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ETHYLENE

OXIDE

Shakti bhardwaj

Contents
Introduction
Uses
Structure
properties
methods of production
Process Flowsheet
Energy Balance
Equipment Design
Cost Estimation
Conclusion
INTRODUCTION
ETHYLENE OXIDE, ALSO CALLEDOXIRANE, IS THE
ORGANIC COMPOUNDWITH THEFORMULAC2H4O.
IT IS A CYCLIC ETHER.
IT IS A COLORLESS FLAMMABLE GAS WITH A
FAINTLY SWEET ODOR
IT IS A 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 EASILYPOLYMERIZES.
ETHYLENE OXIDE ISISOMERIC WITH
ACETALDEHYDE.
TODAY ABOUT 9.6 X 106 TONES OF ETHYLENE
OXIDE ARE PRODUCED EACH YEAR WORLDWIDE.
Uses of ethylene oxide

In production of ethylene glycol and higher


alcohols
As a pharmaceutical intermediate it is
used in the synthesis of choline, 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
GLOBAL INDUSTRIAL USE OF
ETHYLENE OXIDE
STRUCTURE
PROPERTIES AND SPECIFICATION

I.U.P.A.C name- Oxirane


Other names- epoxyethane, ethylene oxide,
dimethylene oxide,
oxacyclopropane
Molecular weight 44
Boiling point at 760 mm Hg, C (F) 10.5o C,
(50.9o F)
Freezing point, C (F) -111.3o
C ,(-168.3o F)
Flash point (TOC), C (F) <-18o
C, (<0o F)
Density at 4C (39.2F), g/ml
0.890
METHODS OF PRODUCTION
Ethylene oxide has been produced
commercially by two basic routes:
From ethylene chlorohydrin(2- chloro
ethanol).
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.
PROCESS FLOWSHEET
Energy balance
RGY BALANCE
S: 1 HOUR OPERATION
GY BALANCE FOR THE REACTOR:
ucts from the reactor:
= 4250 kg = 96.59 kg moles
= 5409.06 Kg =193.18 kg moles
= 92330.29 kg =2885.32 kg moles
= 8500 Kg = 193.18Kg moles
= 5032.63 Kg = 179.71Kg moles
= 3477.24 Kg = 193.18 Kg moles.

wo reactions taking place in this process are given be


reaction
C2H4 + O2 ------------------------------ C2H4O
Side reaction
C2H4 + 3O2 ----------------------------------- 2CO2 + 2H2O
Products
Consider feed entering at 25C:
Tref = 25C
T = 25 25 =0
(m*Cp*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*Cp*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*Cp*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 *
(m) water = 420000 Kgs.

ENERGY BALANCE FOR THE COOLER 1:

In the cooler the products vapours are cooled from


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

(m*Cp*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*Cp*T)products entering the cooler = 3.37*1010
Joules.

Therefore heat removed in the cooler = 6.74 *1010


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 atms =
W1 = V*(P1- P2 ) = 3.82 * 108 Joules.
ENERGYThis
BALANCE TO THE
work will ABSORBER:
be added to the enthalpy.
In So
thethe
absorber the
increase in ethylene1.270*109
enthalpy= oxide is 3.82*108
completely
absorbed in the
Therefore, thewater
energyat leaving
25C. Only the energy is=lost
the compressor1
from the gases, 1.625*109
which areJoules.
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 = 1.546*109Joules
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 25C. In the compressor the fed stream is
compressed to 5 atms.
ENERGY BALANCE TO THE STRIPPER:
Energy leaving
In vaccuum stripperthe
thecompressor = 1.167*109
gases will be Joule
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
column = HF = 1.167*109 J
Temperature of the feed = 35C
From the T-x-y dia. for the Ethylene oxide (EO)-
water system.
The bubble point = 55C
Dew point = 93C
Enthalpy of the gas= HG=yEO*(CpEO*MEO*(TG-
TF ) + EO)
+ yH2O*(CpH2O*MH2O*(TG-TF
) + H2O)
M is the molecular weight of the species, y is the
mole fraction, 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/Kmoles
HG = 1.427*106 J
Cooling water required in the condenser
M*Cp*T=1.427*106J
Water is getting cooled form 25C to 50C
M = 1.427*106 J/(4180*25)=13.65 Kg/hr
HD = yEO*[CpEO*MEO*(35-25)] +
yH2O*[CpH2O*MH2O*(35-25)]
Cp 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*103J
Reboiler duty = QB = D*HD + W*Hw - F*HF + QC =
1.17 *105 J
Equipment
design
DESIGN OF A SIEVE PLATE DISTILLATION COLUMN
FOR THE SEPARATION OF ETHYLENE OXIDE -WATER
MIXTURE
Distillation column pressure = 1 atmosphere
(absolute).
The feed entering is a mixture of 193.18 Kmoles 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 =1.013 *105 Pascals.
Vapour pressure of water PW, Vapour pressure of
Ethylene oxide PEO.
All pressures in Pascals.
Liquid phase mole fraction of EO, x = PT - PW /PEO-
PW
Mole fraction of ethylene oxide in the feed, Xf = 95.133/
290.78 = 0.33
Mole fraction of the ethylene oxide in the distillate, xD
= 0.99

Distillate amount, D = 94.65 Kg moles.


Let W be the number of moles of residue and xW be the
mole fractions of the ethylene oxide in the residue.
By material balance:

F= D + W
290.78 = 94.65+ W
Therefore, Residue W= 196.66 Kg moles.
Component material balance: F*xF = D*xD + W* xW
290.78* 0.33 = 94.65* 0.99 + 196.06* xW
Therefore, Xw = 0.012
Feed temperature = 35C
Molecular weight of Distillate, MD= 0.99*44 + 0.012*
18= 43.74
Molecular weight of Residue, Mw = 0.012*44 + 0.988*
From the T-x-y diagram Dew point = 93C Bubble
point = 55C
At 55C,
93C, the specific
latent heat
heatofvalues
evaporation of EO
of EO and and are;
water water
are; KJ/Kg K and 4.18 KJ/Kg K respectively.
2.17
461.45 KJ/KgK
Average and
CpL value of2154.79 KJ/Kg
the liquid K respectively.
= (2.17 + 4.18)/2= 3.175
KJ/Kg K
Enthalpy of liquid = HL = Cpl* MF * (TL TF) = 1687.83
KJ/K mole.
Enthalpy of vapour =
HG = yEO * MEO{CpEO X*(TG -TF) + EO} +
yH2O * MH2O{CpH2O * ( TG- TF) +H2O}
= 37438.09 KJ/ Kg mole.
The designe is considered at the temperature of the
Feed. HF = 0
(q) = HG HF/ HG HL = 37538.09 0/ 37538.09
1687.83 = 1.05
Slope of the q-line is q/ q-1= 21
The feed is sub-cooled.
From the equilibrium curve;
Intercept of the q-line = xD/Rm+1 = 0.88
Actual reflux ratio is 1.5 times the minimum reflux ratio
R =1.5 X 0.125=0.25
Intercept of the original q-line = 0.792
From the equilibrium curve; the total number of
theoretical trays in the distillation column = 6
(including reboiler)
Enriching section ,No. of trays = 2
Stripping section No. of trays = 3

Calculation of flow streams:


L = L0, liquid flow rate.
L0 = R * D = 0.25 * 94.6 = 23.66 Kg moles.
Material balance on the enriching section: G = L + D
G is the vapour flow rate.
G = 23.66 + 94.65 = 118.31 Kg moles. L- L / F = q
L= (1.05 X 290.78) + 23.66 = 329 Kg moles
G- G/ F = q 1
G= 132.849 Kg moles
Let us assume;
Plate spacing = 600 mm
Hole diameter , dL = 5mm
Hole pitch, triangular = 15mm
Tray thickness = 3mm

Total hole area/ perforated area = Ah/ Ap = 0.1(for


triangular pitch)
Plate diameter is calculated as follows;

(L/G)*(L/G) = 0.06
Unf = Csbf (/20)0.2 (L- G/G)0.5
Unf = vapour velocity through net area at
flood, m/s.
Csb f = capacity parameter = 0.28
() = Liquid surface tension= 37.3
dynes/cm
Therefore, Unf = 2.7 m/s
c d
12% of Ac.
An = 1/ 2.7 = 0.37 m2
Ac = /4 X Dc2
Dc = 0.59 = 0.75 m. (Rounded for a standard value)
Ad = 0.12 X 0.4418 = 0.053m2
Active area Aa = Ac 2 X Ad = 0.3358 m2
Perforated area (Ap)
Weir length = 0.75 X Dc= 0.55 m; (0.6 m, approx. to
standard value)
Weir height, Lw = 50 mm
c = 2 sin-1 (Lw/Dc) = 106.26 ()= 180 - = 73.74
Area of coming zone, Acz = 2 X [0.6 X 50 X 10-3] = 0.06 m
Area of periphery waste,
Awz = 2{[/4 Dc2 /360]-[/4(Dc2 -0.12) /360]} = 0.004 m
Ap = Ac- 2 Ad Acz Awz = 0.2718 m2
Ah/Ap = 0.1
Ah = 0.2718 X 0.1 = 0.02718 m2
Column efficiency
The efficiency calculations are based on the average
conditions properties in each section.
Enriching section:
Average viscosity of the liquid is calculated by using
Kendall- Munroe equation.
m 1/3 = x1 11/3+x2 2 1/3
1 = viscosity of EO = 0.25 cp.
2 = viscosity of water = 0.857 cp
x1 & x2 are the corresponding mole fractions.
m = 0.41 cp.
Vapour phase viscosity m= yi Mi i1/2/ yi Mi1/2 =
0.0093 cp.
Liquid phase diffusivity, Wilke- Chang equation is used.

DL = 7.4 * 10-8 * ( Mwater)0.5 * T/ m * v0.6


V= 46.4
= Association factor = 2.6
T = temperature in K.
DL = 3.775 * 10-5 cm2/sec.
Vapour phase diffusivity
DG = 10-3 * T1.75 (1/Mwater + 1/ MEO)0.5/ P *
[ vEO1/3 + vWater1/3] DG
= 0.188 cm2/sec.
Nscg = G/G*DG = 0.3
Same calculations are carried out for the stripping
section also.
The values are;
m = 0.324 cp
m = 0.011 cp
DL = 5.477 * 10-5 cm2/sec.
DG = 0.232 cm2/sec.
Nscg = 0.468
Operating pressure of the distillation column = 1
atmosphere.
= 101.3 K N/m2
Design pressure = 10 % more than the
operating pressure.
Design pressure, Pi = 1.1 * 101.3 K N/m2
= 0.113 N/mm2
Design temperature = 100 C
M.O.C. of the shell and the covers is Stainless
steel
18Cr/8Ni /Ti stabilized.
Design stress of the material at 100C = 150 N/mm2
Design of the covers to the column:
Standard ellipsoidal head with major axis: minor axis
= 2:1.
The minimum thickness required is given by the
formula
Thickness, e = Pi*Di/[2*J*f 0.2* Pi] +C
Pi = Design pressure = 0.113 N/mm2
Di = Inner diameter of the column = 750
mm
The weld joint is double welded butt joint and radio
graphed.

F = the design stress of the material of construction.


C = corrosion allowance given to the material = 2mm
(generally) Therefore, e = 0.113 * 0.75 /[2* 0.85* 150
0.2* 0.113]
= 2.3 mm.
The minimum required thickness of the cover is taken
as 6 mm.
Calculation of minimum thickness of the shell.
Thickness of the shell, ts = Pi*Di/[2*J*f Pi] + C
= 0.113 * 0.75/
[2*150*0.85 0.113]
= 2.5 mm
construction of the shell is 6 mm.
For stability of the shell the column is divided into
five parts and thickness is increased from top to bottom
of the shell, as 6 mm,
8 mm, 10 mm, 12 mm & 14 mm respectively.
Stress analysis of the material of construction and
the column are carried with the assumptions stated in
the required location and the specification of the
material of construction.
Material of construction = Stainless steel 18Cr/8Ni-Ti
stabilized. Design stress of the material = 150
N/mm2
Density of the material = 7830 Kg/m3
Youngs modulus = 200000 N/mm2
Design pressure = 0.113 N/mm2
Corrosion allowance = 2 mm
Inner diameter of the column = 750 mm
Height of the column between the two tangent lines
= 9000 mm
Shell is butt welded with weld joint efficiency
= 0.85
Top disengaging section = 1000 meters
Bottom separation section = 2000 meters
Skirt height = 3000 mm
No of trays = 13
Tray spacing = 600 mm
Tray support rings =60 x 60 x 100 mm
Insulation = 50 mm thick
Mineral wool density = 130 kg/m3
Maximum wind velocity = 160 Km/hr
Seismic forces = Neglected
Tray loading excluding liquid = 1 KN/m2 of plate area
Tray loading including liquid = 1.2 KN/m2 of plate area
Stress analysis
Axial stress due to pressure = fap = Pi*Di/[4*(ts-C)]
= 0.113 * 750/[ 4* (10 - 2)
= 2.64 N/mm2
Stress due to the dead weight of the vessel:
Dead weight of the vessel =
Wv = Cv**m*Dm*g*(Hv + 0.8* Dm)* ts*10-3
Wv = total weight of the shell, excluding internal
fittings, such as plates.
Cv = a factor to account for the weight of nozzles,
man ways etc.
Thickness of the wall = ts.
m = density of the vessel
material, Kg/m
Dm =mean diameter of the
vessel
= (Di + ts*10-3), m
For a steel vessel; Wv = 240*Cv *Dm *(Hv + 0.8*
Dm)
Hv = 9000 mm, Cv = 1.15, ts = 10 mm, Dm = 760
mm
Wv = 240*1.15*0.76*(9 +
0.8*0.76)*10
= 20153.74 N
Stress due to dead weight of the vessels,
fd = 131723.38 N/m2.
Stress due to the weight of the plates
Plate area, ap = /4 * Di2 = 0.411 m2
Weight of the plate = m*t*ap; t is the
thickness of the plate.
= 101.5 N
Approximate volume of insulation =
*9*0.75*50*10-3
Weight of insulation = 1.06 * 130 *
9.81
= 1351.8 N
The weight of the insulation is doubled to account
the extra fittings.
Stress due to insulation + extra fittings, fins = 2550.
56 N/m2
Total dead weight = 20153.74 +
1321.1+ 2703.6
= 24178.44 N
Total stress due to dead weights = 0.136 N/mm2
The maximum compressive stress will occur when the
vessel is
not under pressure.
Design of the skirt- support for the vessel.

A skirt support consists of a cylindrical or conical


shell welded to the base of the vessel.

A flange at the bottom of the skirt transmits the load


to the foundations. Skirt support is recommended for
vertical vessels, as they do not impose concentrated
loads on the shell; they are particularly suitable for use
with tall columns subject to wind loading.

The skirt thickness must be sufficient to withstand


the dead-weight loads and bending moments imposed
on it by the vessel; it will not be under the vessel
pressure.
Cost estimation
COST ESTIMATION FOR THE PROPOSED
ETHYLENE OXIDE PLANT
The capacity of the plant = 100 TPD
The operating hours per day = 24
Operation days per year = 300 days
The total production per year = 30000 T
For an ethylene oxide plant installed in 1990 the total
capital cost was $ 43 million for a capacity of
50000 T/year.
Here the capacity is 30000 T/year.
CN = C*(R)x
R = 30000/50000 = 0.6
The power factor = (x) = 0.78
Therefore CN = $ 28.9 million
M&S Cost index value for the year 1990 = 924
M&S Cost index value for the year 2011 = 1519.2
Cost in 2011/cost in 1990 = Cost index in2011/ Cost
index
Therefore cost in 2011 =$
47.5 million
Converting the cost into the Indian currency = 212
Crores.
($1 = Rs 44.6/- in 2011).
In 2011 the total capital cost of the ethylene oxide
plant with capacity 30000T/year
= 212 Crores.
= 0.85* 212 =
180.20 Crores.
Working-capital investment (20-10% of the total
capital investment) =
0.15*212= 31.80 Crores.
Fixed capital investment = Direct Costs + Indirect
Costs
Direct costs :-Assumed as 77.5% of Fixed-capital
investment
= 0.775*180.2=
139.66 Crores.
(Equipment + Installation + Instrumentation + Piping
+ Electrical
+ Insulation + Painting (50-60% Fixed-capital
investment)
Direct Costs =
38.41+15.36+6.91+7.68+8.45+15.36+38.41
+ 8.83 = 139.41 Crores.

Indirect costs = expanses which are not directly


involved with material and labour of actual
direct costs)
The assumed value is 10 % direct cost = 13.94
res.
Contingency (5-15% of fixed capital investment)
The assumed value is 1% of the Fixed-capital. = 1.80
res.

ESITMATION OF TOTAL PRODUCT COST


Manufacturing cost = direct production costs +
d charges + plant
rhead costs
Fixed charges (10-20% of the total
duct cost)

The assumed value is 10% of the Fixed-capital


estment
and 3% of the building value
= 18.48 Crores.
Local taxes (1-4% Fixed-capital investment)
= 7.21 Crores.
Total product cost = 29.91/0.2 = 149.55 Crores.

Direct production costs


(about 60% of the total product cost)
= 89.73 Crores.
Manufacturing cost = 89.73 + 29.91 + 14.96
= 134.60 Crores.
Total product cost = 149.55 Crores.
Seller is given a commission of 10% of the market
selling price.
Therefore, the price of ethylene from the factory =
60 /Kg
Total selling price/year = 60*300*100*1000
= 180 Crores.
Total income = Gross earning Total product cost
= 180 149.55 =
30.45 Crores.
Total profit before depreciation and taxes = 30.45
Crores.
Depreciation = 18.48 Crores.
Total profit after depreciation = 30.45 - 18.48 =
11.97 Crores.
Total profit after 46% taxes = 6.464 Crores.
Fixed-capital investment = 180.20 Crores.
Payout period = 4 years
= Fixed-capital investment/ [(Net profit
after tax/year) + (Depreciation)]
= 180.20/[18.48 +
6.464] = 4years
CONCLUSION

It is concluded from our project work that


ethylene oxide production from ethylene & oxygen,
is cost feasible. In this project work we had used
continuous process instead of batch process by the
help of little modification in the earlier process.
Cost estimation for this process is also feasible.