Manufacturing of Ethylene

Oxide

B.Shankaran Guide: Dr.Joshua amarnath

Reg. no: 3019820 HOD, Chemical department
Abstract
This project deals with the Manufacturing of Ethylene
oxide produced by the “Process of direct oxidation of
ethylene”. This method is by far the most widely used method
for the production of ethylene oxide. The reliability of the
process makes it popular. Furthermore, it can be used in plants
that manufacture ethylene oxide and glycols together.

Material balance, Energy balance for Reactor, and

distillation column is carried out. Further we deal in with the
design of Distillation column and for the above said process
in order to produce 100 tons per day of Ethylene oxide. Also
various aspects of the process like material of construction,
health and safety, storage and handling is also discussed along
with Plant economics.
Aim and scope

The objective of the project work is to study the

manufacturing method available for the manufacturing of
Ethylene oxide. This work is also aimed for meeting the
production requirement and to meet the superior quality of the
product which is an important ingredient in intermediate for
many organic syntheses.

This study helps to have insight idea about the

manufacturing of Ethylene oxide. This study also helps to
optimize the manufacturing of Ethylene oxide. This process
increase EO production by supplying oxygen for better
utilization of the system and also reduce the inert gases
quantity in the process to avoid environmental pollution.
Introduction :
• Ethylene oxide, also called oxirane , is the organic
compound with the formula C2H4O.

• It is a cyclic ether, colorless flammable gas with a

faintly sweet odor, three- membered ring consisting
of two carbon and one oxygen atom.

• Because of its special molecular structure, ethylene

oxide easily participates in the addition reaction ,
opening its cycle, and thus easily polymerizes .

• Ethylene oxide is isomeric with acetaldehyde. Today

about 9.6 x 106 tones of ethylene oxide are produced
each year worldwide.
Uses:
• Ethylene oxide is used in production of ethylene
glycol and higher alcohols. As a pharmaceutical
intermediate it is used in the synthesis of chorine,
thiamine and procaine.

• In mixtures with carbon dioxide and halogenated

propellants, finds wide use as a fumigant for food
and cosmetics.

• Derivatives of EO (especially ethylene glycol ) are

commonly used in the plastics industry for
manufacturing bottles and to produce polyester
fibers for clothing and furniture
Methods of Production :
• Ethylene oxide has been produced commercially by
two basic routes
1. From ethylene chlorohydrin (2- chloro ethanol).
2. Direct oxidation process.

• The direct oxidation technology, as the name

implies, utilizes the catalytic oxidation of ethylene
with oxygen over a silver based catalyst to yield
ethylene oxide.

• The process can be divided into two categories

depending on the source of the oxidizing agent. The
air-based process and the oxygen based process .
Flow diagram:
Process Description
• Fresh ethylene and oxygen are combined with a
recycle stream containing unreacted ethylene,
carbon dioxide, nitrogen, and traces of water vapor.

• The combined stream is fed to a reactor, operating

between 225 and 280 °C. The system pressure is
10 atm. The ethylene in the reactor feed must be
maintained between 5 to 10% for satisfactory
catalyst operation.

• The single pass conversion in the reactor may be

adjusted between 20 and 95% to optimize unit
performance.

• The reactor effluent is cooled and sent to an

absorber operating at 35°C.
• Essentially all of the ethylene oxide is absorbed.
Water is fed to the absorber in a 10:1 water : EO
ratio.

• The water-EO mixture is distilled to obtain pure

ethylene oxide product. The gas stream leaving the
absorber is recycled.

• A portion of the recycle stream is purged so that

excessive amounts of nitrogen and carbon dioxide
do not build up in the system.
Material balance:
• The two reactions taking place in this process are
given below.
C2H4 + ½ O2 -----→ C2H4O (main reaction)
C2H4 + 3O2 -----→ 2CO2 + 2H2O (side reaction)

• Component Molecular weights:

Ethylene 28
Oxygen 32
Ethylene oxide (EO) 44
Carbon dioxide 44
Water 18
Nitrogen 28
• Total ethylene oxide to be produced = 100 TPD.
= 100000 Kg/ day.
= 4166.67 Kg/ hr.
Basis: 1 Hour of operation
REACTOR:
• Assuming 2% of the EO produced is lost during the
production.
• Total EO to be produced = 4250 Kg/ hr.
= 96.59 Kg moles/ hr.
• Assuming a conversion of 50% of ethylene fed and
in that 25 % of the ethylene is converted into
ethylene oxide.
• Air to Ethylene ratio is 10:1
 Material Balance For The Reactor

IN Kg OUT Kg

ETHYLENE 10818.1 ETHYLENE OXIDE 4250

OXYGEN 103148.37 ETHYLENE 5409.06

NITROGEN 5032.63 OXYGEN 92330.29

NITROGEN 5032.63

CARBON DIOXIDE 8500

WATER 3477.24

TOTAL 118999 118999

EO SCRUBBER:
• The solubility of EO in water is infinity. So the
amount of water required for the absorption of EO is
the equal amount of EO produced.
• Water used for absorption = 4250 X1.10 = 4675 Kg/hr
(10 % of extra water is used to scrub all the EO
produced.) Total EO scrubbed = 4250 Kg/ hr

Solubility data:
Component Solubility (Kg/ Kg of water)
Nitrogen 1.346 X 10-5
Carbon dioxide 1.379 X 10-3
Oxygen 2.870 X 10 -5
Ethylene 1.482 X 10-2
 Material balance of EO scrubber
IN Kg OUT Kg

ETHYLENE OXIDE 4250 ETHYLENE OXIDE 4228.8

ETHYLENE 5409.06 ETHYLENE 69.28

OXYGEN 92330.29 OXYGEN 0.134

NITROGEN 5032.63 NITROGEN 0.0629

CARBON DIOXIDE 8500 CARBON DIOXIDE 6.4
WATER 3477.24 WATER 8152.24
ABSORPTION
WATER 4675 RECYCLE STREAM 111217.5

TOTAL 123674 123674

RECYCLE STREAM FROM SCRUBBER

IN Kg

ETHYLENE OXIDE 21.2

ETHYLENE 5340

OXYGEN 92330.156

NITROGEN 5032.56

CARBON DIOXIDE 8493.6

TOTAL 111217.5
EO DESORBER:
The amount of water used for absorbing the ethylene oxide in
the absorber is desorbed in the desorber and recycled. 0.5% of the
produced ethylene oxide is also lost with the water.
Material Balance Of EO Desorber

IN Kg OUT Kg

ETHYLENE OXIDE 4228.8 ETHYLENE OXIDE 4206.8

ETHYLENE 69.28 ETHYLENE 69.28
OXYGEN 0.134 OXYGEN 0.134
NITROGEN 0.0629 NITROGEN 0.0629

CARBON DIOXIDE 6.4 CARBON DIOXIDE 6.4

WATER 8152.24 WATER 3477.24

RECYCLE WATER 4675

EO LOST 21.14

TOTAL 12456.92 12456.92

STRIPPER:
Steam at a pressure of 1.5 bars is used for stripping the
vent gases.
Material Balance Of Stripper

IN Kg OUT Kg

ETHYLENE OXIDE 4206.8 ETHYLENE OXIDE 4206.86

ETHYLENE 69.28 ETHYLENE 3477.24

OXYGEN 0.134 WATER 69.28

NITROGEN 0.0629 VENT GAS 6.596

CARBON DIOXIDE 6.4
WATER 3477.24

TOTAL 7760.776 7760.77

 Vent Gas From Stripper

OUT Kg

CARBON DIOXIDE 6.4

NITROGEN 0.0629
OXYGEN 0.134

TOTAL 6.596
 Material Balance Of Distillation Column

IN Kg OUT Kg

ETHYLENE OXIDE 4206.8 ETHYLENE OXIDE 4166.67

WATER+ HEAVY
WATER 3477.24 ENDS 3586.77

ETHYLENE 69.28

TOTAL 7753.38 7753.38

 ENERGY BALANCE
Reactor:
Energy Balance Equation For The Reactor
(m*C p *∆T) Reactants + ∆H +Q ( exo . reaction)
=(m*C p *∆T) Products

Consider feed entering at 25°C:

T ref = 25°C
∆T = 25 – 25 = 0 (m*C p *∆T)Reactants = 0
Q = heat released by exothermic reaction.
Tr is the reaction temperature = 280 °C

∆HR = heat of reaction (E—› E.O) + heat reaction of the side

reaction (m*C p *∆T)products = [(m1* Cp1 )E + (m2* Cp2 )O2 +
(m3* Cp3 )EO + (m4* Cp4 ) CO2 + (m5* Cp5 )N2 + (m6* Cp6 )H2O]
[ Tproducts - Tref ] ∆T
 = [280 – 25] = 255 °C ∑(m*C p *∆T)products
= [4250*1714.54 + 5409*2409.25 + 1065.6*5032
+8500*1046.88 + 92330*988.3 + 1858*3477][255]
= 3.37 *1010 Joules.
∆HR = 1.1058*1010 (for EO) + 1.37*1011
= 1.478 * 1011 Joules ( by constant )

Heat to be removed = ∆HR - ∑ m*C p *∆T

= 1.478*1011 – 3.37*1010
= 1.14*1011 Joules.

Reactor water jacketing

Water (boiling is used for the removal of the heat) (m*Cp*∆T) water
= 1.141*1011 Cp of water = 4180 Joules/Kg-K
∆T= 90 – 25 = 65°C.
(m) water = 420000 Kg .
ENERGY BALANCE FOR THE COOLER 1 :

In the cooler the products vapors' are cooled from

280°C - 35°C. The removed energy is supplied to the recycle
stream. The Cp values are calculated at the temperature of
35°C.

∑(m*C p *∆T)products leaving the cooler

= [4250*1102.95 + 5409*1769.14 +92330.20*918.52 + 8500*858.23
+ 5032.6*1040 + 3477.24*4180][35-25]
= 1.27*109 Joules .

∑(m*C p *∆T)products entering the cooler

= 3.37*1010 Joules .
Therefore heat removed in the cooler
=3.37*1010 –1.27*109 = 3.243*1010 Joules
ENERGY BALANCE TO THE COMPRESSOR 1 in vol %

Average density = 0.026*851.61 + 0.052*212.21+ 0.77*435.36 +

0.052 *464.64 + 0.048*314.076 + 0.052* 993.719
= 157.61 Kg/m3
Work required in the compressor to increase the pressure from
5 - 10 atm
W1 = V*(P1- P2 ) = 3.82 * 108 Joules.

This work will be added to the enthalpy.

So the increase in enthalpy= 1.270*109– 3.82*108

Therefore, the energy leaving the compressor1
= 1.625*109 Joules .
ENERGY BALANCE TO THE ABSORBER :

In the absorber the ethylene oxide is completely absorbed

in the water at 25°C. Only the energy is lost from the gases,
which are not absorbed in the absorbing liquid.
Energy entering the absorber = 1.625*109 Joules.
Energy loss from the absorber = 5340*1769.14 + 92330.156*918.52
+ 21.2*1102.95 +
8493.6*858.23 + 5032.56*1040
= 1.06*108 Joules .
Therefore, energy leaving the absorber with the products
= 1.519 *109Joules

The energy leaving the cooler1 with the recycle stream

= 6.33 * 1010 Joules
ENERGY BALANCE FOR THE DESORBER :
In the desorber the water used for the absorption is
desorbed, the energy loss is the work done by the
compressor 1. Because the desorber is working at pressure of
5 atm.
The energy leaving the desorber = 1.164 * 109 Joules

The energy lost in the desorber = 3.82 * 108 Joules.

ENERGY BALANCE FOR THE COOLER2 & COMPRESSOR2

The cooler is used to maintain the temperature of the

absorbing water at 25°C. In the compressor the fed stream is
compressed to 5 atm .

Energy leaving the compressor = 1.167 * 109 Joule

ENERGY BALANCE FOR THE STRIPPER :
In vaccuum stripper the gases will be vapourized from
water. This is done at constant temperature. So there is no
energy balance for the stripper.
The energy leaving the stripper = 1.167*109 J

ENERGY BALANCE FOR THE DISTILLATION

COLUMN :

Enthalpy of feed to the distillation column,

HF = 1.167*109 J
Temperature of the feed = 35°C

From the T-x-y dia. for the Ethylene oxide (EO)-water system.

The bubble point = 55°C Dew point = 93°C

Enthalpy of the gas , HG= yEO *( CpEO *MEO*(TG-TF ) + λEO ) +
yH2O*(CpH2O*MH2O*(TG-TF ) + λ H2O)

M is the molecular weight of the species, y is the mole fraction, λ

is the latent heat of vaporization of the components.
HG = 0.33*[2.17*44*(93-25)+44*461.45]+
0.67*[18*4.18*(93-25)+2154.79]
=37942.4KJ/ K moles
HG = 1.427*106 J

Cooling water required in the condenser

M*Cp*∆T=1.427*106 J
Water is getting cooled form 50°C to 25°C
M = 1.427*106 J/(4180*25)
= 13.65 Kg/hr
HD = yEO *[ CpEO *MEO*(35-25)] + yH2O*[CpH2O*MH2O*(35-25)]
C p is liquid enthalpy.

HD = 39030.64 J

HL0 = 39030.64 J

Condenser duty = QC = HG – HL0 – HD = 1.35*106 J

Enthalpy of the residue, Hw = 3600.33*4.18*(55-35)

= 301*103 J

Reboiler duty = QB = D*HD + W*Hw - F*HF + QC

= 1.17 *105 J
 DESIGN OF EQUIPMENTS

DESIGN OF A SIEVE PLATE DISTILLATION COLUMN :

Distillation column pressure = 1 atmosphere (absolute).

The feed entering is a mixture of 193.18 Kmole of water &

ethylene-oxide. The distillate is 99.9 mol% pure ethylene oxide
and the residue will contain 0.1 mole% ethylene oxide.

Detailed design: Basis 1Hour operation

Total pressure = PT = 1 atm
 Summary Of Distillation Column
1. Number of Plates in enriching section = 4
2. Number of plates in stripping section = 9
3. Feed plate = 6th plate
4. Plate spacing = 600 mm
5. Height of the column = 9 meters
6. Diameter of the column = 0.75 meters
7. Hole diameter = 5 mm
8. Hole pitch, triangular = 15 mm
9. Tray thickness = 3 mm
10. Number of holes = 1385
11. Weir length = 60 cm
12. Weir height = 5cm
13. Flooding permitted = 80%
14. Down comer back up (with aeration) = 532 mm liquid
15. Down comer back up (without aeration) = 319.0 mm liquid
16. Enriching efficiency = 54.3%
17. Stripping section efficiency = 34.1%
Design of Absorber

Absorber system MEA is used as the absorber and its

14.5% in solution .Amount of gas components present in
absorber before entering the packed column is given by:

Gas composition Mol.Wt vol% kmol

Ethylene 28 190.71 5340

Oxygen 32 2885.31 92330.15
Ethylene oxide (EO) 44 0.4818 21.2
Carbon dioxide 44 193.036 8493.6
Nitrogen 28 179.73 5032.56

Assumption made in this type of absorber is that only co2

is absorbed and all other gases act as a inert in 14.5% MEA
solution.
Column diameter calculation:

From table 18-5 ,page 18-23, of perry

We get
Dp = 38 mm ε = 0.80
Specific surface area = 195 m2/m3 Fp = 170
Now we have
L/G x (ρg/ρl)1/2 = (63.09/12.48)X(0.626/992.06)0.5 = 0.126

Area of cross section ,Ac = 6.45 m2

Diameter of absorber ,Dc = 2.866m

Also to ensure, there is proper wetting column diameter

should be at least 10 times greater then packing diameter and
above value of column diameter satisfies the given condition.
Degree of wetting

We have to calculate the degree of wetting rate

Lw = L/Agρla1
Lw = 63.09/6.45x992.06x195
Lw = 1.24 ft3/hr.ft
Thus wetting is under the specified limit and proper
distribution of liquid is taking place.

Tower height calculation

Z =HOG.NOG
HOG= HG + m.(Gm/Lm).Hl
NOG =∫ (1-Y)cm/(1-Y)(Y-Y*)
NOG =1/2(ln(1-Yt)/(1-Yb)) +∫ dy/Y-Y*

Height of Absorber = 10.4 m

 Summary of absorber design:

Area of cross section ,Ac = 6.45 m2

Diameter of absorber ,Dc = 2.866m
Degree of wetting rate , Lw = 1.24 ft3/hr.ft
Height of Absorber , Z = 10.4 m
 COST ESTIMATION

Production per year = 30000 ton /year

Cost of product = Rs1,00,000 / ton
Gross sales for one year = 30000*100000
= Rs 300 cr
Fixed capital investment = Rs 300 cr

Fixed capital = Direct cost + Indirect cost

Direct Cost
It is taken as 70% of fixed capital = Rs 210 cr

Equipment Cost = Rs 75 cr
Land Cost = Rs 3 cr
Installation & Painting Cost = Rs 30 cr
Instrumentation Cost = Rs 11.25 cr
Electrical cost = Rs 26.25 cr
Building, Process & Auxiliary = Rs 30 cr
Service Failures & Yard Improvement = Rs 31.5 cr

Indirect Cost
Engg Supervision = Rs 42 cr
Construction Expenses = Rs 10.5 cr
Contigency = Rs 10.5 cr

Estimation Of Production Cost

Total annual income = Rs.300 cr
Total gross earnings = Rs 90 cr
Production cost = Total annual income - Gross earnings
= 300- 90
= Rs 210 cr
Manufacturing cost =Direct cost + Fixed charge + Plant overhead

Direct Production Cost = Rs 157.5 cr

Raw Material = Rs 42 cr
Operating Labour = Rs 31.5 cr
Direct Supervising & Clinical Labour = Rs 13.65 cr
Utility = Rs 21 cr
Maintenance & Repaire = Rs 31.5 cr
Operating Supply = Rs 4.2 cr
Patents & Loyalties = Rs 31.5 cr
Fixed Charge = Rs 42 cr

Depreciation Cost
For machinery = Rs 30 cr
For building = Rs 9 cr
Insurance Cost = Rs 30 cr
Rent Value = Rs 6.3 cr
Plant Overhead = Rs 10.5 cr
General Expenses = Rs10.5 cr
Distribution & Selling Cost = Rs 14.7 cr
Research & Development = Rs 2.1 cr
Financing = Rs 4.2 cr
Lab Charge = Rs 69.3 cr
Gross Earning Cost
Tax payable = Rs 27 cr
Net Profit = Total gross earning - tax payable
= 90 - 27 = Rs 63 cr
Depreciable fixed capital investment
Pay Back Period = ------------------------------------------------------
( Avg. profit + Avg. depreciation)
= 300 / ( 63 + 39 )
= 2.94 years
 SUMMARY AND CONCLUSION

In this project, manufacturing of Ethylene oxide by “Direct

oxidation of ethylene” was discussed in detail. And quality
improvement of the product by a Sieve Plate distillation column
was also dealt. Mass and energy balance calculations, design
of distillation column and design of absorber were done by
which product quality is increased and environment pollution is
reduced.

This product is used as a Intermediate for many organic

syntheses due to its high purity and Derivatives of EO
(especially ethylene glycol) are commonly used in the plastics
industries. Cost estimation of the process shows the payback
period as 2.94 years.