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 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. Abstract
2. Introduction
3. Objective
4. Results and Discussion
5. Conclusion
6. Reference
7. Appendix
1.0 ABSTRACT
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 determine the reaction details such as conversion, selectivity and kinetic data for
the selected catalysts.
- 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 conduct mass and energy balance of the catalytic in a process simulator

3.0 INTRODUCTION

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%. 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been replaced by direct catalytic oxidation method. 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, three catalyst will be discussed to

decide which catalyst is most suitable.

Two mechanisms are proposed to explain the kinetic data for the isomerization and

oxidation of ethylene oxide and thermodynamic data were used to establish the most reasonable

one. The isomerization of ethylene oxide adsorbed on the catalyst to acetaldehyde is the

mechanism postulates the rate-determining step which would be preceded by rapid

chemisorption of ethylene oxide on the catalyst. The oxygen is used to oxidized the

acetaldehyde to carbon dioxide and water.

The value of the apparent ∆S*, which in this case would be the sum of ∆Si + ∆Si *, is

quite reasonable in relation to literature values for chemisorptive processes. Less reasonable

partitionings of energy must be employed in order to rationalize the value of 𝐸𝑎 . In order to

get the value about 10 kcal/mol, 𝑞𝑖 , which is the sum of q(adsorption) + q (chemisorption),

must be negative and at least the order of magnitude of 𝐸𝑎 which is:

𝐸𝑎 = 𝐸𝑎 (true) + 𝑞𝑖

q adsorption should be approximately thermoneutral and the Q chemisorption should have to

be at least about 10 kcal for the mechanisms to be valid. Since ethylene oxide is the only very

weakly adsorbed and q chemisorption is therefore small, this oxidation process of ethylene

oxide is unsatisfying.

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][6]

4.0 RESULTS

4.1 LITERATURE REVIEW

4.1.1 CATALYST

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

The catalyst used commonly 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

The reaction is carried out in a plug flow reactor. Working with the optimum operating
temperature and pressure of 428F to 500 F and 330 psig, this reaction is said to produce the
maximum yield. Based on the plotted graph, the selectivity of the reaction is 73% and the
conversion based on the ethylene is 5.53%. The reaction are below as stated :

Table 4.1.1.1 : Specification of the reaction in a plug flow reactor

Catalyst Silver with alumina (Ag/Al2O3)
Operating temperature 428 F to 500 F
Operating pressure 22.4552 atm
Conversion based on ethylene 5.53%
Selectivity based on ethylene 73%
Reactor Plug flow reactor

Conversion based on ethylene: 5.53%

𝑋 − 3.8 220 − 210

=
6.4 − 3.8 225 − 210
Selectivity: 73% (interpolate from graph)

Figure 1: Conversion against Selectivity Graph [6]

Reactor: Plug flow reactor

Power law kinetic used to model this reaction.

r1 = k1 [C2H4] [O2]0.5

r2 = k2[C2H4] [O2]3
𝐸𝑎
𝑘𝑖 = 𝐴𝑒 −𝑅𝑇 , i=1,2

Table 4.1.1.2: Kinetic Data for Silver with Alumina

Reaction rate constant Activation Energy Pre-Exponential Factor

k1 28 kcal/mol 9.547 × 109 [mol/L]-0.5/sec

k2 31 kcal/mol 1.593 × 1011 [mol/L]-1/sec

The second reaction is carried out in a fixed bed reactor. The reaction details are below as
stated in table 3.

Langmuir-Hinshelwood kinetics is used to model this reaction.

𝐾1 𝑃𝑜 𝑃𝑒
𝑟1 =
1 + 𝐾3 𝑃𝑜 + 𝐾4 𝑃𝑒

𝐾2 𝑃𝑜 𝑃𝑒
𝑟2 =
1 + 𝐾3 𝑃𝑜 + 𝐾4 𝑃𝑒

Table 4.1.1.3 : Specification of the reaction in a fixed bed reactor

Catalyst Silver supported on alumina, promoted by a Calcium

additive [7]
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

Table 4.1.1.4: 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)

Based on the table 4 below, the most suitable catalyst that can be used is silver
catalyst due to high conversion of ethylene and high selectivity. 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.
 Table 4.1.1.5: Summary for Comparison

Catalyst Silver Supported on Alumina,

Silver with alumina
Condition Promotedby Calcium Additive

Operating Temperature 428 F to 500 F 210 C to 292 C

Operating Pressure 330 psig 1 atm

Conversion based on 5.53% 70%

ethylene

Selectivity Selectivity: 73% 50.3 %

Reactor Plug flow reactor Fixed bed reactor

4.1.2 REACTOR DESIGN

Most of the modern ethylene oxide production based on oxygen-based reaction using

fixed-bed reactor (plug flow reactor). It is because of four main reason. 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.

PFR is one of the ideal reactors which provides higher conversion. In an ideal PFR,
there is no mixing along the axial length although there would be lateral mixing of the
reactants along the radial direction. PFR is a reactor where the concentration of the reactant is
maintained high as it flows from one end to another. Hence PFR is mostly preferred for
positive order (n>1) reactions. When the rate of reaction is maintained higher, volume of the
reactor would be greatly reduced., thereby minimizing the total fixed and variable costs.

A packed bed reactor (PBR) is preferred for heterogenous reactions, where the solid-
fluid contact greatly influences the rate of reaction. 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. In
the case of PBR, there are conditions which makes the reactor a non-
ideal. Channelling and dead zones are the conditions which leads to non ideal reactor
conditions. These conditions are more prevalent in a PBR. A non- ideal reactor conversion
will always be less than an ideal reactor. [8]

Therefore in this case, plug flow reactor is more suitable reactor in this case. [3][5]

3.2 Calculation

Assumption

1) The reactant is pure reactant.

2) Pure oxygen is used as feed instead of air.

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) Agency for Toxic Substances and Disease Registry (ATSDR). Toxicological Profile for
Ethylene
Oxide. U.S. Public Health Service, U.S. Department of Health and Human Services,
Atlanta, GA.
1990. https://www.atsdr.cdc.gov/toxprofiles/tp137.pdf

6. U.S. Environmental Protection Agency. Evaluation of the Inhalation Carcinogenicity of Ethylene

Oxide (CASRN 75-21-8) In Support of Summary Information on the Integrated Risk
Information
System (IRIS). National Center for Environmental Assessment, Office of Research and
Development.
Washington, DC. EPA/635/R-16/350Fa. 2016.
https://cfpub.epa.gov/ncea/iris/iris_documents/documents/toxreviews/1025tr.pdf

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. Reactor design ,44 (1), pp21-30

APPENDIX

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