Optimal Thermal Design of an

Autothermal Ammonia Synthesis Reactor

Akira Murase', Howard 1. Roberts2, and Alvin 0. Converse

Thayer School of Engineering, Dartmouth College, Hanouer, N . H . 03755

The following optimization problem i s considered: To maximize profit by optimal choice

of heat transfer coefficient as a function of reactor length, feed gas temperature,
and reactor length, subject to the physical laws governing the behavior of an autothermal
ammonia synthesis reactor and upper and lower bounds on the heat transfer coefficients.
Assumptions are made about the economics that reduce the profit objective to a weighted
sum of reactor length and ammonia yield. The results are presented graphically in
parametric form to permit application with little additional computation. The effect
of a variable heat transfer coefficient i s considerable. For a reactor 5.18 meters long
increase in ammonia yield is 5.4%; a t constant yield the reactor can b e shortened
b y 17%. The assumptions about the economics are then relaxed. Economic groups
are defined which characterize the profit objective. The optimal design i s insensitive
t o some groups over the range of interest, so that valid simplifications of the objective
function can be made.

T h e treatment of variational problems has received con- can affect the temperature profile only indirectly through
siderable attention in the chemical engineering literature the mechanical design of the heat transfer system-and
in the past decade. These can be classified as control the process-variable-based objectives do not always corre-
or design problems. I n chemical engineering, one would spond to economic objectives. McEwan and Beveridge
expect the most useful results to come from the solution (1965) offer an exception. Hence, it was decided to formu-
of the design rather than the control problems, because late the problem in terms of design variables and economic
in controlling a process one can, through feedback, correct objectives.
and control by specifying the control algorithm (the func- Annable (1952) compared the performance of an
tional relationship between corrective action and error) autothermal ammonia synthesis reactor (Figure 1) with
and not the control action function-e.g., valve stem posi- the maximum yield that could be obtained if one had
tion us. time. The solution to the variational control prob- direct control of the temperature profile. He found that
lem would yield the control action function, and while
there are cases-e.g., batch processes-in which this would
be useful, in most process control problems we are free
to exert corrective action after the process has started
and error has been measured. This is obviously not true
in design problems; the configuration is first set and then
the process is operated. This situation is more compatible
to the nature of variational problem solutions. Thus it
was decided to study variational problems that arise in
design.
Beginning with Temkin and Pyzhev (1960) and Denbigh
(1944, there has developed a considerable literature (Aris,

KFJ
1961) on the processing conditions under which a chemical
reaction should be carried out in order to obtain maximum Heat Exchanger
yield or selectivity. Although this work is of great value,
there are two shortcomings: The process variables such
as temperature, pressure, and concentration are not under
direct control of the designer-for example, the designer
Product Gas 4 Feed G o s
2 0 0 -350AT M
N H 3 = I 7-22Oo/
' Present address, Nippon Light Metal Co., Ltd., Tokyo, Japan.
' Present address. University of Natal, Durban, South Africa. Figure 1 . Ammonia synthesis reactor

Ind. Eng. Chern. Process Des. Develop., Vol. 9, No. 4, 1970 503
conversion could be increased by 14%. Obviously, one \
\
does not have direct control of the temperature profile, \ Equil. Temp
but it could be affected by the configuration of the heat
transfer surface-e.g., added insulation and/or fins.
Indeed, Dyson (1965) considered the general problem
of determining the heat transfer coefficient us. length func-
tion that would maximize the yield in an autothermal
reactor.
In this paper, the Maximum Principle is applied to
the design of a variable heat transfer coefficient, ammonia
synthesis reactor. Economic factors are included in the
analysis. A simplified computational procedure is de-
veloped and results are presented in graphical form to
permit design of reactors of this class with little additional
computation. I t was found that the yield could have
been increased by 5.4%,had the TVA reactor, as described
by Baddour et al., (1965) and Eymery (1964), been de-
signed with a variable heat transfer coefficient.
In addition to being a contribution to the specific field ) IA IB Jc
of ammonia synthesis reactor design, it is hoped that
the paper contributes to the more general field of economic
)
- Distance
Bottom

autothermal reactor design. Figure 2 . Schematic of temperature profiles and NHI mole
Simulation fraction in TVA NH3 synthesis reactor

Process Description. The Haber process is operated a t

high pressure and produces ammonia from the following Pressure drop across the reactor is negligible compared
catalyzed reaction: to the total pressure of the system.
N? + 3 HZ = 2 NHj Energy Balances. FEEDGAS. Referring to Figure 3, an
A schematic diagram of the TVA reactor (Eymery, energy balance on the feed stream yields the following
1964) is presented in Figure 1. The reaction zone (shaded) equation:
contains the catalyst. A number of cooling tubes are
inserted vertically through the reaction zone. The feed
gas comes in from the lower part of the reactor and
flows up through the heat exchanger and cooling tubes
to the top of the reactor. Then, changing direction, it where
flows down through the reaction zone and heat exchanger u = over-all heat transfer coefficient, kcal/
to the outlet. (m .hr C)
As with all reversible exothermic reactions, the tem- SI = surface area of cooling tubes per unit length
perature a t which the reaction rate is maximum decreases of reactor, meters
as the conversion increases. The relationship between this T, = temperature of reacting gas, O C
ideal temperature and the conversion is presented in Ti = temperature of feed gas, C
Figure 2. Even though one would like to maximize the W = total mass flow rate, kg/hr
reaction rate a t each instant, it is impossible t o obtain C,i = specific heat of feed gas, kcal/ kg C
this ideal temperature profile by control of the available x = distance along axis
design iiariables. The countercurrent flow does, however,
REACTING
GAS. Similarly, for the reacting gas,
cause the temperature to decrease in the bottom part
of the reactor because of heat transfer between the reacting
and feed gases. I t is possible to enhance this effect by
causing the heat transfer coefficient to vary along the
feed gas tube. I t is this enhancement that is considered
in this paper.
Assumptions. The following assumptions are used: -Tube wall
The Temkin-Pyzhev (1960) equation for the rate expres-
sion is valid.
The model is one-dimensional-i.e., the temperature and
concentration gradients in the radial direction are neglect-
ed.
Heat and mass diffusion in the longitudinal direction
are negligible.
The temperature of the gas flowing through the catalyst
zone is equal to the temperature of the catalyst particles.
The heat capacities of the reacting gas and the feed Reacting Gas Feed Gas
gas are constant. (T,) (Tf)
The catalyst activity is uniform along the reactor and
equal to unity. Figure 3. Heat flow from reacting gas to feed gas

504 Ind. Eng. Chem. Process Des. Develop., Vol. 9, No. 4,1970
where
-1H = heat of reaction, kcallkg mole of Nz
S? = cross-sectionalarea of catalyst zone, m
R = reaction rate, kg moles of N r / (hr m)
C,. = heat capacity of reacting gas
hlaterial Balance. Referring to Figure 3, consider the
incremental distance in the catalyst zone. Performing a
Y 2material balance yields
where N\ = mass flow of nitrogen per unit area of catalyst
zone, kg moles/ (m. h r ) .
On a semiempirical basis, the Temkin-Pyzhev (1960)
equation for the ammonia synthesis is given as
where
f = catalyst activity
P H p\,
9
P L H= partial pressures of H?,N r ,and N H
K , , K , = rate constants; K , = f 6exp. ( - E , I R T )
Reduction of Differential Equations to Dimensionless
Form. Using the dimensionless groups
where
C; = total flow at top of reactor, kg molesim hr
T,, = reference temperature
L = reference length
The system equations can be written as
2001
To P
I :o
Distance ( M I
Figure 4. Comparison of temperature profiles
dX i
GI=- =1
ds
where the variable, s, is to be viewed as a general distance
along the path or extent of the phenomena (In this
particular problem it is identified, as shown in Equation
9, with the dimensionless reactor length) and where
Kc = L G
K1 = S1.L W * C p ,
K? = Si*LW.Cpf
Kj = ( - A H * S ? ) / ( C . C p , ) ( LTo)
Results. The temperature profile computed is compared
with the measured plant profile in Figure 4. The data
used in the simulation are presented in Appendix A.
Design Problem
Objective Function. Let:
V1(X0,X I ) = value of the product, considered t o be a
function of the composition, X n , and the
temperature, XI, only, the pressure
being regarded as fixed
V 2 ( X 2 )= value of the feed gas, considered to be
a function of the temperature, X r , only,
the pressure and composition being
regarded as fixed
C , ( X , ) = annual cost of the reactor, considered to
be a function of the length, X i , only,
the pressure being regarded as fixed
The following objective function is used in this study.
2:o 3.. 0 410 i.0
Bot tom
Ind. Eng. Chem. Process Des. Develop., Vol. 9, No. 4, 1970 505
 J = [Vi - V?- C,]/n Z 2 = unit value of
(10)
feed gas
I dZ2
- = -[Z1K1 + Z?Ke]u(l4c)
where n is a normalization constant to be evaluated a t \ ds
a later step. temperature
Formal Statement. MAXIMIZE. J = [VI - V 2 - C , ] / n
By optimal choice of
Zn = unit value of dZ,
-=1
reactor length f ds
u(s) = heat transfer coefficient as a function of axial
position
According to the Maximum Principle (Rozonoer, 19691,
X L ( S ) = inlet feed gas temperature
if J is to be maximized, H ( s ) must be extremized with
X , ( S ) = reactor length
respect to u(s) a t each point, 0 5 s 5 S.
Subject to Equations 6 through 9 For convenience we define

0 5 u(s) 5 u* (104
K H [Z1K1 + Z?K?] (15)
From Equation 13 H is linear in u and the coefficient
Xi(0) = X2(0);feed and reacting gas of u is KH(Xi - X2).
temperatures must be equal at top (lob) Since ( X , - X , ) > 0 , 0 5 s 5 S, the general design
X,,(O)given (10c) policy is as follows:
If
Xi(S) = kiX*(S)+ h2[Xo(0) - Xo(S)];
KH < 0, then uopt = u*
over-all enthalpy balance (10d)
KH > 0, then uopt = 0 (16)
KH = 0, then uopt is not specified by the maximum
where principle-Le., extremization of H .
This last case, in which KH = 0, is known as the singular
case. I t is of interest only if it persists. Z1 = Z2 = 0
is sufficient to cause K H = 0. For this condition to persist,
it is sufficient to have dZ,/ds = d Z 2 / d s= 0. From Equation
14, d R / a X , = 0 is sufficient. This is a particularly
interesting condition, since it defines the ideal temperature
discussed above. This condition allows one to evaluate
Adjoint System and General Design Policy uOptwhen KH = 0.
The corresponding solutions t o Equations 6 t o 9 and
For convenience we define the so-called adjoint varia-
14 must satisfy the eight boundary conditions. Three of
bles,
these are imposed on the state variables:

X o ( 0 )= a", a known value

X1(0)= X 2 ( 0 ) ,continuity
and the Hamiltonian Xi(0) = 0, reactor length measured from
the top
We now derive the remaining five boundary conditions
on the adjoint variables. The boundary conditions on
I t can be shown (Equations 9 and 10) that the adjoint variables are obtained from the following
definition:
dJ max
Z , ( s )= ~

ax,(s)'
From Equations 6 to 9 and 11,
where J,,, is the maximum value of J .
H = -[ZlKi + Z?K2][Xi- X ? ] U- Now, a t s = 0 the above constraints apply. Treating
[ZoKo - ZiK?]R + 23 (13) these constraints by the method of Lagrange multipliers
From Equations 12 and 13, (Converse, 1970) we form the Lagrangian
L = Jmax [ X ( O ) ]- xi[Xn(O) - ao] -
20 = unit value of 1 dZn A?[XI(O)- XZ(O)]- X,X,(O)
N2flow ,f ds=

Z1 = unit value of or ZO(O)= X1-i.e., is unknown.

reacting gas
( dZ1
-= [ZIKI + ZrKrIu +
temDerature I ds

or Z1(0) = h2-i.e., is unknown.

506 Ind. Eng. Chem. Process Des. Develop., Vol. 9, No. 4, 1970

or
Z,(O) = -A, = -Z(O)-i.e., Z?(O)is set by Z I ( 0 )
(17)
iiL dJ,,,
- xi = 0
3x1 ax,
or Z1(0)= hi-i.e., is unknown.
At s = S there are no explicit state constraints. The
over-all enthalpy balance does apply, but this is taken
into account through the integration of the state equations.
Hence
The above four equations plus Equation 17 constitute
the five boundary conditions on the adjoint equations.
The normalization constant, n, is chosen to make
Z,,(S) = 1 (18)
This vields
I t is important to recognize the role played by the
adjoint variables. They really are evaluators and the
external economics influence the design through the bound-
ary conditions of the adjoint variables. The above partial
derivatives are unit prices-Le., interstage transfer prices.
The economic analysis presented in Appendix B
indicates that Zl(0) N 0 and Z z ( 0 ) N= 0. The effect of
this approximation was studied by Roberts (1969) and
found to be negligible. From Equation 14d, Z3(s) is con-
stant. In determining the optimal ( u ) s we are therefore
free to select &(S) to be any value, since it merely changes
the value of H by a constant value and therefore does
not affect the design policy-Le., u ( s ) . In computing the
optimal length of the reactor, dC,/aX,j is important and
the optimal length could be determined from Equations
11 and 21, recognizing that aC,/aX, is a function of X.3.
Although the adjoint boundary conditions are known
a t s = S, three of the four state boundary conditions
are known a t s = 0. Formally, one could guess three
of the state variables a t s = S (setting the fourth in
accord with Equation 10d), and integrate the state and
adjoint equations to s = 0, iterating the guessed values
until the boundary conditions at s = 0 are met. Such
mixed boundary value problems are difficult to solve
numerically, and we therefore seek t o limit the number
of boundary conditions to be matched.
Since X i is absent from all G,, its absolute value is
unimportant. The length of the reactor is given by XI(S)
- Xi(0) and the value of X , i ( S ) can be chosen to be
any value. If one guesses a value for X o ( S ) and assumes
that the singular case will persist for a finite region con-
nected to s = S, say si 5 s s S, then XI(S) can be
evaluated from dRdXl = 0. The following algorithm can
now be followed:
1. Guess si.
2 . Guess X , ( S ) .
3. Integrate the state and adjoint equations until XO
= X,(O), which is fixed. This identifies the top of the
reactor. During this integration u ( s ) is chosen so that
dR ax, = 0 in the region s1 s 5 S. For s s s1 it
is set equal u" or .u, depending on the sign of K H .
4. Is Xl(0) = X2(0)?
Yes: X o ( S )is satisfactory.
No: Reset X o ( S )and return to step 3.
5. Iterate on s1until J is maximum.
Murase (1968) found that because of instability in the
numerical integration of the adjoint equations, the itera-
tion on s I did not converge; the following general design
policy seemed to apply.
For s l S s g S. choose u ( s ) so that aRlaX1= 0.
For s25 s 5 sl, set u ( s ) = u*.
For 0 5 s 5 sz,set u ( s ) = 0.
Intuitively, this is a satisfying policy. At the top, the
heat transfer coefficient is set a t its lowest value in order
t o increase the reacting gas temperature. This is followed
by a section in which the coefficient is large, in order
to bring the reacting gas temperature back down to the
ideal temperature. At this point, the coefficient is set
in a variable manner, so that the ideal temperature profile
is followed in the rest of the reactor. This has intuitive
appeal when one is trying to maximize the yield. When
one is trying to maximize economic return as in this
case, this policy is correct only because ZI(S) N Z , ( S )
N 0; else the singular policy a t the bottom of the reactor
would be incorrect.
Results
Murase (1968) used the above design policy to solve
problems in which the conversion is fixed and the reactor
length is to be minimized.
The state equations were integrated from s = 0 to
s = S in accord with the following algorithm.
1. Set X o ( 0 )and X 3 ( 0 )to known values.
2. Guess X I(0).
3. Set X 2 ( 0 )= Xl(0).
4. Guess s2.
5. Integrate over 0 5 s 5 s2 with u ( s ) = 0.
6. Integrate from s = s2 with u ( s ) = u" until an ideal
temperature is reached-Le., the temperature a t which
aR dXl = 0. Call this point sl.
7. Integrate from s1 until Xo = known final value,
with u ( s ) set so as to cause a R l a X , = 0.
8. Iterate on s2 until reactor length is minimum.
9. Iterate on Xl(0) until reactor length is minimum.
Murase (1958) carried out these calculations for 0.10
5
- X o ( S ) 0.22. The results for X o ( S )= 0.20 (the value
obtained from the simulation of the TVA reactor) are
presented in Figure 5 . The loci of sz,sl, and X s ( S ) are
shown as a function of the top temperature. From this
figure the optimal conditions are: top temperature =
451"C, si = 0, s1 = 2.17 meters, and minimum length
= 4.29 meters. The corresponding bottom temperatures
were found to be 474" and 249C for the reacting and
Ind. Eng. Chem. Process Des. Develop., Vol. 9, No. 4, 1970 507
 600
*\.
5501
'.
'*,/Ideal Temp Profile

50C

0
0
v

Q,
L
3

I
z 400
0
Q

300- , lL4.fS ,
E
I .O 2.0 3.0 4.0 5.0 6.0 7.0 8.0 9.0 IC
) ?
Minimum Reactor Length ( M I 30C

Figure 5. Top temperature vs. minimum reactor length and

locations of first and second switching points
s = SA s = S I , Given N,, ( S ) = 0.200728, bottom temperature of reacting
gos = 473.7 ' C, of feed gas, 249" C
I
20c I
1.0 2.0 3.0 4.0 5 .O

feed gas streams, respectively. As presented in Figure Distance (M)

7, this composition with the simulated, constant-beat-
Figure 6. Temperature profiles of optimal trajectory
transfer-coefficient,TVA reactor indicates that the reactor and plant case
could have been shortened by 1 7 5 in order t o obtain
the same yield, or the yield increased by 5.4% with the
same length. The corresponding temperature and heat If Y o = Xo,Y1= T . , Y L= T,, then from Equations
transfer coefficient profiles are presented in Figures 6 and 5 through 8
8.
The calculations are greatly simplified by the fact that d Yo = - R
the design policy displayed in Figure 8 is not affected
-
dt
by the outlet ammonia conversion. Hence, one could solve
the economic problem by choosing the reactor length so
that Equation 17 is satisfied, or what is easier, so that
J is maximum. This can be done with use of Figures
7 and 9. Figure 7 presents the relationship between optimal d Y? - -I [ Y ,- Y,]u,
___ -
ammonia mole fraction and reactor length. Figure 9 pre- dt CP.f
sents the corresponding values of feed and reacting gas
temperatures, thus permitting evaluation of J as a function By definition,
of reactor length. The corresponding hot spot locations dYj dt = 1 (27)
and temperatures are presented in Figure 10. A logical
The Y , obey the same boundary conditions as the X,;
extension of this work would be the case in which this
hence the solutions are similar. Murase (1968) solved this
temperature is constrained to be less than, say, 500"C,
problem in the same manner as the previous one. From
in order to prevent catalyst deactivation. These results
are all for an ammonia concentration in the feed gas
of 0.05 mole fraction. Murase (1968) carried out similar
calculations for a value of 0.01. Proceeding in this manner,
one could optimize the entire process recycle loop.

Extension of Range of Application

The results thus far have been restricted to the given
gas flow rate and reactor geometry. T o remove these
restrictions, the state equations are transformed as follows:
Let
t-sLG (22)
I I

(23)

where Mi molecular weight of the feed. Figure 7. Ammonia mole fraction profile

508 Ind. Eng. Chem. Process Des. Develop., Vol. 9, No. 4, 1970
 0,25t- - - ----I
9
N
H Figure 8. Ammonia mole
i fraction v s . reactor length
I
a n d optimal heat transfer
- 500: \
coefficient v s . reactor length
Y
v

c
a
0
3

I I
0.05J L o
1.0 2.0 3.0 4.0 5.0 6.0 7.0 8.0
M i n i m u m Reactor Length ( M I

Figure 9 . Ammonia mole

fraction vs. optimal temper-
atures of reacting gas a t
bottom

400 500 600

Optimal Temperature of Optimal Temperature of
Feed G a s ("C) Reacting Gas ("C)

the resulting relationship between u1 and t (see Figure

l l ) , one can obtain u ( s ) for any known W, S1, Sz,and
Di. The lower limit of u 1 is the same as u-namely,
zero. As can be seen from Equation 23, the upper limit
of u , depends on SI, D,, and S 2 as well as the upper
limit on u. For this reason the following range of values
for the upper limit on u was investigated: ul* = 350,
613.2 (corresponds to the case reported above), 1000, 1500,
and 2000, referred to as cases A through E , respectively.
The resulting design relationships are presented in Figures
11 through 15.
Conclusions

If the ideal trajectory were followed along the whole

length of the reactor, the exit ammonia mole fraction
would be 0.218 for a reactor length of 5.18 meters. This
represents an improvement of 8.52% of the conversion
achieved in the plant (0.20) and is the upper limit of
the improvement which can in practice be obtained.
This upper limit is displayed in Figure 16, together 0 I .o 500 550 600
with the percentage improvement obtained by the optimal Location of Max. Temp of Reacting
trajectory for various values of u * . The value of high Max. Temp(M) Gas VC)
u * is apparent.
In terms of the general problem, this means that a Figure 10. Ammonia mole fraction vs. maximum temperature
large value of u I is desirable above the switch point; and its location

Ind. Eng. Chem. Process Des. Develop., Vol. 9, No. 4, 1970 509
this can be achieved in a number of ways (Equation Consideration of an economic objective function
22). indicates approximately the same general design policy
I. Increase u above the switch point. as a minimum length objective function subject to fixed
11. Increase SIabove the switch point. conversion. The solutions to this problem are presented
111. Decrease S2 above the switch point. graphically, permitting design without numerical integra-
I1 and I11 can be achieved by increasing the number tion of the state differential equations. The procedures
of cooling tubes above the switch point, whereas in our whereby the results of this latter problem can be used
initial problem only I was considered. to solve the original economic problem are described above.

0
Case E
2000
0
E 1

Figure 1 1 . Variable U , ,

3 c I I I I

0 5 .O 10.0 15.0 20.0 2 5 .O 3

Minimum t ( l ) x 1 0 4 (m3hr/kg moles)

Figure 12. Ammonia mole

fraction vs. modified mini-
mum reactor length t
Minimum t ( 1 )
a

-;
._
.-
o*'ol/ \ 'Case D
Case E
"
0
0.05'
Y I I I I
5.O 10.0 15.0 20.0 25.0 ?

(+J)
t = s LS x IO (m3hr/kg moles)

c 0.254

Figure 13. Ammonia mole

fraction vs. optimal tempera-
ture of reacting gas a t bottom

Q
0
the Bottom

0.05-
450 500 550 600
Optimal Temperature o f t h e Reacting Gas ("CHat the Bottom)

510 Ind. Eng. Chem. Process Des. Develop., Vol. 9, No. 4, 1970
 Figure 14. Ammonia mole fraction v s . optimal temperature of feed
gas a t bottom

a w m m a
a a
m 0 $ 02
% 0 $ In
0
0 0 00 s 0
0

520 540 560 580 600 0 5 IO

Maximum Temperature o f It's Location t x 104
Reacting G a s ( O C )

Figure 15. Ammonia mole fraction vs. maximum temperature of reacting gas a n d
its location

Appendix A. Data Used in Simulation

Eymery (1964) presented plant dimensions and

operating conditions in an actual plant. The same condi-
tions are used here.
Reactor Dimensions.
Catalyst Zone
Total volume 4.07 m'
Reactor length 5.18 m
Reactor basket diameter, Do 1.1 m

:i
Reactor basket cross-section area 0.95 m2
Catalyst zone cross-section area, S2 0.78 m'

Number of tubes
Tube outside diameter, 0 2
Tube inside diameter, D1
Cooling Tubes
84
50.8 mm
38.1 mm
i
aE 0 500 1000 1500 2000

Tube heat exchange area (outer) 69.4 m2 U" ( K c a l / h r . M * " C )

Tube heat exchange area (inner), SI 52.0 mi
Figure 16. Ammonia production increase vs. maximum limit
Heat Transfer Coefficient, u. Baddour (1965) gave the for U"
heat transfer conductance ( U S ) = 57.300 B t u / h r for O F On basis of plant case

Ind. Eng. Chem. Process Des. Develop., Vol. 9 , No. 4, 1970 5 1 1

this reactor. On the basis of the cooling tube inside Reactor Cost. Data published in 1956 were used as a
diameter, guide to reactor cost. Costs were obtained by extrapolating
data for 1500-psi steel pressure vessels to 4500 psi (Aries
(US) - 57.300 x 4.882 x 0.092903 - and Newton, 1955). For the reactor under consideration
u=-- -
SI 51.9185 with cross-sectional area of 0.95 sq meter, the costs are
given in Table I as a function of reactor length. The
costs in this table are corrected costs according to the
process industry indices (Chemical Engineering, 1968).
Marshall and Stevens Process Industries Index 1954
u = 500 is used in this p a p e r = 186
Operating Conditions. Marshall and Stevens Process Industries Index 1967
= 263
Feed Compositions, Mole Fraction
Tank reactors and pressure vessel costs (Peters and
H? iV2 NH, CH? A*, Trimmerhaus, 1968) are normally related as follows: Log
Computation 0.2175 0.6525 0.05 0.04 0.04 (cost) = K1 + K2 log (capacity). Cost = K 1 .(capacity) K? ,
Plant data 0.219 0.65 0.052 0.79 normally K 1 < 1.
Pressure, P = 286 atm Therefore, by least squares regression, the following
Top temperature, T.," = T,"= 421" C model was found to fit the data well, with a standard
Mass flow rate, W = 26,400 k g / h r deviation of $2.668.
(Space velocity, V. = 13,800 hr I )
Density of the feed gas, D,= 10.5 kgikg-mole Cost of reactor ($1 = A + ( B + CX,)'
' (B3)
Exit ammonia concentration (mole fraction) = 0.200728
Properties of Reaction System. A = -1.07532 x 10'
HEATCAPACITY B = 0.1305 x 10"'
Reacting gas C = 0 719 kcal/kg O C C = 0.7489 x loi1
Feed gas $/= 0:707 kcalikg O C

REACTION
KINETICS Equation B3 gives the capital cost of the reactor. For
El = 20,800 kcalikmole of NP, E? = 47,400 kcal/ an annual cost, an econ?mic life of 10 years and an interest
kmole of K 2 (Annable, 1952) rate of 10% are pssurnd, such that
f i = 1.78954 X lo", f2 = 2.5714 X 10'' Annual reactor cogt = [A + ( B + CX,)'
'ID (B4)
-AH = 26,600 kcalikg mole of N a where D = 0.16275 (Taylor, 1964).
f = 1 OBJECTIVE FUNCTION. From Equations B1, B2, and
B4,
Appendix B. Determination of Economic
Obbctive function and Partial Derivatives VI ( S ) G K , - K,X,(S) + K6X1 ( S ) 035)
where
Value of Product Gas. By assumption, the value of the
product gas is dependent on its temperature and ammonia Kq = 2GS2NiCAvF ( 0 ) - Cp,,. T,WLLTiCHXi
content-i.e., first-order approximations are used: C H ,cost Ki = 2GSzNiCA
of heating, and C.4, cost of ammonia, are considered fixed,
whereas in fact they vary with temperature and ammonia Ks = Cp3,ToWNiC~
concentration, respectively. V J ( S )= K ; - K i X , ( S ) (B6)
VI = V , ( X ! ,XI)
,
By assertion

.W Ni CH
(kgihr) (hr/yr) ($/kcal)
/
Heating value, $/yr
Ni C.4
Dimensionless ammonia hr/yr $/kg N H I
flow, kg NH:i/kg

Sale value, $lyear

Value of Feed Gas, The feed gas composition is consid-

ered fixed; hence, its value is considered to be a function
of temperature only-Le., Table I . Costs
V?= V , ( X , ) Reactor Length, Meters Cost, S x IO-'
0.398 72.879
By assertion, 1.591 141.471
vj = - x:~"
cn,iT,,[x,(s) IWN, (B2) , 3.986 235.785
z i 7.970 330.099

5 12 Ind. Eng. Chern. Process Des. Develop., Vol. 9, No. 4, 1970

where All other values in the cost equations are the same
as those used by Roberts (1969). Substituting values into
Equation B6,

K : + K , = 11.9877
Ki = 55.063
where Kb = 0.2964
K - = 0.2944
Ka = 3.475 x lo-
Kg = 1.987 x l o -
Then from Equation 3 and above Acknowledgment
J , = /KI + K ; ]- K , X , ( S )+ K & I ( S ) - Grateful acknowledgment is made for partial financial
K - X ? ( S )- [ K , + KsXi(S)] (B8) support provided by National Science Foundation Grant
62-7326, by the South African Council for Scientific and
ECONOMIC DERIVATIVES Industrial Research, and the hippon Light Metal Co.,
From Equation B5, Ltd., Tokyo, Japan. The work is obviously dependent
on the fine facilities of the Kiewit Computation Center,
Dartmouth College, Hanover, N. H. Tapes of programs
used by Murase (1968) can be obtained a t cost from
From Equation B6, the center.
Literature Cited

Annable, D., Chem. Eng. Sci. 1 (4), 145 (1952).

Aries, R . S.. Newton, R . D., Chemical Engineering Cost
Estimation, p. 16, McGraw-Hill, New York, 1955.
From Equation B7, Aris, R., Optimal Design of Chemical Reactors, Aca-
demic Press, New York, 1961.
Axton Cross Corp., Manchester, N. H., 1968.
Baddour, R . F., Brian, P. L. T., Logeais, B. A., Eymery,
J. P., Chern. Eng. Sei. 20, 281 (1965).
Chern. Eng. 222 (July 15, 1968).
From Equations 19 and 20, together with the above equa- Chilton, C. H., Cost Engineering in the Process
tions. Industries, p. 113. McGraw-Hill, New York, 1960.
Converse, A. O., Optimization, p. 174, Holt, Rinehart
K6 & Winston, New York, 1970.
Z , ( S )= - -= 0.0054 Denbigh, K. G., Trans. Faraday Soc. 40, 352 (1944).
Ki Dyson, D. C., Optimal Design of Reactors for Single
K- Exothermic Reversible Reactions, Ph.D. thesis, London
Z , ( S ) = - = 0.0054 University, 1965.
K- Eymery, J., Dynamic Behavior of an Ammonia Synthesis
Reactor, D S c . thesis, M.I.T., 1964.
McEwan, M. W., Beveridge, C. S. G., Chem. Eng. Sci.
Cost Data. COSTOF HEAT.Based on the cost of heating 20, 987 (1965).
oil. the cost of heat is taken to be Murase, A., Optimal Thermal Design of Autothermal
CIi = $4.453 x 10 - per kcal Ammonia Synthesis Reactors, M. E. thesis, Dartmouth
College, Hanover, N . H., 1968.
COSTOF AMMONIA. Gaseous industrial ammonia is sold Peters, M. S., Trimmerhaus, K. D., Plant Design and
for S70 per ton (Axton Cross Corp., 1968), so that Economics for Chemical Engineers, p. 300, McGraw-
C , = $1.3147 per kgemole Hill, New York, 1968.
Roberts, H. L., Economic Aspects of the Optimal Ther-
N ,is taken to be 8330 hours per year. mal Design of an Autothermal Ammonia Synthesis
COST O F HEAT EXCHANGE. The annual cost of heat Reactor, postdoctoral report, Thayer School of
exchange equipment has been a&umed proportional to Engineering, Dartmouth College, Hanover, N . H., 1969.
the heat exchange duty. A rough calibration fot the case Rozonoer, L. I., Automation Remote Control (USSR) 20,
T (SI= 127 C gave the capital cost of the heat exchanger, 10 (1959).
adjusted according to Marshall and Stevens process Taylor, G. A., Managerial and Engineering Economy,
industries indices to be $4850 (Chilton. 1960). p. 197, Van Nostrand, Princeton, N . J., 1964.
Temkin, B. I., Pyzhev. V., Acta Physicochim. (USSR)
Amortization a t 1 0 5 for 10 years gives an annual cost 12, 327 (1960).
of $790. Comparing this figure with the total cost of
heating in Equation B2 gives RECEIVED
for review January 2, 1969
F = 1.01 ACCEPTED June 11, 1970

Ind. Eng. Chem. Process Des. Develop., Vol. 9, No. 4, 1970 5 13