Gibbs Free Energy Calculation & Thermodynamic Feas

ΔG = ΔH + TΔS
Where,
Where,
ΔG
ΔG is
is the
the Gibbs
Gibbs free
free energy
energy
ΔH is the change in Enthalpy
H° 298 85.865 J/mol ΔS is the change in Entropy
S° 298 71.6 J/mol.K
ΔH = Hid - H°
ΔS = Sid - S°
Where,
Where,
H°
H° &
& S°
S° are
are standard
standard states
states at
at standard
standard temperature
temperature 298K
298K
Hid
Hid &
& Sid
Sid are
are ideal
ideal values.
values.

Column1 Column2 Column3 Hid 328 = H° + ∫130_(𝑇^0)^𝑇▒ 〖𝐶 _𝑃^𝑖𝑑 ⅆ𝑡

328
Cp 328 95.56 J/mol.K
T 328 K Sid 328
328
= S° + ∫129_(𝑇^0)^𝑇▒ 〖𝐶 _𝑝^𝑖𝑑 ⅆ𝑡
T° 298 K ln⁡〖𝑃 /𝑃^0 〗
R 8.314
P 9 atm
P° 1 atm

Hence,
Hid 328 2952.665 J/mol
Sid 328 194.485982
ΔH= Hid - H° 2866.8
ΔS= Sid - S° 122.885982

ΔG = ΔH- TΔS
ΔG -37439.8021 J/mol Since,
Since, ΔG
ΔG is
is negative
negative the
the reaction
reaction is
is feasible.
feasible.
-37.4398021 KJ/mol
Thermodynamic Feasibility

standard
standard temperature
temperature 298K
298K

𝑇^0)^𝑇▒ 〖𝐶 _𝑃^𝑖𝑑 ⅆ𝑡 〗

^0)^𝑇▒ 〖𝐶 _𝑝^𝑖𝑑 ⅆ𝑡/𝑇 〗−𝑅

tion
tion is
is feasible.
feasible.
 Justification of Conversion

VCM PVC
CA° We assume to operate the system Adiabati
Inlet moles 0
Outlet moles CA = CA°(1-Xa) CB = CA° * Xa Hinin + QGen
Gen
= HOut
Out
+ QRem
Rem

CA° (kg/hr) 1000

ΔT 30

At 298K (J/kg.K) At 328K (J/kg.K)

Cp VCM 1374.07 1529.02
Cp PVC 1217.07 1260.99
Cp Water 4101.6 4076.8

Hin = m Cp ΔT
in
Hin (J/hr) 45870600 = CA° * CpVCM * (T - TDatum
Datum
)
A°

QGen (J/hr) 1536 Xa QGen

Gen
= (-ΔHB) * Xa * FA°
B A°
Hout (J/hr) 54419575- 10028725Xa = (-(96000)) * Xa * 0.016
= 1536 Xa J/Hr
Xa 0.8523182995936
HOut = mA * CpVCM * ΔTOut + mB * CpP
Out A Out B
= CA° ( 1-Xa) CpVCM * ΔTOut + (CA
A° Out A
= 1000 (1 - Xa) * 1554.845 * (3
= 54419575 - 10028725 Xa J/h

H
Hinin ++ Q
QGen = HOut
Gen = HOut
45870600 + 1536 Xa = 544419575 - 10028725 Xa

Xa = 0.8523
Hence the conversion is 85.23%
me to operate the system Adiabatically.

Gen
Gen
= HOut
Out
+ QRem
Rem

m Cp ΔT
CA° * CpVCM * (T - TDatum
Datum
)
A°

(-ΔHB) * Xa * FA°
B A°
-(96000)) * Xa * 0.016
1536 Xa J/Hr
mA * CpVCM * ΔTOut + mB * CpPVC * ΔTOut
A Out B Out
CA° ( 1-Xa) CpVCM * ΔTOut + (CA° * Xa) * CpPVC * ΔTOut
A° Out A° Out
1000 (1 - Xa) * 1554.845 * (333-298) + 1000 Xa * 1268.31 * (333 - 298)
54419575 - 10028725 Xa J/hr
 Water Water
BASIS FEED (VCM) PVC PRODUCED Initiator (FEED) (Produced)
KG/hr 5000.00 4261.50 25.00 10075.75 9.77
Tons/hr 5.00 4.26 0.03 10.08 0.01
Tons/day 120.00 102.28 0.60 241.82 0.23
Tons/year 39600.00 33751.08 198.00 79799.94 77.41

VCM + Water → PVC

Conversion 0.85

FEED Kg/hr
VCM 5000.00
WATER 10075.75 POLYMERIZATION
INITIATOR 25.00 Reactor
TOTAL 15100.75 Conversion= 85.23%
 VCM RECOVERY
MATERIAL
(99%)
VCM
WATER
TOTAL

MATERIALS Kg/hr
PVC 4261.50
VCM 738.50
WATER 10075.75
Stripping
Column
INITIATOR 25.00
TOTAL 15100.75

Steam
 MATERIAL BALANCE

Kg/hr
731.12
302.27
1033.39

MATERIAL Kg/hr
PVC 4261.50
VCM 7.39
WATER 9773.48
DEWATERING
INITIATOR 25.00
TOTAL 14067.36

MATERIAL Kg/hr
WATER 8796.13
INITIATOR 25.00
TOTAL 8821.13

90% water is being removed

 MATERIAL Kg/hr
VCM 7.39
Water 967.57
AIR 68330.00
TOTAL 69304.96

MATERIAL Kg/hr
PVC 4261.50
VCM 7.39
WATER 977.35
DRYER
TOTAL 5482.35

removed Column1 Column2

AIR 68330.00
 PRODUCT OBTAINED

MATERIALS Kg/hr
PVC 4261.50
Water 9.77
Total 4271.27
 ENERGY BALANCE for

ENERGY BALANCE EQUATION: H in + Q Gen = H out + Q Rem

The reaction is Exothermic and the reactor considered

is Isothermal.

FEED Kg/hr mol/hr CP (J/mol.K) ΔT HIN (J/hr)

VCM 10000.00 0.16 59.96 30.00 287.81
H2O 20151.50 1.10 4.18 30.00 138.07
INITIATOR 50.00 0.00 454.39 30.00 2.73
TOTAL 30201.50 428.61

PRODUCT Kg/hr mol/hr CP (J/mol.K) ΔT HOUT (J/hr)

PVC 9000.00 0.16 62.10 30.00 298.08
VCM 1000.00 0.16 59.96 30.00 287.81
WATER 20151.50 1.10 4.18 30.00 138.07
INITIATOR 50.00 0.00 454.39 30.00 2.73
TOTAL 30201.50 726.69

Now, we will find the mass of water need to be maintained in the jacket and the
temperature of water to be maintained to maintain the temperature in the reactor
constant.
constant.

So
So we
we have
have QRem
QRem == m m ** Cp
Cp ** ΔT
ΔT
Where,
Where,
m
m == mass
mass of
of the
the water
water in
in the
the jacket.
jacket.
Cp of Water = J/mol.K
Cp of Water = J/mol.K
Taking
Taking the
the initial
initial temperatur
temperatur ofof the
the water
water T1
T1 == 298
298 K
K i.e
i.e to
to be
be the
the normal
normal the
the normal
normal temperature
temperature of
of the
the water
water
T1 -T2 = 298 -T2 K
So by assuming T2 to be less than 80°Deg so that the water inside the jacket may not get evaporated.

Hence, we get the mass of the water in the jacket of the reactor at list of temperatures of the water in the jacke
Taking
Taking the
the initial
initial temperatur
temperatur ofof the
the water
water T1
T1 == 298
298 K
K i.e
i.e to
to be
be the
the normal
normal the
the normal
normal temperature
temperature of
of the
the water
water
T1 -T2 = 298 -T2
T1 -T2 = 298 -T2 K K
So
So by
by assuming
assuming T2T2 to
to be
be less
less than
than 80°Deg
80°Deg so
so that
that the
the water
water inside
inside the
the jacket
jacket may
may not
not get
get evaporated.
evaporated.
Hence,
Hence, we
we get
get the
the mass
mass of
of the
the water
water in
in the
the jacket
jacket of
of the
the reactor
reactor at
at list
list of
of temperatures
temperatures of
of the
the water
water in
in the
the jacke
jacke

Data: Column1 T2 ( K)
Qrem 12757.92 353
Cp 4.184 348
T1 298 343
338
333
ALANCE for REACTOR

Now,
QGen
Gen
= -(-ΔHRR) * xAA * FAA°°
= -(-96000) * 0.85 * 0.16
= 13056 J/hr

Q gen 13056.00

Since,
H inin + Q Gen
Gen
= H out
out
+ Q Rem
Rem

428.61 + 13056 = 726.69 + 〖 𝑄〗 _𝑅𝐸𝑀

〖 𝑄〗 _𝑅𝐸𝑀 = "12757.92 " J/hr

Q rem 12757.92

temperature
temperature of
of the
the water
water to
to enter
enter the
the jacket
jacket of
of the
the reactor.
reactor.
get evaporated.

es of the water in the jacket.

 temperature
temperature of
of the
the water
water to
to enter
enter the
the jacket
jacket of
of the
the reactor.
reactor.
get
get evaporated.
evaporated.
es
es of
of the
the water
water in
in the
the jacket.
jacket.

ΔT Mass (kg)
55 55.440292021554
50 60.9843212237094
45 67.7603569152326
40 76.2304015296367
35 87.1204588910134
 REACTOR MECHANICAL DESIGN

Specifications of the Reactor

Identification Column1
Name of the Equipment Autoclave Reactor
Equipment type Stirred type Reactor
Operation Batch Operation
Operating Temperature 54°C - 70°C
Operating Pressure 0.4 - 1.2 Mpa
VCM, PVC, Water,
Material handled
Benzoyl Peroxide, Steam
Material of Construction SS316
Ref: Chemical Engineering D
Max. allowable Working Stress(SS316)
18700.52
[Psi]
[KPa] 128900.00

Total Mass in the Vessel:

VCM
We + PVC
We have
have + Initiator
calculated
calculated the =
the Volume
Volume from
from the
the Design
Design Equation
Equation for 30201.50
for Batch
Batch Reactor.
Reactor.
V
V == 50
50

VF (Volume of Feed) 10.00

Volume of20%
Assuming Feedallowance,
(Vfeed):
Assuming 20% allowance,
We
We get,
get, Volume
Volume of
of the
the Vessel
Vessel == 1.2
1.2 ** Volume
Volume of
of Feed
Feed

Volume of the Vessel (V): 12.00

Dimensions:

(𝐻𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑇𝑎𝑛𝑘 "(HT)" )/(𝐷𝑖𝑎𝑚𝑒𝑡𝑒𝑟 𝑜𝑓 𝑇𝑎𝑛𝑘 "(DT) " ) =

"HT"
T" /"
DT " = 1.5
/" T

For the Volume of the Tank (V TT ) we have:

𝑉_𝑇= (𝜋𝐷_𝑇^2 𝐻_𝑇)/4= (𝜋𝐷_𝑇^2×1⋅5𝐷_𝑇)/4 =

(1.5𝜋𝐷_𝑇^3)/4
Since we know VTT we are calculating DT.T.
 For the Volume of the Tank (V TT ) we have:

𝑉_𝑇= (𝜋𝐷_𝑇^2 𝐻_𝑇)/4= (𝜋𝐷_𝑇^2×1⋅5𝐷_𝑇)/4 =

(1.5𝜋𝐷_𝑇^3)/4
Since we know VTT we are calculating DT.T.

DT (Diameter of tank) (m) 2.17

In inches 85.43

HT (Height of tank) (m) 3.25

In inches 127.95

For
For the
the height
height of
of the
the liquid
liquid in
in the
the Vessel
Vessel (H
(HLL ):
):

𝐻_𝐿=(4𝑉_𝐹𝑒𝑒𝑑)/(𝜋𝐷_𝑇^2 )

Now,
HL (Height of Liquid) (m) 2.71
In inches 106.69

For
For Volume
Volume of
of the
the Head
Head (V)
(V)

𝑉=(𝜋𝐷_𝑇^3)/24

VH (Volume of Head) 1.33

Total
Total Volume
Volume of
of the
the Vessel
Vessel ::
(VVessel
Vessel
) = VVessel
Vessel (Excluding
(Excluding Head)
Head)
+ VBottom
Bottom Head
Head
+ VTop
Top Head
Head

Total Volume of Vessel ( Vvessel) 14.67

Max.
Max. Internal
Internal Pressure:
Pressure:

P = Patm
atm
+ 𝜌𝐻_𝐿𝑖𝑞⋅𝑔⁄𝑔_𝑐

Maximum Internal Pressure (P) (Pa) 1266756.33

In Psi units 183.73
 Design Pressure = 10% of Internal Pressure for safety
PTT = 1.10 P

Design Pressure (PT) (Psi) 202.10

Shell
Shell Thickness
Thickness (( ttss ):
):

t_s=(P×r_i)/(S_w×E_J−0.6P) + Corrosion
Allowance (1/16 inches)

Shell Thickness (tS) (Inches) 0.52

In mm 13.21

Outside
Outside Diameter
Diameter (D
(DOO)) == D
DTT ++ 2
2 (t
(tss))

Outside Diameter (DO) (Inches) 86.48

In mm 2196.59

Head
Head Thickness
Thickness (( tthh ):
):
For
For torispherical
torispherical Head:
Head:

tss = (0⋅885𝑃×𝐷_𝑇)/(𝑆_𝑤 𝐸_𝐽−0.1𝑃)

Head Thickness (tS) (inches) 0.82

In mm 20.83

Bottom Thickness (tb) = (ts) (mm) 13.21

in inches 0.52
ECHANICAL DESIGN

Ref: Chemical Engineering Design by Sinnot & Towler

Using
Using the
the max.
max. ratio,
ratio, Perry's
Perry's Chemical
Chemical Engineers
Engineers Handbook
Handbook 8th
8th Edition
Edition 18-14
18-14
For SS316
Property Values
Density (ƍ) (kg/m3) 969.00
g (m/s2) 9.81
Patm (Pa) 1241000.00
Identification Values
Internal radi: (DT /2) 42.72

Working Stress (Psi) 18700.52

Max. Internal Pressure 202.10

Joint Efficiency (EJ) 1.00 Plant
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neering
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