Acknowledgment

This is an assignment for the course Chemical Process Simulation and Design (EP313)

using Unisim software (Version R 390) by Honeywell. Throughout the semester, we have acquired

the soft skill of using Unisim to create steady-state and dynamic models for plant design,

performance monitoring, troubleshooting, business planning, and asset management.

In order to complete the assignment, we have seek for a lot help and guidance from lecturer.

Here, we would like to grab this opportunity to express our thankfulness and gratitude to our

lecturer, Mr MohdNazri bin MohdFuad, from the Faculty of Engineering, Technology and Build

Environment (FETBE), UCSI University. Numerous consultations and patient was given to us in

answering each of our doubt.

We would like to extend our gratitude to all those who has contributed successfully in

completing this assignment. Furthermore, our team members had always suggested valuable

amendments and comments to improve this assignment.

My appreciation and gratitude are extended to Director and Head of Department of

Chemical Engineering from UCSI University for including Chemical Process Simulation and

Design courses in such a way that students are not only study from the book but also acquired soft

skill knowledge that able to be applied in future career industry.

Chapter 1: Introduction

1.1 Objective

- To design and simulate Ethylene Oxide plant using Unisim software

- To understand the processing steps and operating condition for the production

- To achieve the target production of mass flow rate and purity of Ethylene Oxide

1.2 Properties of Ethylene Oxide

(a) Physical properties

Name Ethylene oxide

Other name Ethene oxide, Oxtrane

Structural formula CH2OCH2

Molecular weight 44.053

Critical pressure 7191 kPa

Boiling point 286.3°K

Vapor Pressure 1094 mm Hg at 20 ᵒC

Vapor Density 1.52

Density 0.8711 at 20/20 ᵒC

Gibbs energy of formation - liquid -267 kJ/kg

Heat of formation - liquid -1766.5 kJ/kg

Standard heat of combustion, liquid (HHV) -29076 kJ/kg

Standard heat of combustion, gas (LHV) -27649 kJ/kg

Standard heat of combustion, gas (HHV) -29647 kJ/kg

Decomposition temperature (at 760mmHg) -773°K

(b) Physical properties of aqueous ethylene oxide solutions

EO Content Melting point (°C) Bubble point (°C) SG at 10/10°C (Flash

wt% point)

0 0 100 1.0000

0.5 - - -

1 -0.4 - -

2 - - -

3 -1.3 - -

5 -1.6 58 0.9977

10 5.6 42.5 0.9944

20 10.4 32 0.9816

30 11.1 27 0.9658

40 10.4 21 0.9500

60 7.8 16 0.9227

80 3.7 13 0.9005

100 -111.7 10.4 0.8828

(c ) Heat of reaction of Ethylene Oxide reaction at 25°C

kJ/kg

Combustion

Liquid HHC -29,076

Gas LHC -27,649

 Gas HHC -29,647

Decomposition -3051

Isomerization to acetaldehyde -2621

Polymerization -2324

Hydrolysis -2064

1.3 Identification of raw material

Basically the production of ethylene oxide is from oxidation of ethane, raw material used

are only ethylene and pure oxygen gas. It is done through a process known as direct oxygen

process. In 1914, BASF has manufactured the first ethylene oxide using ethylene chlorohydrin

(reaction of ethylene chlorohydrin with calcium hydroxide) as an intermediate, and now it is

replace with direct oxidation process as this route tends to produce higher yields and less downtime

(ICIS, 2010). Below proposed with the physical properties of ethylene with meet the specific

condition requirement for the process.

(a) Physical properties of ethylene

Ethylene

Formula C2H4

Molecular Weight (lb/mol) 28.05

Critical Temp. (°F) 49.1

Critical Pressure (psia) 742.7

Boiling point (°F) -154.8

Melting point (°F) -272.5

Psat @ 70°F (psia) Signifies at 70°F, the compound is above its

critical temperature

Liquid Density @ 70°F (lb/ft3) Signifies that at 70°F, the compound is below

the normal boiling point and only the

equilibrium vapor is present at 1 atmosphere

Gas Density @70°F 1 atm (lb/ft3) 0.0730

Specific Volume @ 70°F 1 atm (ft3/lb) 13.70

Specific Gravity 0.992

Specific Heat @ 70°F (Btu/lbmol-°F) 10.28

(b) Physical properties of oxygen

Oxygen

Formula O2

Molecular Weight (lb/mol) 32.00

Critical Temp. (°F) -181.8

Critical Pressure (psia) 729.1

Boiling point (°F) -297.3

Melting point (°F) -361.9

Psat @ 70°F (psia) Signifies at 70°F, the compound is above its

critical temperature

Liquid Density @ 70°F (lb/ft3) Signifies at 70°F, the compound is above its

critical temperatur
 Gas Density @70°F 1 atm (lb/ft3) 0.0828

Specific Volume @ 70°F 1 atm (ft3/lb) 12.08

Specific Gravity 1.1

Specific Heat @ 70°F (Btu/lbmol-°F) 7.03

In direct oxidation process, the silver alumina catalyst is used as well to increase the rate

of reaction and increase the conversion rate. Silver catalyst was investigated to support on a

series of alumina which they were pretreated at different temperature between 300-1800°C

before entering the conversion reactor for ethylene oxide production process. Steady activity and

selectivity at a set of reaction conditions were depends on the surface area of catalyst which was

a function of the thermal treatment of alumina.

1.4 Identification of product and its current market needs

Ethylene oxide is known as oxirane (by IUPAC) which is an organic compound, which is

a colorless and flammable gas by direct oxidation process of ethylene in the presence of a silver

catalyst. Due to its molecular structure, ethylene oxide is easily involved in addition reaction, thus

allowing it to be easy polymerized into larger compound. Therefore, it has a range of uses in the

chemical sector.

Figure 1: Molecular structure of ethylene oxide

The major industrial appliances of ethylene oxide as a raw material in their production or

intermediates, listed below: (Shell Chemicals, 2009)

(i) Ethylene glycols – used to produce antifreeze, polyester and polyethylene

terephthalate (PET)

(ii) Polyethylene glycols – used to make perfume, cosmetics and pharmaceuticals

(iii) Ethylene glycol ethers – used as key component of brake fluids and paints

(iv) Ethanol amines – used in produce soap and detergent

(v) Ethoxylates – used in produce detergent, surfactant and emulsifiers

From above, the synthesis of ethylene glycols is the major application of ethylene oxide

worldwide. It’s share of overall uses from various region in the world, such as, from 44% in

Western Europe, 63% in Japan, and 73% in North America to 90% in the rest of Asia (Chemical

Intelligence, 2009).

From the Transparency Market Research publication, growth will be sustained by robust

demand for PET resins and polyester fibers, as well as demand for automotive antifreeze. In year

2011, the value of ethylene oxide market is at $29 billion dollar, compound annual growth from

year 2013 to 2018 is projected at 5.7%, thus, at the end, the market of ethylene oxide will valued

at $42.6 billion by the end of projected period.

Figure 2: Pie chart of

ethylene oxide in 2017

From the pie chart above, the most dominant country of using ethylene oxide is Asia Pacific in

terms of volume as well as revenue. This scenario is mostly due to industrialization progress in

Asia Pacific region which is foreseen to reach $49 billion dollar by 2020. Follow by North America

region, those countries in the region also setting up their plant and focus on the growth of this

compound since robust demand from the appliances of PET.

1.5 Identification of processing steps

In this assignment, the process selected is direct oxidation process from ethylene using silver

alumina catalyst. All ethylene oxide direct oxidation plants are based on the original process

chemistry discovered by Lefort in 1931. The direct vapor-phase oxidation of ethylene to ethylene

oxide over a silver catalyst at 220-300°C and 10-30 bar pressure produces few bi-products other

than carbon dioxide and water.

Figure 3: Process Block Diagram

The reaction between ethylene and oxygen occurs under a pressure of 101.3kPa and 225°C in a

conversion type of reactor.

The major reactions are:

(i) main reaction: 2C2H4 + 2O2 → 2 C2H4O

(ii) side reaction: C2H4 + 3 O2 → 2CO2 + 2H2O

High purity oxygen is mixed with fresh ethylene and fed into a conversion reactor with

conversion rate of 15%. The effluent gas, containing ethylene oxide is not pure enough and is

mixed with other composition of products. These effluent is heat exchanged with cold reactor fed

gas before it enters the absorber to continue on the separating process. In the absorber, the

ethylene oxide is dissolved in the absorber water to produce a dilute aqueous solution and then is

compressed to proceed to stripper column. The vapor product from the stripper column is sent to

carbon dioxide stripper to strip out the carbon dioxide gas, while the liquid product is sent to

another stripper column to strip out high purity ethylene oxide form water. Another distillation

column is need to get more purifier ethylene oxide, which is 99.5% purity. The bottom distillate

product from the column will be water, these water from stripper column and distillation column

will recycle back to be used in absorber.

The main disadvantage and inefficiency of the direct oxidation process is the lower

selectivity of ethylene oxide per unit of feed ethylene consumed, result from the loss of 20-25%

of the ethylene to carbon dioxide and water. Though, in this process, the carbo dioxide will be

recycle back.
1.6 Identification of reactor type and reactor’s operating condition

There are few types of reactor in Unisim software. The type of reactor applied in this

manufacturing process is conversion reactor. This reaction is the simplest reaction type that can

be simulated, since it does not require any thermodynamic knowledge, just to input the correct

stoichiometry and conversion of the basis reactant.

There are two major reaction occurs in this process, one is the stoichiometric reaction,

when two moles of ethylene react with half mole of oxygen will produce one mole of ethylene

oxide with the conversion rate of 15%. When ethylene is reacts with excess oxygen, which is one

mole ethylene and three moles oxygen with the conversion rate of 5%, side products will formed

such as carbon dioxide and water.

The selectivity of ethylene oxide from this reaction is set to be 75% and 25% selectivity

of carbon dioxide to achieve 99.5% purity of product obtained.

For the reactor, the reaction has to be set optimum temperature and pressure to ensure the

conversion of ethylene to carbon dioxide is in a right amount in order to obtain the target 99.5%

purity of ethylene oxide. A low reaction temperature is chosen as 225°C with 101.3kPa to ensure

higher yields are obtained towards the end of process with silver alumina as catalyst in the

reaction.

1.7 Identification of separation methods and operating conditions

In direct oxidation process of ethylene to produce ethylene oxide, after the conversion

reaction, the effluent products might not pure enough, thus, several separators need to be

introduced to obtain high purity ethylene oxide. Such as, after the conversion reactor, the effluent

products is heat exchanged with cold reactor fed gas and enter to the absorber at 50°C and
101.3kPa. In the absorber, the ethylene oxide is dissolved in absorber water to produce a dilute

aqueous solution. The top vapour product from the absorber which contains higher mole fraction

of ethylene is sent to stripper column to strip out the carbon dioxide, left unreacted ethylene. The

bottom liquid product from the absorber send to another stripper column to strip out ethylene

oxide from water. Both the product gases from the absorber enter the stripper column at around

28.52°C and 101.3kPa. Finally, the ethylene oxide from the stripper column is not totally pure,

thus, it is sent to distillation column again to separate ethylene oxide and water. The temperature

and pressure operating for the distillation column is 30°C and 80kPa respectively. Both water

from the stripper column and distillation column are recycled back to use in the absorber.

Chapter 2: Methodology

1. Identification of Chemical Components

For producing the ethylene oxide, reactant and product were added in the main

component list in Unisim which are ethylene, oxygen , ethylene oxide, water and Carbon

dioxide.

Figure 1 : Identification of chemical components

2. Selection of fluid package

Fluid package is crucial for calculating the thermodynamic or fluid properties of the

components in simulation. Hence, for this case study, PRSV was selected as the fluid

package in Unisim.

Figure 2: Selection of PRSV Fluid package

3. Setting up the reactions

There are one main reaction and one side reactions. The main reactions is where the

ethylene reacts with oxygen gas to produce ethylene oxide. The side reaction is where the

ethylene reacts with oxygen gas to produce carbon dioxide and water. The total

conversion for the ethylene is 20% where the selectivity of ethylene oxide is 75% and the

selectivity for carbon dioxide is 25%. Hence, the conversion for each reaction side is

calculated by multiplying the total conversion with the selectivity. The conversion for

ethylene in main reaction is 15% where for side reaction, the conversion is 5%. These

values are added into Unisim to set the conversion for both reaction.
 Figure 3 and 4: The main reaction and side reaction and their conversion

4. Process model Development

Figure 5: The Process Model Development

Firstly, two feed streams which were ethylene and oxygen were added into Unisim as

the reactant. Then, the oxygen was compressed and mixed with the ethylene to become one

stream. The stream was then heated to compensate with the conversion reactor’s operating

conditions. The conversion reactor was set with the reaction set (one main reaction and one

side reaction) in order to simulate the reaction. After the reactor, the output stream was in

vapor fraction and consists of the mixture of product and reactants.

 The vapour stream was then cooled down and transferred to the Carbon dioxide (CO2)

Absorber where the top inlet was the water source and the bottom inlet was the stream from

the reactor. After passing through the absorber, product which was ethylene oxide was

carried away with the water stream to the bottom outlet where the unreacted reactants and

the side product gases which was carbon dioxide were coming out on the top of the carbon

dioxide absorber. The gas stream from the top of the absorber was then transferred to the

Carbon dioxide (CO2) stripper to remove the remaining Carbon dioxide from the stream

which left with the unreacted reactants. These unreacted reactants would be sent to another

similar plants as the reactants.

The bottom outlet stream from CO2 absorber was then transferred to the water stripper

to remove any water inside the stream where total of 91% water content is removed and

recycled back to the top of CO2 absorber to reduce the water usage. The top product from

the water stripper would mainly consists of Ethylene oxide and small amount of water.

Then, it was transferred to the distillation column to separate the ethylene oxide and the

water where the reflux ratio, pressure and temperature were adjusted to achieve the target

purity of the ethylene oxide in top outlet.

5. Simulation of base case operation to achieve target production (50000 metric tons per

year with 99.5 purity of ethylene oxide)

a) Feed stream

Two feed streams which were ethylene and oxygen was added in Unisim with the same

temperature and pressure condition around 25oC and 1.013bar. The molar flow rate was

adjusted to 1000kgmole/hr and 500 kgmole/hr for ethylene and oxygen respectively.
 Figure 6 and 7:- The properties of the feed stream

b) Compressor , mixer and heater

The oxygen was then compressed to 16.6 bar with 75% adiabatic efficiency. The

compressed oxygen was then mixed with the ethylene to form mixed stream and heated

up to 225oC to achieve the requirement for the reactor’s operating conditions.

Figure 8 : The inlet for entering the conversion reactor.

c) The Conversion reactor

For the conversion reactor, the reaction set was added into the reactor and energy

stream was attached to produce products with specific temperature. In Unisim, 300o

C was added into the vapour outlet of the reactor. The heat stream for the reactor

obtained was negative which indicated that the reaction is exothermic where it released

heat from the reactor in order to achieve the outlet temperature that specified.
 Figure 9 :- The properties of vapour outlet

Figure 10:- The composition obtained after the reactor.

d) Cooler and CO2 absorber

In order to conserve the energy, Cooler was added to reduce the vapour temperature to

around 50oC where the heat stream from the cooler can be used for heat recovery. Then,

the stream was attached to the CO2 absorber at the bottom inlet where water inlet with

molar flow of 1x106 kgmole/hr was attached on the top inlet of the absorber in order to

separate the ethylene oxide and the by-product away.

 Figure 11:- The mass flow for each components in bottom products.

Figure 12:- The mass flow for each components in upper products.

e) Water Stripper and CO2 Stripper

In Unisim, there is no simulation object for stripper to be operated. Hence, component

splitter would be used to be represented as the stripper where it would separate any

unwanted components from the stream. For water stripper, it would be separate the

water at the bottom product around 99% of water content in order to recycle the water

back to the CO2 absorber. The top product would be mainly ethylene oxide and

remaining water content. For CO2 stripper, it would be remove any remaining CO2

from the gas stream and left with the unreacted gases so that it can be sent to another

similar plant as reactants. In Unisim, the split was adjusted in order to simulate like the

stripper functionality.
 Figure 13, 14 and 15:- The properties of the oulet and its configuration for the water

Stripper

Figure 16, 17 and 18:- The properties of the oulet and its configuration for the CO2

Stripper

f) Distillation Columns

The most crucial equipment in the process as it would help in separating the

components and also increase the purity of the ethylene oxide production. In Unisim,

The number of stages were 10 where the inlet stage was at stage 5 from the top. The

condenser pressure was configured at 0.78 bars and 0.98 bars for reboiler pressure

where the pressure drop was around 0.2 bars. For the parameter in the monitor section,

the reflux ratio was adjusted to 0.35 and the component mole fraction is 0.995 for

ethylene oxide on the top outlet. Top product would be ethylene oxide where the bottom

product would be the water which would be mixed with the recycle stream and recycled

back to the CO2 absorber.

Figure 19, 20, 21 and 22:- The configuration of distillation column and its product

Hence, the mass flow obtained for the ethylene oxide was around 6124.4 kg/hr.

Assume operating day for one year is 342 days.

𝑘𝑔 1 𝑚𝑒𝑡𝑟𝑖𝑐 𝑡𝑜𝑛𝑠 𝑑𝑎𝑦 ℎ𝑜𝑢𝑟𝑠

Mass flow = 6124.4 ℎ𝑟 𝑥 𝑥 342 𝑦𝑒𝑎𝑟 𝑥24
1000 𝑘𝑔 𝑑𝑎𝑦

= 50269.0752 metric tons per year.

≅ 50000 𝑚𝑒𝑡𝑟𝑖𝑐 𝑡𝑜𝑛𝑠 𝑝𝑒𝑟 𝑦𝑒𝑎𝑟.

Hence , purity of 99.5% with 50000 metric tons per year of ethylene oxide was

produced based on this simulation.