water to form 2-chloro-1propanol.

1-chloro-2-propanol emerges for about 85%, because this isomer is formed via
a secondary carbocation, while 2-chloro-1-propanol is formed via a primary
carbocation. Usually this desired main reaction represents 90% or more
of the yield. Besides, there are two side reactions, which together emerge
for up to 10%. The intermediate can react with the chloride ion to form
1,2-dichloropropane (Figure 9). The other side reaction produces isomers of
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dichloro-dipropyl ether out of a reaction with propylene chlorohydrin (Figure

10).
Cl

Cl

H3 C
CH3

+ Cl
Cl
Figure 9: Reaction of the chloronium ion with chloride to form 1,2dichloropropanol.

Cl
CH3

Cl

+ H3 C

+ Cl

H3 C

+ HCl
O

Cl

Cl

CH3

Figure 10: The formation of dichloro-dipropyl ether.

The next step can be called epoxidation, dehydrochlorination or saponification. The chloropropanol reacts with a base, which is added in excess. This
could be calcium hydroxide or sodium hydroxide, dissolved in water. The
reaction is as following (Figure 11):
OH
+ HCl + 2OH

CH3

CH3

Cl

+ 2Cl + 2H2 O

Figure 11: Reaction of chloropropanol with a base to form propylene oxide.

The issue with the saponification is that the propylene oxide decomposes
when a base is present. Therefore...[3]

Distillation

Changing the Antoine parameters makes no sense in the final version, but
we will discuss that later. The parameters are only present to show us the
Antoine parameters. The boiling temperatures are valid for 1 bar, but we
solved the assignment for 4.428 bar, since we could only find Vapor Liquid
Equilibrium (VLE) data for water and ethylene oxide at this pressure. We
made a plot and polynomial approximation of a VLE graph.[9] This graph
can be seen in Figure 12.
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Figure 12: VLE graph of EtO and water.

Next, we want to evaluate the temperature of the feed. This can be done
by solving equation 1.[10]
Xeto p0eto + Xwater p0H2 O = 4.428

(1)

This can be done...

Therefore, we made a polynomial approximation of the Antoine parametes of
ranges of temperatures we could find. Then we extrapolated these. We put
this approximation in equation 1 to solve it. This makes a better polynomial
approximation than using only one set of parameters. The parameters used
are displayed in table 1.[11]

A
B
C
Temperature range

Ethylene oxide 1
4.386
1115.1
-29.015
185-280 K

Ethylene oxide 2
5.48696
2022.83
62.656
280-305 K

Water
4.6543
1435.264
-64.848
256-373 K

Table 1: Antoine parameters of water and ethylene oxide

3.1

Determination of the adiabatic temperature rise

Because the oxidation of ethylene to ethylene oxide is an exothermal reaction, there is a lot of energy that is released in the reaction. We want to
know what the temperature rise of the reactor is when we dont let any heat
flow in or out (adiabatic). Weve used an enthalpy balance to determine the
adiabatic temperature rise. We use the steady-state open-system energy
balance (equation 2).[7]
s
H + E k + E p = Q W

(2)

E k (kinetic energy) and E p (potential energy) can be neglected because

these terms are very small in comparison to H (internal energy). In our
s (work) term is approximately zero and because we want the
process the W
adiabatic temperature rise, the Q (heat flow) term is also zero. So we get
H = 0, which means:
H in = H out
(3)
We use the heat of formation method to calculate the enthalpy balance. So
we can rewrite equation 3 to:
X

in H in =

out H out

(4)

In this equation we just take the sum of the enthalpy of each individual
component, which can be calculated by multiplying the molar flow with the
enthalpy per mol. In the mass balance section, we already calculated the
molar flows of every single compound in our spreadsheet. These values are
displayed in Table 2.
Compound
Ethylene (g)
Oxygen (g)
Methane (g)
Carbon dioxide (g)
Water (g)
Ethylene oxide (g)

in (mol/s)
2114.286
185.0
6147.692
287.8681
0
0

out (mol/s)
1902.857
0
6147.692
351.2967
63.42857
179.7143

Table 2: Molar flows over the reactor

To calculate the enthalpy per mole we need the heat of formation for the
different compounds. The heat of formation is given at 298 K and 1 atm.
Weve used the data of the NIST Webbook[11] (Table 3).
Because we arent working at standard temperatures, we also have to know
the heat capacities of the compounds, and because these arent constant
at different temperatures we need the heat capacities as a function of the
temperature. Its true that we also didnt work at standard pressures, but
because we work with gases and our working pressure isnt very extreme
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Compound
Ethylene (g)
Oxygen (g)
Methane (g)
Carbon dioxide (g)
Water (g)
Ethylene oxide (g)

Heat of formation f H (kJ/mol)

52.47
0
-74.87
-393.52
-241.83
-52.64

Table 3: Heat of formation at p0 and T0 of the compounds in the reactor.

Compound
Ethylene (g)
Oxygen (g)
Methane (g)
Carbon dioxide (g)
Water (g)
Ethylene oxide (g)

A
-6.387880
31.32234
-0.703029
24.99735
30.09200
-23.25802

B
184.4019
-20.23531
108.4773
55.18696
6.832514
275.6997

C
-112.9718
57.86644
-42.52157
-33.69137
6.793435
-188.9729

D
28.49593
-36.50624
5.862788
7.948387
-2.534480
51.03350

E
0.315540
-0.007374
0.678565
-0.136638
0.082139
0.386930

Table 4: Parameters for the Shomate equation.

(compared to p0 ), we can neglect the V P term. We use the Shomate
equation to express the heat capacity as a function of temperature (Equation
5)
Cp = A + B t + C t2 + D t3 + E/t2

(5)

t is defined in Equation 6, where T is the temperature in Kelvin.

t = T /1000

(6)

A, B, C, D and E are constants. These constants are compound specific.

The constants for the compounds in our reactor are in Table 4.[11]
ZT2

H = f H +

Cp dT

(7)

T1

The adiabatic temperature rise depends also on the Tin , we set Tin = 523
K[1] and want to calculate Tout . So Tout is our variable in equation 4. We
used our Matlab code Determination_of_adiabatic_Temperature_rise.m
and the data above to calculate Tout . When we fill in the data with Tin
= 523 K we get Tout = 628.385 K, so the adiabatic temperature rise =
105.385 K.

3.2

Temperature rise in the reactor

If the temperature in the reactor rises, the single pass conversion will rise,
because the reaction will occur faster. When the conversion rises the selectivity will decrease. So a temperature rise will lead to a lower selectivity.
This means that we produce more by-products. When our selectivity decreases the production cost will increase so we dont want the selectivity to
decrease. The temperature is allowed when the reactor is strong enough to
hold these circumstances, but economically we dont want a temperature
rise in our reactor.

3.3

Constant reactor temperature

Because we want a constant temperature in our reactor and the reaction is

exothermal we have to cool down the reactor. To calculate the amount of
heat we have to absorb we again use an enthalpy balance. This time the Q
(heat flow) isnt zero so we get the equation:
X

in H in

out H out = Q

(8)

In table 2 we can find the in and out again, because these dont change
when we let the heat flow out. The H in and H out can be calculated because
temperature in reactor is constant = 523 K. We just use equation 7 again
(calculations done with Matlab file: Energybalance_ethyleenoxide.m). The
results are in table 5.
Compound
Ethylene (g)
Oxygen (g)
Methane (g)
Carbon dioxide (g)
Water (g)
Ethylene oxide (g)

H in (kJ/mol)
64.6064
6.8060
-65.5838
-384.4319
-234.0780
-38.3405

H out (kJ/mol)
64.6064
6.8060
-65.5838
-384.4319
-234.0780
-38.3405

Table 5: H in and H out of the compounds in the reactor.

in H in = 4.8666 105 kJ/s

(9)

out H out = 5.3835 105 kJ/s

(10)

This gives a heat flow Q = 5.1687 104 kJ/s So we have to absorb 5.1687 104
kJ per second. We use water at room temperature (298 K) to cool down
the reactor, because this is a cheap substance with very few risks. Another
advantage of cooling down the reactor with water is, that we can re-use the

steam for heating up other streams of the process. To calculate the amount
of steam at 373 K that we can produce, we need the heat of vaporization
and the heat capacity of liquid water. To express the heat capacity as a
function of the temperature, we use the Shomate equation again (Equations
5 and 6). The constants for liquid water are depicted in table 6.[11]
A
B
C
D
E

-203.6060
1523.290
-3196.413
2474.455
3.855326

Table 6: Shomate parameters for liquid water.

The heat of vaporization of water Hvap = 40.68 kJ/mol. To calculate the
amount of heat needed to vaporize 1 mol of water at room temperature we
use:
Z373

Cp dT = 46.3401 kJ/mol

Hvap +

(11)

298

When we divide Q by this amount we get the amount of water, we can

vaporize by cooling down the reactor = 1.1154 103 mol/s.

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