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Case Study 101 PDF
Case Study 101 PDF
Volume Two:
Case Studies and Design Data
HOWARD F. RASE
W. A. Cunningham Professor of Chemical Engineering
The University of Texas at Austin
Original Illustrations by
JAMES R. HOLMES
Associate Professor of Engineering Graphics
The University of Texas at Austin
A WILEY-INTERSCIENCE PUBLICATION
Problem Statement
5
6 CS-101 STYRENE POLYMERIZATION
Initiation
M+M rn
~ (caIlAH) (1)
H H Ph
k
A' + M ~ R'
1 (4)
M'+M ~ R'
1 (5)
Propagation
R /.' + AH k"
--------> Pr + R l' (8)*
The rate of initiation is
(CS-l.l )
By using the stationary state hypothesis, expressions for concentrations
of A', M', AH, and R r ' can be obtained as functions of monomer concentra-
tions so that Eg. CS-l.l can also be written in these terms (1)
(CS-1.3)
(CS-1.4)
(CS-l.7)
or
- k.[M]+
(DP)-l = Cm + -'--
A (CS-1.8)
(CS-1.9)
where M n is the number average molecular weight. Cm, which accounts
for chain transfer, also varies with conversion.
Cm = C mu + B1X (CS-l.10)
Equations for the several constants are given in Table CS-l.l.
B1 = -1.013 x 10
-3 (473.12 -
logl0\ 202.5
T)
kj = 2.19 X 10 5 exp (-13,81O/T), (l./g-mole)Z sec- 1
emo = 2.198 x 10- 1 exp (- 2820/Tl
T = OK
8 CS-101 STYRENE POLYMERIZATION
Thermodynamics
Reactor Type
Heat Balance
104F Mcp JI;, - To) + UAh(T. - 1j) = (-I1H MhJF MX M) (CS-1.l2)
where F M is the molar flow rate of monomer fed, CPM is the heat capacity of
monomer, and T., To, 1j are the exit, entrance, and cooling medium tempera-
tures, respectively.
Since the heat capacities of monomer and polymer are approximately
the same, the heat of reaction at 25C can be used in Eq. CS-1.l2.
OPERATING TEMPERATURE AND CONVERSION 9
Fluid Properties
6,. = e :JIP~
l
pr -
PM(l - X M )
(CS-1.16)
where PM and Ppr are the densities of monomer and polymer, respectively.
'1r is the ratio of viscosity of polystyrene in styrene to that of pure styrene at
the same temperature, ['1Jr is the intrinsic viscosity of polystyrene of same
molecular weight and type in toluene at 30C in dl./g, and wpr is the weight
fraction as mass of polymer/mass of styrene.
The viscosity is very sensitive to temperature and concentration. Equation
CS-l.18 is corrected to agree with the original plot of experimental data given
in the reference. Ideally the value of ['1Jr should be determined for the
product in question in the laboratory. For illustrative purposes we select a
value of 0.7.
l
are 3623 cp and 13406 cp, respectively. Styrene viscosity at 150C is 0.22 cp (5).
Thus it is seen that viscosity increases dramatically above X M = 0.4, and
heat-transfer rate will decline rapidly such that it will not be possible to
remove the heat of polymerization. Hence for safety reasons the design will
be set at X M = 0.4 as a maximum, and subsequent calculation will reveal that
this is operable.
10 CS-101 STYRENE POLYMERIZATION
Reactor Volume
A 750 gal stainless-steel tank (60 x 60 in.) is selected from Table 8.8,
D = 60 in., D 1 = (1/3)60 = 20 in. with 160 rpm for good heat transfer
(838 ft/min tip speed, see Table 8.10). One 20-in. flat-blade turbine is selected
initially for analysis.
D),! fl flw ,
= 0.73 (0055)[(0.451 )(3623)(2.42)JO.33
20/12 . 0.055
(53.5)( I60)(60)(20/1 2)2JO.65( )0.24 _
~
fl
- 26.4
(fl )0.24
~
X
[ (3623)(2.42) flw flw
_ PM/1000 0.786 2 3
P= I + 6"X M
= I _ (0.209)(0.4) = 0.858 g/cm or 53.5Ib/ft
Ar = 0.055 BTU/(hr)ft 2 OF ft- 1 @ 150 a C for ethylbenzene (API Data Book)
REQUIRED HORSEPOWER 11
Assuming h = 10
Tw - 45 = 0.044 or
150 - Tw
for which J1 from Eq. CS-1.l8 is 52,477 cp
Required Horsepower
Mixing Effectiveness
fhP
R err = c~ --;; = c
)4.05
3623 = 0.033c
REFERENCES