Steady-State Nonisothermal Reactor Design Chap 8

444

andusedtodesignCSTRs(i.e.,toobtainthereactorvolumeoroperatingtem-
perature). If necessary, the CSTR is either heated or cooled by a heating or
coolingjacketasshowninFigure8-2,orbyacoilplacedinsidethereactor.
Reactions are frequently carried out adiabatically. often with heating or

::::[pnt:ofr:;'[greodceus:::r::vmo[::ng°£gnfi;e::c::sthmeatreer::i:°:ucvhesasse[[n\¥;tohb]teT:
P8-4,theworkdonebythestirrercanusuallybeneglected.Aftersubstituting
Fniiatinn (8-42) for 6 , the energy balance can be w'ritten as
Equation (8-42)

®,cp,(T-T,o) (8-51 )
uA(Ta-T) -XtLH°T`x(TR) + AC p(T -
CSTR u'ith heat
exchange

and negligible stirring work. both a

Under
ull\+,I conditions
,\,+I+ ---. _-__of adiabatic operation

and W5 are zero, and the energy balance becomes

Adiabatlcof°:e:ast'T°R
-x[AH&x(rR)+Acp(I-rR)]=£o,ap,(I-7`,0)
hf="

nonisothermal ic:aiiu,
The procedure for nonisotnermzii reactor uv.,a..
design ,___
can
. be_ 1illustrated by con-
___._ i_ T^t\lo a_1.

sidering the first-order Irreversible liquid-phase reaction shoun in Table 8+

ThealgorithmforworkingthrougheithercaseAor8issummarizedinFiguri]
8-4. Its application is illustrated in the following example.
From here on, for the sake of brevity we will let
'.`

•1 -- i
'-I

unless otherwise specified.

Example 84 Production of Propylei.e Glycol in an Adiabatic CSTR

Propyleneglycolisproducedbythehydrolysisofpropyleneoxide:

CH,~CH~CH:` + H:O ±2£9i+ CH2-CH-CH3

\;/ 6H 6H
Over800millionpoundsofpropyleneglycolwereproducedin1997andth
Over 800 milllon Pounus iu pil;I;71~„-a
__-_I-,--
I)-^h`,1pnp olvrnl makes uP abou

Production` uses, pricewasapproximatelySO.67perpound.Propyleneglycolmakesupabout

and economics the
|l|C major
||,(+J\,` deri\'atives
`.r,- ___ of
_ prop)Jlene
. . oxide. The reaction takes place readily
_,I-.-I,. nr:i
temperature u'hen catalyzed by sulfuric acid.
You are the engineer in charge of an adiabatic CSTR producing pr
91ycolbythismethod.Unfortunatel}J,thereactorisbeginningtoleak,andy
replaceit.(Youtoldyourbossse\eraltimesthatsulfuricacidwascorrosive
replace it. (You told your DOss s[`.ia, I ,,,.. ~ ...__
•-` f---^nctr``rtir`n \ There is a nice overflow' (
mildsteelwasapoormaterialforconstruction.)Thereisaniceoverflow'C
300-galcapacitystandingidle:itisglass-linedandyouwouldliketouseit.
See. 8.3 Nonisothermal continuous-Flow Beactors 445

You are feeding 2500 Ib/h (43.04 lb mol/h) of propylene oxide (P.O.) to the
reactor. The feed stream consists of (I) an equivolumetric mixture of propylene
oxide (46.62 ft3/h) and methanol (46.62 ft3/h), and (2) wac?r containing 0.I wt %
H2Soj. The volumeinc flow rate of water is 233.I ft3/h, which is 2.5 times the
methanol-P.O. flow rate. The corresponding molar feed rates of methanol and water
are 71.87 and 802.8 Ib mol/h. respectively. The water-propylene oxide-methanol
mixture undergoes a slight decrease in volume upon mixing (approximately 3%).
but you neglect this decrease in your calculations. The temperature of both feed
streams is 58°F prior to mixing, but there is an immediate 17°F temperature rise
upon mixing of the two feed streams caused by the heat of mixing. The entering
temperature of all feed streams is thus taken to be 75°F (Figure E8-4.I).

Propylene oxide Fjio

Methanol Fwo

Figure E8-4.I

Furosawa et al.5 state that under conditions similar to those at which you are
operating, the reaction is first-order in propylene oxide concentration and apparent
zero-order in e,`cess of water with the specific reaction rate

k = Ac-£' Rr = |6.96 x |012(c-32+co/Rr) h~l

The units of E are Btu/lb mol.

There is an important constraint on your operation. Propylene oxide is a
rather low-boiling substance (b.p. at I atm, 93.7°F). With the mixture you are using,
you feel that you cannot exceed an operating temperature of 125°F, or you will lose
too much oxide by vaporization through the vent system.
Can you iise the idle CSTR as a replacement for the leaking one if it will be
operated adiabatically? If so, what will be the conversion of oxide to glycol?'

Solution

(All data used in this problem were obtained from the fJcz#c/book a/ CAcm.sfry czncJ
Pky's!.cs unless otherwise noted.) Let the reaction be represented by

A+B ) C

rusawa, H. Nishimura, and T. Miyauchi, /. C'fecm. Eng. /p7!.. 2. 95 (1969).

446 Steady-State Nonisothermal Reactor Design Chap. 8

A is propylene oxide (C`p.A = 35 Btu/1b mol . °F) 6

8 is Water (CpB = 18 Btu/lb mol . °F)

C is prop}'lene glycol (Cpc = 46 Btu/1b mol . °F)

M is methanol (Cp\, = 19.5 Btu/1b mol . °F)

In this problem neither the exit con\'ersion nor the temperature of the adia-
batic reactor is given. By application of the material and energ}J balances uJ`e can
solve two equations with two unknowns (X and 7`). Solving these coupled equations`
we detemine the exit conversion and temperature for the glass-lined reactor to see
if it can be used to replace the present reactor.

I . Mole balance and design equation:

I+o-F\+ r A,V -0

The design equation in terms of X is

v-f¥ _'-A
(E8-4.I )

2. Rate la",:
-rA -kcA (E8-4.3 )

3. Stoichiometr}' (liquid-phase. u = t;o ):

(E8-4.-?)
C`.i -CAo(1 -X)

4. Combining )Jields
FA.X _ U9±
\/- (E8-4.i)
-.Y)
A.cAoti -xj -rf

5. Sol`'ing for X as a function of r and recalhng that i = V/L)o gi\Jes

•k `Ae-E RT (E8-4.5 ,
XMB - iiiI =
1 + TAG-I, Rr

This equation relates temperature and con\Jersion through the mole balance.
6. The energy balance for this adiabatic reaction in which there is negligible
energy input provided by the stirrer is

-x[Af7£^(rfl) + A¢p(r-rA)] = £o,ap,(I-r,0) t8-."

Sol\'ing for X` we obtain

£®.-cp,(T-T,a) (E8-4.(l\
XEB-
-[AfJR^ (7.A) + ACp (7` -TR)]

6:]Pal.:ne:g€?co¥;gees[t]'_Toa::£]:::F:hr;a°n::erL:'::I,°dnst::tv:hea8ie::sm£Je::Lt:'a:fa::I?-I:]`f°':I)``(-,

ut ca|/g.°C ±|5%.

ul
 See. 8.3 Nonisotliermal continuous-Flow Beactors 443``

This equation relates X and r through the energy balanc`e. We see that there
are two equations [Equations (E8-4.5) and (E8-4.6)I that miist be solved for
the two unknowns, X and I:
7. Calculatious:
ai. Heat of reaction al [empera[ure T..I

AHRx(T)~-AH%x(TR)+ACp(T-TR) (8-27)

H.i(68°F) : -66,600 Btu/lb mol

fr8 (68°F) : -123.000 Btu/1b mol

H€ (68°F) : -226,000 Btu/lb mol

zr£.` (68oF) = -226,ooo -(-123,ooo) -( -66,6oo)

= -36,400 Btu/lb mol propylene oxide

ACp = Cpc-CpB-Cp^ (E8-4.7)

= 46 -18 -35 = -7 Btu/lb mo| .°F
AfJfx(I) = -36,400 -(7)(r -528)

b. S/oi.cAi.omcfry (CAo , 0[ , T): The total liquid volumetric flow rate entering
the reactor is

uo=L/Ao +UMo +L'Bo

= 46.62 + 46.62 + 233.1 = 326.3 ft3/h (E8-4.8)

V = 300 gal = 40. I ft3

V 40.1 ft3
-0.1229 h
uo 326.3ft3/h

FAo 43.04lbmol/h
LJo 326.3 ft3/h

= 0.1321b mo|/ft3
(E8-4.9)

FMo 71.87ltimol/h
formethanol: ®M ==° = -I.67
FAo 43.04lbmol/h

FBo 802.81bmol/h
For water: ®8 = - 18.65
flo 43.04lbmol/h

c. Energy balance terms:

zotcp,. = ap.i + oBcpB + oMcp,M

= 35 + (18.65)( 18) + (1.67)( 19.5)

= 403.3 Btu/lb mo| . °F EEEEEEE

7 ff; and fJ€ are calculated from heat-of-combustion data.
 Steady-State Nonisothermal Reactor Design Chap. 8

7`o = rco + ArmLx = 58C'F + 17°F = 75eF

(E8-4.11 )
- 535OR

rR = 68OF = 528cR

The conversion calculated from the energy t)alance. XEB . for an adiabatic
reaction is found by rearranging Equation (8-52):
<L®,-C,,(T-Ti±
(E8-4.6)
XEB - -
AIICRXLTR)+LCp(I-T

Substitutingalltheknownquantitiesintothemoleandenergybalancesgivesus
mol . °F) ( I - 535)OF
XEB-
|lii 36.400 -7 (I -528)I Btu/1b mol
Plot XEB as a
function of 403.3(I- 535) (E8-4.12,,
temperature -528)
36,400 + 7(7-

The conversion calculated from the mole balance` XMB, is found from Equa-
tion (E8-4.5).
-32,400/ 1.987r)
x 1012 h-l)(0.1 229 h) exp (
XMB- h) exp (-32.400/1 .987r)
Plot XMB as a I + (16.96 X 1 012 h-I)(0.1229
function of -16.306/ I)
x loll) exp ( (E8-4.13 ,
temperature
1 + (2.084 X 10]2) exp (-16.306/I)

8. Solving. There are a number of different wa}'s to solve these two simultd-
neous equations [e.g.. substituting Equation (E8-4.12) into (E84.13)]. To
give insight into the functional relationship between X and I for the mole
and energy balances. we shah obtain a graphical solution. Here X is plotted
as a function of I for the mole and energy balances. and the intersection iif
the two cur\'es gives the solulion where both the mole and energy balani`e
solutions are satisfied. In addition. by plotting these tuio curves we can lean
if there is more than one intersection (i.e„ multiple steady states) for whii`h
both
Dulll the energy
11,1 uli~,eJ balance
---. ^-^and
______
``faAmole balance
t^ cn`vp for X are satisfied.
and T` If qulte
it would be nupencal
Pot-
root-finding techniques w'ere used to solve for X and T` it 1 than one. We shall
sible to obtain only one root \\hen there is actually more choose 7- and then
discuss multiple steady states further in Section 8.6. We Figure E8-4.2. The
calculate X (Table E8-4.1). The calculations are plotted in

T.`BLE E8,4.1

XEB
X}1B
[Eq. (E8-4.12)]
[Eq. (E8-4.13)]
 -~,.38
449
See. 8.3 Nonisothermal continuous-Flow Beactors „

The reactor cannot

be used t]ecause it
will exceed the
specified maximum
temperarure
of 585 R

Figure E8-4.2

virtually straight line corresponds to the energy balance [Equation (E8-4.12)I

8J . I .i ' and the curved line corresponds to the mole balance [Equation (E8-4.13)].
- We observe from this plot that the only intersection point is at 85% conver-
imulta- sion and 613°R. At this point both the energy balance and mole balance are
3)I. To satisfied. Because the temperature must remain below 125°F (585 R), we
le mole cannot use the 300-gal reactor as it is now.
plo,,ed
/
=tion of
balanl.e
in lean Example 8-S CSTR with a Cooling Coil
r u.hil-h
meril-al A cooling coil has been located for use in the hydration of propylene oxide .dis-
i,e p(,`- cussed in Example 8-4. The cooling coil has 40 ft2 of cooling surface and the cool-
\,-e shall ing water flow rate inside the coil is sufficiently large that a constant coolant
nd then temperature of 85°F can be maintained. A typical overall heat-transfer coefficient for
1.2-Thl` such a coil is 100 Btu/h.ft2.°F. Will the reactor satisfy the previous constraint of
125°F maximum temperatiire if the cooling coil is used?

Solution

lf we assume that the cooling coil takes up negligible reactor volume, the conver-
sion calculated as a function of temperature from the mole balance is the same as
that in Example 8-4 [Equation (E8-4.13)].

_-------_
1. Combining the mole balance, stoichiometry, and rate law, we have `

` _ . - _ _ _ _ -_.

111111111111111-