EKC 336

CHEMICAL REACTION ENGINEERING

INTERGRATED DESIGN

Title: Plant Design Production of Ethylene Oxide (EO)

LECTURER INCHARGE: ASSOCIATE PROFFESSOR IR. DR. LEO CHOE PENG

DATE SUBMISSION: 12 DECEMBER 2018

Group 12
GROUP MEMBERS:
KOKILAN A/L BALAN 133628
MUHAMMAD AKMAL BIN MOHAMED ARIFFIN 133647
TING SING KIONG 133689
YAZRI AZDI BIN RASDI 133693
TABLE OF CONTENT

NO CONTENT PAGE NUMBER

1.0 Objective 1
2.0 Introduction 2
3.0 Literature Review 3-6
4.0 Reactor Selection and Calculation 7-10
5.0 Aspen Plus Calculation 11-13
6.0 Conclusion 13
7.0 Reference 14
8.0 Appendix 15-22

Notation
r1: Ethylene oxide reaction
r2: Combustion reaction
ki: Reaction rate constant in power law kinetic, i=1,2
Ki: Reaction rate constant in Langmuir-Hinshelwood kinetics, i=1,2,3,4
A: Pre-exponential factor
Ea Activation energy
R: Gas constant
T: Temperature
Po: Partial pressure of oxygen
Pe: Partial pressure of ethylene
2.0 OBJECTIVE
The objectives of this case study are:
- To propose a suitable catalyst and their temperature range commonly used in ethylene
oxide production.
- To find the most suitable reactor to carry out the reaction.
- To calculate the conversion and concentration of each species for the temperature range
of each of the catalyst.
- To study the effects of temperature on the production through Aspen Plus

1
1.0 INTRODUCTION
Generally ethylene oxide is used as an intermediate in the production of chemicals such
as ethylene glycol which is used to manufacture polyester fiber for clothes, upholstery and
carpet. Ethylene oxide derivatives are used as ingredients in household and industrial cleaners,
personal care items such as cosmetics and shampoos. Besides that, Ethylene oxide is primarily
used to sterilize medical and pharmaceutical products that cannot support conventional, high-
steam sterilization procedures. [5]
Ethylene oxide production can be processed through chlorohydrin and direct oxidation.
Chlorohydrin process which known as Wurtz-process. Production of ethylene oxide began in
1914 by the chlorohydrin process in which ethylene chlorohydrin is converted to ethylene oxide
by reaction with calcium oxide. The chlorohydrin process is carried out in packed towers at 27-
43°C and 2-3 atm pressure at a yield of 85-90%. In this process, the concentration of
chlorohydrin in the chlorohydration reaction solution have to be maintained below 7 wt.% to
avoid formation of by-products such as ethylene dichloride and dichlorodiethyl ether.
However, this method is no longer used on an industrial scale and has been replaced by direct
catalytic oxidation method. This method is discovered by Lefort in 1931. Direct oxidation is
carried out at 220-300°C and 10-30 bar pressure and produces few by-products such as carbon
dioxide and water. [1][2]
There are two reaction in direction oxidation method. The first reaction is oxidation of ethylene
to ethylene oxide. The second reaction is combustion of ethylene. [3]
C2H4 + ½ O2 → C2H4o (Reaction 1)
C2H4 + 3O2 → 2CO2 + 2H2O (Reaction 2)
Up to the present, silver has been considered as the most efficient catalyst for direct oxidation
of ethylene to ethylene oxide. However, pure silver catalyst shows low selectivity to ethylene
oxide. Hence, addition of promoters into pure silver catalyst have been introduced to improve
the selectivity to ethylene oxide. [4] In following discussion, two catalyst will be discussed to
decide which catalyst is most suitable.

2
3.0 LITERATURE REVIEW
Various dimension and specifications of catalyst can be varied to obtain the desired
product. Such parameters depend on various factors such reactor type, size of catalyst,
operating temperature of the reactor and etc. Two different articles were chose to undergo a
literature review process to understand the specification of the silver catalyst used in the
ethylene oxide production.

3.1 SILVER WITH ALUMINA (Ag/Al2O3) [3][6]

In the first article, the reaction with silver with alumina catalyst is carried out in a plug flow
reactor. Based on first article, the catalyst that used in this ethylene oxide production has the
following characteristics:
- 0.475 cm× 0.475 cm fused alumina pellets coated with silver
- The pellets containing 10% by weight silver.
- 543gram of catalyst is used.
The reaction detail is stated as below:
Table 1: Silver with alumina (Ag/Al2O3)
Catalyst Silver with alumina (Ag/Al2O3)
Operating temperature 428 F to 500 F
Operating pressure 22.4552 atm
Conversion based on ethylene Calculation step:
X − 3.8 220 − 210
=
6.4 − 3.8 225 − 210
X = 5.53%
Selectivity based on ethylene 73% (interpolate based on diagram below)
Reactor Fixed bed reactor

Figure 1: Conversion against Selectivity Graph [6]

3
Power law kinetic used to model this reaction.
r1 = k1 [C2H4] [O2]0.5
r2 = k2[C2H4] [O2]3
Ea
k i = Ae−RT , i=1,2

Table 2: Kinetic Data for Silver with Alumina

Reaction rate constant Activation Energy Pre-Exponential Factor
9.547 × 109 [mol/L]-0.5/sec
k1 28 kcal/mol
(3.4369×1013) [kmol/m3]-0.5/hr
1.593 × 1011 [mol/L]-1/sec
k2 31 kcal/mol
(5.7348×1014) [kmol/m3]-0.5/hr

4
3.2 SILVER SUPPORTED ON ALUMINA, PROMOTED BY A CLACIUM ADDITIVE.
[7]

In the second article, the catalyst used is silver supported on alumina, promoted by a calcium
additive carried out in a fixed bed reactor. Based on second article, the catalyst that used in this
ethylene oxide production has the following characteristics:
- 10% silver supported on alumina, promoted by a Ca additive
- Specific surface area, 0.225625𝑚2
- Total pore volume, 0.06𝑐𝑚2 g-𝑐𝑎𝑡 −1
- Spheroidal pellets, 6mm in diameter
- Prevailing pore radius, 200Å

Table 3: Silver supported on alumina, promoted by a Calcium additive

Catalyst Silver supported on alumina, promoted by a Calcium
additive
Operating temperature 410 F to 558 F
Operating pressure 1 atm
Conversion based on ethylene 70% (at 507 F)
Selectivity based on ethylene 50.3 % (at 507 F)

Reactor Fixed bed reactor

Langmuir-Hinshelwood kinetics is used to model this reaction.

K1 Po Pe
r1 =
1 + K 3 Po + K 4 Pe
K 2 Po Pe
r2 =
1 + K 3 Po + K 4 Pe

Table 4: Kinetic Data for Silver Supported on Alumina, Promoted by Calcium Additive
Reaction rate constant Activation Energy Pre-Exponential Factor
K1 8087 cal/mol 13.53 mol/ (h.g-cat.atm2)
K2 13559 cal/mol 2253.00 mol/ (h.g-cat.atm2)
K3 7378 cal/mol 0.0004507 mol/ (h.g-cat.atm2)
K4 7897 cal/mol 0.0051330 mol/ (h.g-cat.atm2)

5
3.3 SUGGESTION FOR CATALYST
Based on the table 4.1.5, it is observed that both catalysts can be operated with similar range
temperature but large different in operating pressure. From this perspective, silver with alumina
[3]
might be better choice, due to in industry scale, the reaction is carried on in high pressure. .
In general, high conversion of ethylene can prevent the waste of feed. Hence, it can reduce the
cost. High selectivity mean more desired product can be obtained. The more desired product
produced, the more the profit earned. Besides, the reaction is eco-friendly, since less carbon
dioxide be produced. However, the prevention of waste that caused by low conservation can
be overcome by install recycle steam back to reactor. Therefore, the best catalyst should have
higher selectivity instead of high conversion. Hence, silver with alumina is the better choice in
this condition.

Table 5: Summary for Comparison

Catalyst Silver Supported on Alumina,
Silver with alumina
Condition Promoted by Calcium Additive
Operating Temperature 428 F to 500 F 210 C to 292 C
(220C to 260 C)
Operating Pressure 330 psig 1 atm
(22 atm)
Conversion based on 5.53% 70%
ethylene
Selectivity Selectivity: 73% 50.3 %
Reactor Fixed bed reactor Fixed bed reactor

6
4.0 REACTOR SELECTION AND CALCULATION
4.1 REACTOR SELECTION

Most of the modern ethylene oxide production based on oxygen-based reaction using fixed-
bed reactor (packed backed reactor). A packed bed reactor (PBR) is preferred for heterogenous
reactions, which solid catalyst is used. A PBR is a cylindrical vessel filled with solids (a
reactant). The other reactant is allowed to enter in to the bed through the bottom. [8]
There are four main reasons packed backed reactor is used in modern ethylene oxide
production. The first reason is the higher productivity and selectivity. Second reason is lower
initial capital costs needed because plug flow reactor is requiring less volume than continuously
stirred tank reactor. The reactor cost will increase with volume hence initial capital cost can be
reduced through using plug flow reactor. Third reason is less expensive catalyst required.
Lastly, less air pollutants resulting from the purge gas. [3]

4.2 CALCULATION
Based on the ICIS news, Malaysia’s PETRONAS Chemicals Group (PCG) produced 140,000
tonne/year ethylene oxide at Kerteh, Terengganu. Hence, in this report, 140,000 tonne/year
ethylene oxide will used as target of our calculation’s production rate. The molar flow rate of
the ethylene and oxygen molar are fixed to investigate the effect of catalyst towards the
production rate. Discussion is done by compare the production that calculated by polymath and
normal industry scale.

4.2.1 CALCULATION STEP

First, atomic mass of carbon, oxygen and hydrogen are obtained from Nist webbook periodic
table. Hence, calculate the molar mass of each component.
Table 5: Atomic Mass and Molar Mass of component
Atom Atomic Mass
C 12.011
O 15.999
H 1.006
Component Molar Mass
C2H4O 44.0450
C2H4 28.0460
O2 31.9880

7
Next, convert production rate unit from tonne/ year to kilomole/hour.
140,000 𝑡𝑜𝑛𝑛𝑒 1000𝑘𝑔 1𝑦𝑒𝑎𝑟 1 𝑘𝑚𝑜𝑙 362.850 𝑘𝑚𝑜𝑙
× × × =
𝑦𝑒𝑎𝑟 1𝑡𝑜𝑛𝑛𝑒 (365 × 24)ℎ𝑜𝑢𝑟 44.0450𝑘𝑔 ℎ𝑜𝑢𝑟

From the reference [3], the feed of ethylene and oxygen is 25.9 KIb/hr and 29.6 KIb/hr
respectively. Next, molar flow rate of feed is done by doing unit conversion. In this reference,
it mentioned that the mole percentage of ethylene and oxygen should be remained at 25% and
8% respectively to prevent reactant explode directly. Hence, inert need to be introduce should
is argon.
25900𝐼𝑏 0.453𝑘𝑔 1 𝑘𝑚𝑜𝑙 418.34𝑘𝑚𝑜𝑙
𝑒𝑡ℎ𝑦𝑙𝑒𝑛𝑒 = × × =
ℎ𝑟 1𝐼𝑏 28.0460𝑘𝑔 ℎ𝑟
29600𝐼𝑏 0.453𝑘𝑔 1𝑘𝑚𝑜𝑙 419.18𝑘𝑚𝑜𝑙
𝑜𝑥𝑦𝑔𝑒𝑛 = × × =
ℎ𝑟 1𝐼𝑏 31.9880𝑘𝑔 ℎ𝑟
Taking oxygen as basic to calculate amount of ethylene and argon needed.
100 1309.9375𝑘𝑚𝑜𝑙
𝑟𝑒𝑎𝑙 𝑒𝑡ℎ𝑦𝑙𝑒𝑛𝑒 𝑛𝑒𝑒𝑑𝑒𝑑 = 419.18 × × 0.25 =
8 ℎ𝑟
100 3510.6325 𝑘𝑚𝑜𝑙
𝑎𝑟𝑔𝑜𝑛 𝑛𝑒𝑒𝑑𝑒𝑑 = 419.18 × × 0.67 =
8 ℎ𝑟
Following step, calculate the initial concentration of the total feed by using ideal gas laws. The
temperature and pressure inlet for reactor is 533.15 K (260C) and 2229150 Pa respectively
which given in reference [3] as well. Another extra temperature is used which is 493.15K
(220C) to study the effect of temperature toward the production rate. Both 260C and 220C
is within the temperature that suitable for catalyst function.
𝑃 2229150 502.898𝑘𝑚𝑜𝑙
𝐶𝑜1 = = =
𝑅𝑇 8.314 × 533.15 𝑚3
𝑃 2229150 543.686𝑘𝑚𝑜𝑙
𝐶𝑜2 = = =
𝑅𝑇 8.314 × 493.15 𝑚3
Last using polymath, to calculate the concentration and the conversion. The coding is shown
at appendix. Weight of catalyst set as 0.534kg based on reference [3]
In this calculation, few assumptions have been made:
1) The reactant is pure reactant.
2) Pure oxygen is used as feed instead of air.
3) The process is at steady state condition.
4) No radial variation in properties of the system.
5) The process is isothermal and pressure constant throughout the reaction.

8
4.2.2 POLYMATH SOLUTION AND DISCCUSION

Figure 2: Result from Polymath (Top Left: Silver with alumina at 220 C, Top Right: Silver
with alumina at 260C, Bottom Left: Silver Supported on Alumina, Promoted by Calcium
Additive at 220C, Bottom Right: Silver Supported on Alumina, Promoted by Calcium
Additive at 260C) *shown in appendix as well

9
 Table 6: Required information
Catalyst Silver with alumina Silver Supported on
Alumina, Promoted by
Calcium Additive
Required Information Temperature

220 C 260 C 220 C 260 C

Concentration of Ethylene 120.6846 111.6554 0.1354 0.1251
(m3/kmol)
Concentration of Oxygen 8.099 E-11 4.483E-72 0.0432 0.0399
(m3/kmol)
Concentration of Ethylene 1.0235 0.9124 0.0005 0.0007
Oxide (m3/kmol)
Concentration of Carbon 28.8627 26.5414 2.23E-06 4.245E-06
dioxide (m3/kmol)
Concentration of water 28.8627 26.5414 2.23E-06 4.245E-06
(m3/kmol)
Flow rate of ethylene oxide 9.8542 9.4982 4.6658 7.4011
(kmol/hr)
Conversion 11.2937 11.27091 0.3570 0.5667

Based on the Figure 2 and Table 6, both catalysts cannot reach the desired production rate
362.850 kmol/hr. Few possibilities cause this scenario occurred. First possibility is the feed
that fixed for polymath is too low. Hence, adjustment through trail and error method is done,
and the minimum total feed required to achieve the production rate is 50000 kmol/hr. However,
it seen like not so logic because the ethylene feed that needed is 350000 kg/hr. This amount
required the high cost fee. The polymath result for this feed condition is shown in appendix.
The other possibility is the catalyst that used in the PETRONAS Chemicals Group’s plant is
different with the one that proposed. Since catalyst have different properties and different
kinetic data, hence the different catalyst might be one of the possibilities.

From data that obtained, it showed that in the same feed condition, silver alumina perform
better compare to silver supported on alumina, promoted by calcium additive. The production
rate that obtained by reaction that use silver alumina the conversion is higher compare to
another catalyst. From the point of view of single catalyst, the silver alumina performed better
at low temperature because production is 9.8542 kmol/hr at 220C and the conversion is higher
as well, while silver supported on alumina, promoted by calcium additive have better
performance at high temperature due to production is 7.4011kmol/hr at 260C and the
conversion increase 0.2097% from temperature increase from 220C to 260C.

10
5.0 ASPEN PLUS SIMULATION
5.1 ASPEN PLUS SET UP STEP
To simulate the process by Aspen, firstly, selected the component that involve in the reaction.
Then choose SRK method to solve the simulation. Next, draw the block diagram in ‘simulation
main flowsheet’ part. Feed condition and the reaction condition that used are same with the
polymath calculation. Hence, key in data in the ‘inlet stream’. Following step is write the
stoichiometry equation and key in the silver alumina’s catalyst kinetic data in ‘reaction
session’. When key in kinetic data, selected the reaction phase as vapour phase. The reactor
that have been chose is multiple tube plug flow reactor. In the setup under ‘blocks’ section,
choose the ‘reactor with specific temperature’. 8821 number of tubes with diameter 31.3mm is
[9]
used. The length for each tube is 8.2. Last step, press the run button to run the simulation.
The result can be obtained. Graph is plotted by using Excel.
5.2 ASPEN PLUS SIMULATION DISCUSSION
Table 7: Data obtained from Aspen Plus and Conversion Calculation
Aspen Plus Results Temperature
Result Inlet 220 C 240 C 260 C 280 C 300 C
Flow rate of Ethylene 1309.94 1289.52 1252.76 1167.010 1000.55 755.604
(kmol/hr)
Flow rate of Oxygen 419.18 408.958 390.553 347.626 264.329 141.817
(kmol/hr)
Flow rate of Ethylene / 20.407 57.1564 142.886 309.323 554.255
Oxide (kmol/hr)
Flow rate of Carbon / 0.012 0.032 0.074 0.126 0.157
dioxide (kmol/hr)
Flow rate of water / 0.012 0.032 0.074 0.126 0.157
(kmol/hr)
Conversion (%) / 1.5 4.56 10.91 23.62 42.32
*Example of conversion calculation is shown below.
𝑚𝑜𝑙𝑒 𝑜𝑓 𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡 𝑟𝑒𝑎𝑐𝑡𝑒𝑑
𝐶𝑜𝑛𝑣𝑒𝑟𝑠𝑖𝑜𝑛 = × 100%
𝑚𝑜𝑙𝑒 𝑜𝑓 𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡 𝑓𝑒𝑑
1309.94 − 1167.010
= × 100% = 10.91%
1309.94

11
 Figure 3: Flow Rate of Ethylene Oxide against Temperature

Conversion against Temperature

45
40
Conversion (%)

35
30
25
20
15
10
5
0
200 220 240 260 280 300 320

Temperature (C)

Figure 4: Conversion against Temperature

From the table and graph above, it is obviously shown that the flow rate of ethylene oxide and
conversion is increase when temperature. Oxidation of ethylene is exothermic reaction. In an
[6]
exothermic reaction, the conversion will increase when the temperature increase. When
temperature increase, the heat energy is supplied to feed molecules to overcome the activation
energy and form the product. Hence, it is reasonable, when temperature increase, conversion
and production rate increase. The highest flow rate of ethylene and conversion is 554.255
kmol/hr and 42.32% respectively at 300C. Through this, it is suggested to operate the reactor
with high temperature. However, the catalyst that proposed through literature review, working
temperature of catalyst is around 220 C to 260 C. Hence maximum temperature that
recommended is around 260 C.

12
However, through comparison the Aspen plus calculation and polymath calculation, there is a
bit different. In polymath, it showed that the production rate and conversion decrease when
temperature increase. While in Aspen Plus, the production rate and conversion increase when
temperature increase.

6.0 CONCLUSION
In short, silver catalysts play an important role in ethylene oxide production. Different addictive
is added to increase to selectivity of ethylene oxide. From literature review, different catalysts
showed different properties and different condition is required for catalyst to perform well. The
suggested reactor is fixed bed reactor (packed bed reactor) since this reaction involve required
catalyst. Through all the discussion above, silver alumina showed better performance compare
to the silver supported on alumina, promoted by calcium additive because it has higher
selectivity, better production rate that calculated through polymath and higher conversion.
From polymath calculation, the silver alumina performed better in lower temperature instead
of high temperature. Through Aspen Plus simulation, it showed that the production rate and
conversion increase when temperature increase.

13
Reference:
1) Rebsdat.S, Mayer.D (2012).Ethylene oxide Ullmann’s Encyclopedia of Industry Chemistry
4th edition [online] volume 13, pp 543-572. Available at
http://www.ugr.es/~tep028/pqi/descargas/Industria%20quimica%20organica/tema_5/oxido_e
tileno_a10_117.pdf [Accessed 25 Nov. 2018].
2）Hanna Perzon. (2015) A Simulation Model of a reactor for Ethylene Oxide production.
Thesis. Department of Chemical Engineering Lund University, Lund, Sweden
3) Xiongtao.Y, Qiang. X, Kuyen.L, and Chirag D. Sagar (2010). Dynamic Simulation and
Optimization for the Start-up Operation of An Ethylene Oxide Plant. Industrial & Engineering
Chemistry Research,49(9), pp 4360–4371
4) Zhenhao.L, Lin.Z, Jian-Feng.C, and Daojian.C (2018). Enhanced Ethylene Oxide Selectivity
by Cu and Re Dual-Promoted Ag Catalysts. Industrial & Engineering Chemistry Research,
57 (12), pp 4180–4185.
5) Toxicological profile for ethylene oxide. (1990). [Atlanta, Ga.]: U.S. Dept. of Health &
Human Services, Public Health Service, Agency for Toxic Substances and Disease Registry.
6) Robert.E.K and Lapkin.M (1970) . Kinetics and mechanism of ethylene oxidation.
Reactions of ethylene and ethylene oxide on a silver catalyst. J. Phys. Chem.,74 (7), pp 1493–
1502
7) Petrov.L, Eliyas.A and Shopov.D (1985) A Kinetic Model of Steady State Ethylene
Epoxidation Over a Supported Silver Catalyst. Applied Catalyst,18(1), pp87-103
8) Dr Sanju Nanda (2008) Reactors and Fundamentals of Reactor Design for Chemical
Reaction. Report. Dept. of Pharmaceutical Sciences Maharshi Dayanand University, Haryana,
India.
9) Zhou, X. and Yuan, W. (2005). Optimization of the fixed-bed reactor for ethylene
epoxidation. Chemical Engineering and Processing: Process Intensification, 44(10), pp.1098-
1107.

14
APPENDIX
Coding for Polymath (Silver Supported on Alumina, Promoted by Calcium Additive)

15
Trial and Error Method to obtain Desired Production Rate (using silver alumina)

16
Silver alumina at
temperature =
220 C

Silver alumina at
temperature =
260 C

17
 Silver Supported
on Alumina,
Promoted by
Calcium Additive
at temperature =
220C

Silver Supported
on Alumina,
Promoted by
Calcium Additive
at temperature =
260C

18
Reactor Design

Feed condition

Block diagram in Aspen Plus

19
When temperature is 220 C.

When temperature is 240C.

20
When temperature is 260C.

When temperature is 280C.

21
When temperature is 300C.

22