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 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2 Ethylene oxide production . . . . . . . . . . . . . . . . . . . . 3
2.1 Reaction . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2.2 Chlorohydrin process . . . . . . . . . . . . . . . . . . . 3
3 Distillation . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
3.1 Determination of the adiabatic temperature rise . . . 7
3.2 Temperature rise in the reactor . . . . . . . . . . . . . 9
3.3 Constant reactor temperature . . . . . . . . . . . . . . 9
1
1 Introduction
In this project we researched the production process of ethylene oxide (ab-
breviated EtO, C
2
H
4
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 ecient
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 pro-
duction rate. For this process we evaluated mass balances, where dierent
variables are discussed, like the inuence 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 nal product. At the end, the en-
ergy 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 ows in the system set up?
Besides the production process of ethylene oxide, the production of propy-
lene oxide (abbreviated PO, C
3
H
6
O) also is evaluated. We qualitatively
compare this process to the production process of EtO. The dierences and
similarities will be discussed with the following question:
How much diers the production of PO from that of EtO?
O
Figure 1: The molecular structure of ethylene oxide
2
2 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 H
2
C CH
2
+ O
2
Ag
2
O
Figure 2: The formation of ethylene oxide out of ethylene and oxygen cat-
alyzed by a silver catalyst
2
O
+ 5 O
2
4 CO
2
+ 4 H
2
O
Figure 3: Combustion reaction of ethylene oxide.
H
2
C CH
2
+ 3 O
2
2 CO
2
+ 2 H
2
O
Figure 4: Combustion reaction of ethylene.
The process in which ethylene oxide is produced, is schematically represented
in Figure 5. In this gure, all mass ows 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 basi-
cally of three steps: chlorohydration, epoxidation and purication. In the
chlorohydration step, propylene gas and chlorine gas are mixed stoichiomet-
ric, while reacting as following to a chloronium ion intermediate (Figure
6):
This intermediate can react in three ways to dierent products. The de-
sired products are two isomers of propylene chlorohydrin, namely 1-chloro-
2-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.
CH
3
CH
2
+ Cl Cl
CH
3

Cl
+

Cl
Figure 6: The reaction of propylene with chorine to form the chloronium
ion.
CH
3

Cl
+ H
O
H +

Cl
H
3
C
OH
Cl
+ HCl
Figure 7: Reaction of the chloronium ion with water to form 1-chloro-2-
propanol.
CH
3

Cl
+ H
O
H +

Cl
H
3
C
Cl
O H
+ HCl
Figure 8: Reaction of the chloronium ion with water to form 2-chloro-1-
propanol.
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
4
dichloro-dipropyl ether out of a reaction with propylene chlorohydrin (Figure
10).
CH
3

Cl
+

Cl
H
3
C
Cl
Cl
Figure 9: Reaction of the chloronium ion with chloride to form 1,2-
dichloropropanol.
CH
3

Cl
+ H
3
C
O H
Cl
+

Cl
H
3
C
Cl
O
CH
3
Cl
+ HCl
Figure 10: The formation of dichloro-dipropyl ether.
The next step can be called epoxidation, dehydrochlorination or saponica-
tion. 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):
CH
3
OH
Cl
+ HCl + 2OH

CH
3
O
+ 2Cl

+ 2H
2
O
Figure 11: Reaction of chloropropanol with a base to form propylene oxide.
The issue with the saponication is that the propylene oxide decomposes
when a base is present. Therefore...[3]
3 Distillation
Changing the Antoine parameters makes no sense in the nal 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 nd 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.
5
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]
X
eto
p
0
eto
+X
water
p
0
H
2
O
= 4.428 (1)
This can be done...
Therefore, we made a polynomial approximation of the Antoine parametes of
ranges of temperatures we could nd. 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]
Ethylene oxide 1 Ethylene oxide 2 Water
A 4.386 5.48696 4.6543
B 1115.1 2022.83 1435.264
C -29.015 62.656 -64.848
Temperature range 185-280 K 280-305 K 256-373 K
Table 1: Antoine parameters of water and ethylene oxide
6
3.1 Determination of the adiabatic temperature rise
Because the oxidation of ethylene to ethylene oxide is an exothermal reac-
tion, 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
ow 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]

H +

E
k
+

E
p
=

Q

W
s
(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
process the

W
s
(work) term is approximately zero and because we want the
adiabatic temperature rise, the

Q (heat ow) 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:

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 ow with the
enthalpy per mol. In the mass balance section, we already calculated the
molar ows of every single compound in our spreadsheet. These values are
displayed in Table 2.
Compound
in
(mol/s)
out
(mol/s)
Ethylene (g) 2114.286 1902.857
Oxygen (g) 185.0 0
Methane (g) 6147.692 6147.692
Carbon dioxide (g) 287.8681 351.2967
Water (g) 0 63.42857
Ethylene oxide (g) 0 179.7143
Table 2: Molar ows over the reactor
To calculate the enthalpy per mole we need the heat of formation for the
dierent 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 dierent 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
7
Compound Heat of formation
f
H (kJ/mol)
Ethylene (g) 52.47
Oxygen (g) 0
Methane (g) -74.87
Carbon dioxide (g) -393.52
Water (g) -241.83
Ethylene oxide (g) -52.64
Table 3: Heat of formation at p
0
and T
0
of the compounds in the reactor.
Compound A B C D E
Ethylene (g) -6.387880 184.4019 -112.9718 28.49593 0.315540
Oxygen (g) 31.32234 -20.23531 57.86644 -36.50624 -0.007374
Methane (g) -0.703029 108.4773 -42.52157 5.862788 0.678565
Carbon dioxide (g) 24.99735 55.18696 -33.69137 7.948387 -0.136638
Water (g) 30.09200 6.832514 6.793435 -2.534480 0.082139
Ethylene oxide (g) -23.25802 275.6997 -188.9729 51.03350 0.386930
Table 4: Parameters for the Shomate equation.
(compared to p
0
), we can neglect the

V P term. We use the Shomate
equation to express the heat capacity as a function of temperature (Equation
5)
C
p
= A+B t +C t
2
+D t
3
+E/t
2
(5)
t is dened 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 specic.
The constants for the compounds in our reactor are in Table 4.[11]
H =
f
H +
T
2

T
1
C
p
dT (7)
The adiabatic temperature rise depends also on the T
in
, we set T
in
= 523
K[1] and want to calculate T
out
. So T
out
is our variable in equation 4. We
used our Matlab code Determination_of_adiabatic_Temperature_rise.m
and the data above to calculate T
out
. When we ll in the data with T
in
= 523 K we get T
out
= 628.385 K, so the adiabatic temperature rise =
105.385 K.
8
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 selec-
tivity will decrease. So a temperature rise will lead to a lower selectivity.
This means that we produce more by-products. When our selectivity de-
creases 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 ow) isnt zero so we get the equation:

in


H
in

out


H
out
=

Q (8)
In table 2 we can nd the
in
and
out
again, because these dont change
when we let the heat ow 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 le: Energybalance_ethyleenoxide.m). The
results are in table 5.
Compound

H
in
(kJ/mol)

H
out
(kJ/mol)
Ethylene (g) 64.6064 64.6064
Oxygen (g) 6.8060 6.8060
Methane (g) -65.5838 -65.5838
Carbon dioxide (g) -384.4319 -384.4319
Water (g) -234.0780 -234.0780
Ethylene oxide (g) -38.3405 -38.3405
Table 5:

H
in
and

H
out
of the compounds in the reactor.

in


H
in
= 4.8666 10
5
kJ/s (9)

out


H
out
= 5.3835 10
5
kJ/s (10)
This gives a heat ow

Q = 5.1687 10
4
kJ/s So we have to absorb 5.1687 10
4
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
9
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 -203.6060
B 1523.290
C -3196.413
D 2474.455
E 3.855326
Table 6: Shomate parameters for liquid water.
The heat of vaporization of water H
vap
= 40.68 kJ/mol. To calculate the
amount of heat needed to vaporize 1 mol of water at room temperature we
use:
H
vap
+
373

298
C
p
dT = 46.3401 kJ/mol (11)
When we divide Q by this amount we get the amount of water, we can
vaporize by cooling down the reactor = 1.1154 10
3
mol/s.
10
Bibliography
[1] Siegfried Rebsdat, Dieter Mayer, Ullmans Encyclopedia of Industrial
Chemistry - Article Ethylene Oxide. DOI: 10.1002/14356007.a10_117.
published: 15-03-2001, consulted: 21-01-2014.
[2] J. P. Dever, K. F. George, W. C. Homan, H. Soo, Kirk-Othmer:
Encyclopedia of Chemical Technology - Artice Ethylene Oxide. DOI:
10.1002/0471238961.0520082504052205.a01.pub2. published: 14-03-
2004, consulted: 21-01-2014.
[3] David L. Trent, Kirk-Othmer: Encyclopedia of Chem-
ical Technology - Artice Propylene Oxide. DOI:
10.1002/0471238961.1618151620180514.a01.pub2. published: 4-01-
2001, consulted: 21-01-2014.
[4] Dietmar Kahlich, Uwe Wiechern, Jrg Lindner, Ullmans Ency-
clopedia of Industrial Chemistry - Article Propylene Oxide. DOI:
10.1002/14356007.a22_239.pub2. published: 15-10-2012, consulted:
21-01-2014.
[5] Prof. Dr. Rainer Herges and Dr. Torsten Winkler, Epoxidation
of Alkenes with Peracids. URL: http://www.chemgapedia.de/
vsengine/vlu/vsc/en/ch/2/vlu/oxidation_reduktion/epxo_per_
1.vlu/Page/vsc/en/ch/2/oc/reaktionen/formale_systematik/
oxidation_reduktion/oxidation/addition_sauerstoff/
epoxidierung_mit_persaeuren/mechanismus.vscml.html. pub-
lished: 2000, consulted: 21-01-2014.
[6] Shell Oil Company, Patent Preparation Method SMPO Process. Publi-
catio number: US6989469 B2. published: 24-01-2006, consulted: 21-01-
2014.
[7] Richard M. Felder, Ronald W. Rousseau, Elementary Principles of
Chemial Reactions, 2005 edition. ISBN: 987-0-471-68757-3. published:
2005, consulted: 21-01-2014.
[8] University of Alicante, Conversion: Fundamentals and the dier-
ence between single pass and overall conversion. URL: http://
11
www.youtube.com/watch?v=Wgkv8uqQ3wk. published: 14-03-2004, con-
sulted: 21-01-2014.
[9] Y.-L. Huang , T. Merker , M. Heilig , H. Hasse , and J. Vrabec, Molec-
ular Modeling and Simulation of Vapor-Liquid Equilibria of Ethylene
Oxide, Ethylene Glycol, and Water as Well as their Binary Mixtures.
DOI: 10.1021/ie300248z. published: 30-04-2012, consulted: 22-01-2014.
[10] A.B. de Haan, H. Bosch, Fundamentals of Industrial Separations, Edi-
tion 2. ISBN: 9789081097321. published: 2007, consulted: 21-01-2014.
[11] National Institute of Standards and Technology, NIST Chemistry Web-
Book. URL: http://webbook.nist.gov/. published: dierent dates,
consulted: 21-01-2014.
12