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Deokl N. Saraf
Depadmnt of Chemical Engineering, Indian InstirUte of Technolcgy, Kanpur 2080 16, India
Models of various important process units comprising an ammonia plant, which were validated against extensive
plant data, have been unified in an overall plant simulation. This simulation has been used to check the performance
of two plants, each at two levels of operation, one of which is based on naphthas whereas the other one uses
natural gas as the raw material. The calculated compositions, temperatures, and flow rates at various points along
the process stream, including the recyle around the ammonia synthesis reactor, are in very good agreement with
the corresponding measured values. This shows the generality and accuracy of the process unit models as well
as that of the overall simulation. Effects of errors in the models on calculated rate of ammonia production, pressure,
and concentration of inerts in the ammonia synthesis loop are also illustrated.
balance equations for this reactor are the same as those B M'k,mOIelhr
C
for PR except that no heat is supplied to the process gas
in SR. Integration of the model differential equations,
along the length of SR yields temperature, composition,
and pressure throughout the catalyst bed, in close agree-
ment with the measured values (Singh, 1978).
Shift Conversion
The conversion is expressed by eq 2. It is carried out
in two consecutive adiabatic reactors which use different
catalysts and work under different conditions of temper-
ature. In the first reactor, Le., the high temperature shift
reactor (HT), which uses a chromia promoted iron oxide
catalyst, reaction is carried out ,between 350 and 500 "C. Figure 2. Recyle scheme of ammonia synthesis.
The low temperature shift reactor (LT) uses a CuO-ZnO
catalyst with various promoting components and operates The outlet from one reactor makes the feed to the sub-
in the range of 180-250 O C . sequent one. Air and steam added at SR and H T inlets,
The rate of shift reaction over the shift catalysts (of respectively, are accounted for by mass balance. Tem-
FPDIL, India) are given by the general expression perature changes associated with heat removal in between
any two reactors is not considered; instead the measured
values of temperature after cooling are used in simulation
calculations. The ammonia synthesis reactor involves
recyle of a major part of the product gas. This recyle gas
where Rf,A , Pf,Sf,and E f f are factors which account for mixed with makeup synthesis gas, i.e., methanator exit,
the effects of reduction in specific surface area due to is the synthesis reactor feed.
sintering, aging, pressure, H a concentration in process gas, The recyle scheme of the ammonia synthesis reactor is
and diffusional resistances, respectively; u2.and e, are shown schematically in Figure 2. The flow and compo-
preexponential factor and intrinsic energy of activation for sition of purge, recyle, and feed is obtained from the fol-
reaction 2, and xco and x*co are mole fractions of CO in lowing component and overall mass balance equations.
the reactor and in equilibrium conditions. Due to low The components are numbered for the following equations
operating temperature and insignificant presence of HzS, as: 1, N,; 2, H,; 3, NH3; 4, CH,; and 5, Ar.
reduction in rate due to sintering and H2S are negligible Mass Balance around Synthesis Loop (Figure 2).
for the LT; i.e., Rf and S, are both equal to 1 for the LT. Paj" = i@.(xip - ( U ~ ~ . X P-) a3rWr*
Values of u2 and e, and the various factors in the rate j = 1, 2, 4, 5
expression 2 are different for HT and LT. Details for (24)
evaluating the various factors numerically along with va- Mass Balance around Point A (Figure 2).
lidations of the models against extensive plant data are
available in the references (Singh and Saraf, 1977,1980). P . x j m + iW.x; = Mf-xif j = 1, ..., 5 (25)
Ammonia Synthesis Mass Balance around Point D (Figure 2).
Equation 3 describes the reaction, and the following
modified Temkin equation (Dyson and Simon, 1968) gives Me.x; = (W+ i W ) - x f j = 1, 2, 4,5 (26)
the intrinsic rate of reaction
M e . ~ 3=
e (Mp + iW).x3' + MP'* (27)
Component Balances for Various Streams.
5
Table I. Measured and Calculated Data for Naphtha Based Ammonia Plant
process inlet PR case I case I1
number of PR tubes 160 pressure, kg/cm 24.8 24.3
diameter of PR tubes 115.3 mm i.dJ147.7 mm 0.d. temperature, "C 443 440
heated length of PR tubes 11.36 m SR inlet air temperature, "C 231 231
SR catalyst 25 tonsl19.4 m3 H T inlet temperature, "C 377 364
HT catalyst 75 tonsl58.2 m3 L T inlet temperature, "C 202 200
LT catalyst 73 tons/56 m3 synthesis reactor inlet temperature, "C
synthesis catalyst 57.2 tons/20.9 m 3 1st bed 395 389
2nd bed 412 428
process inlet PR case I case I1 3rd bed 406 404
process naphtha flow, kg/h 1 4 100 11900 pressure at synthesis reactor inlet, 228 214
steam flow, kg/h 67200 56000 kg/cm2
loop. The three variables selected for the purpose are in the various cases (bottom lines of the tables), are based
concentration of inerts in the recyle stream, i.e., ( x l + x;), on weight measurements and are independent of the
concentration of ammonia in the recyle stream, i.e., x i , and concentration measurements of ammonia in various
the concentration of ammonia at the reactor exit. The streams of the synthesis loop (Figure 2). Therefore the
values of the first two variables are taken from the plant rate of ammonia production based on the measured con-
data whereas that of ammonia concentration in the exit centration of ammonia in the process streams may not
stream is assumed and the flow rate and composition of necessarily equal the measured rate of ammonia produc-
the feed stream are calculated. The synthesis reactor tion reported in the bottom lines of Tables I through 111.
model evaluates the ammonia exit concentration. The Measured flow, temperature, and composition of the
assumed and calculated values are matched by an iterative process gas at the exit from PR, SR, HT, LT, and the
procedure to arrive at the final results. synthesis reactor, for all the cases, compare very well with
the corresponding calculated values. For all the four cases,
Results and Discussion measured and calculated pressure drops across the PR and
Validation of the Simulation. The calculated and SR are also in very good agreement. Similar agreements
measured values of process and operating variables at exist for the flow and composition of various streams
various points in two ammonia plants, each at two levels around the synthesis loop. The maximum difference be-
of operation, are presented in Tables I and 11. It should tween the calculated and measured rates of ammonia
be noted that the measured rates of ammonia production, production are within 4 % . In addition to being small, the
Ind. Eng. Chem. Process Des. Dev., Vol. 20, No. 3, 1981 429
Table 11. Measured and Calculated Data for Natural Gas Based Ammonia Plant
process inlet PR case I case I1
number of PR tubes 200 temperature, "C 456.4 447.4
diameter of PR tubes 96 mm i.dJ133.8 mm 0.d. air temperature at SR inlet, 460.0 460.0
heated length of PR tubes 12.2 m "C
SR catalyst 14.83 tonsl12.4 m3 steam added at HT inlet, 7200 6000
HT catalyst 53.5 tonsl44.23 m3 kglh
LT catalyst 70.3 tonsI50.2 m3 HT inlet temperature, "C 361 351
synthesis catalyst 52.8 tonsl20.26 m3 LT inlet temperature, "C 198 200
synthesis reactor inlet tem-
process inlet PR case I case I1 perature, "C
process natural gas inlet, N m3/h 13 920 12 014 1st bed 385 406
steam flow, kg/h 61000 55000 2nd bed 433 430
pressure, kg/cmz 35.0 32.3 3rd bed 415 401
pressure at synthesis reactor 235 210
inlet, kglcm
press., t e p p , S/G flow N
location CO CO, H, CH, N, Ar NH, kg/cmz C ratio m3/h
Table 111. Compositions and Flow Rates to the Ammonia tion in Table I1 Case I, shows a higher calculated value at
Synthesis Reactor Based on Measured Flow and the HT exit, a lower value at the PR exit and in the
Composition of Makeup Gas make-up gas and almost equals the measured values at all
process gas stream
flow N
other points. As another example, the calculated methane
H, CH, N, Ar NH, m3/h concentration at the PR exit is observed to be less than
the corresponding measured values in three cases (Table
makeup exptl 74.59 0.80 24.32 0.29 72 900 I, Case I and Table 11, Cases I and 111),whereas in the
synthesis remaining case (Table I, Case 11) the reverse is true.
gas Similar observations can be made for concentrations of
inlet NH, exptl 65.90 6.54 22.03 2.51 3.02 248 000
reactor calcd 69.48 6.59 18.71 2.38 2.87 259603 other components and temperatures as well. Thus it can
outlet NH, exptl 53.46 7.32 18.12 3.10 18.00 216 000 be claimed that the overall simulation represents the plant
reactor calcd 57.64 7.52 14.11 2.73 18.00 226332 very well.
total ammonia produced tonslday: plant, 619; calculated, The above discussed results may be expected in view of
601 the fact that models for each of the process units, namely,
PR, SR, HT, LT, and ammonia synthesis reactor, have
differences between measured and calculated values are independently been validated against extensive plant data.
randomly distributed. For example, methane concentra- The ranges for the variables used in the present study are
430 Ind. Eng. Chem. Process Des. Dev., Vol. 20,No. 3, 1981
1 0.5 09 1.3
change in the H2/N2ratio in the makeup gas results in a Figure 6. Effect of Hz/N2 ratio on synthesis reactor pressure.
many times greater change in the H2/N2ratio in the re-
actor and all the streams in the recyle loop. the rate of makeup gas production, and the concentration
It is clear from the results in Figures 3 through 7 that of inerts and H2/N2 ratio in the makeup synthesis gas.
the performance of an ammonia plant is very sensitive to Low rate of makeup synthesis gas production, higher inerts
432 Ind. Eng. Chem. Process Des. Dev., Vol. 20, No. 3, 1981
Singh, C. P. P.; Saraf, D. N. Ind. Eng. Chem. Process Des. Dev. 1977, 16, Singh, C. P. P.; Saraf, D. N. Ind. Eng. Chem. Process Des. Dev. 1980, 10,
313. 393.
Singh, C. P. P.; Saraf, D. N. I d . Eng. Chem. Process Des. Dev. 1979a,
18, 1.
Singh, C. P. P.; Waf, D. N. Ind. Eng. Chem. Process Des. Dev. 1979b, Received f o r review October 12, 1979
18, 364. Accepted March 16,1981
Extraction characteristics of trioctylphosphine oxide (TOPO) dissolved in commercial kerosene for recovery of acetic
acid from dilute water solutions were studied. Some basic thermodynamic properties such as viscosity, density,
interfacial tension, and primary settling time of the extraction system were measured. Extraction isotherms at 20
OC were obtained for 3, 5 , and 18 wt % of TOPO in kerbsene. Finally, a simulation of countercurrent extraction
of water solution, containing 5 wt % acetic acid, and regeneration of the solvent was performed on laboratory
scale equipment.