Thermal Denitration of Ammonium Nitrate Solution in A Fluidized-Bed Reactor
Thermal Denitration of Ammonium Nitrate Solution in A Fluidized-Bed Reactor
Thermal Denitration of Ammonium Nitrate Solution in A Fluidized-Bed Reactor
pubs.acs.org/IECR
ABSTRACT: Ammonium diuranate (ADU) filtrate, which contains mainly ammonium nitrate (80−100 g/L), is generated
during hydrometallurgical processing of uranium. This filtrate stream poses a disposal problem because of its high nitrate content
and residual radioactivity. Fluidized-bed thermal denitration is considered as a suitable chemical-free disposal option for the
aqueous waste nitrate stream. Hence, investigations to explore the decomposition of ammonium nitrate in a fluidized bed have
been carried out. To enable theoretical analysis and performance evaluation of the process, a mathematical model was developed. The
model is based on two-phase theory of a bubbling fluidized bed. Model calculations were used to predict the axial concentration
profile of ammonium nitrate in the emulsion and bubble phases and the axial temperature profiles of gas bubbles, emulsion gas,
and emulsion particles. The mechanism of decomposition of ammonium nitrate in a fluidized bed was explored, and the con-
version of ammonium nitrate was estimated. Model predictions were compared with experimental data available from a bench-
scale plant. Good agreement was obtained between the model predictions and the experimental measurements. A steady-state
parametric study indicated that conversion is enhanced with an increase in bed temperature and feed concentration. It was found
that operation at higher feed concentration leads to local hot spots. The required reaction-zone length for complete conversion of
ammonium nitrate vapor in the emulsion phase was found to decrease significantly with increased bed temperature. No marked
effect of u/umf on conversion was observed. Optimum values of process parameters to maximize the conversion were derived.
© 2012 American Chemical Society 8394 dx.doi.org/10.1021/ie202018t | Ind. Eng. Chem. Res. 2012, 51, 8394−8403
Industrial & Engineering Chemistry Research Article
voidage at minimum fluidizing conditions εmf = 0.3507Ar 0.0337Remf −0.0704 Subramani et al.11
average bubble size at bed height z db = 0.21z 0.8(u0 − umf )0.42 exp[− 0.25(u0 − umf )2 − 0.1(u0 − umf )] Cai et al.12
bubble rise velocity ub = u0 − umf + 0.711 gdb Davidson and
Harrison13
fraction of the bed in bubbles u0 − umf Kunii and Levenspiel14
δ=
ub − umf
gas interchange coefficient ⎛u ⎞ ⎛ D0.5g 0.25 ⎞ Kunii and Levenspiel14
Kbc = 4.5⎜ mf ⎟ + 5.85⎜ 1.25
⎟
⎝ db ⎠ ⎝ db ⎠
⎡ Dε (0.711 gd ) ⎤
Kce = 6.77⎢ ⎥
mf b
⎢⎣ db 3 ⎥⎦
⎡ Toi et al.17
⎛ 2hpg ⎞⎤
heat-transfer coefficient between the bubble and emulsion
Cpgρg umf + ubγpCppρp ⎢1 − exp⎜⎜− 3τb ⎟⎥
phases 1 3 1
hbe =
⎛
⎜1 +
3εmf ⎞4
⎟
4 ⎢
⎣ ⎝ Cppρp d p ⎟⎠⎥⎦
⎝ u b / (εmf u mf )−1 ⎠
phases have been developed from fuel combustion models.8−10 in at a height 800 mm above the distributor when u/umf ≥ 7.
In the thermal denitration process, the feed solution is Depending on the temperature, decomposition of ammonium
introduced into the fluidized bed as a spray. It is assumed that nitrate can follow various modes of reaction, as follows:18−20
liquid droplets in the spray are deposited on the surface of hot 169 ° C
emulsion particles and vaporized. Hence, ammonium nitrate NH4NO3 ⎯⎯⎯⎯⎯⎯→ NH3 + HNO3
vapor is released into the emulsion phase, travels through the
ΔG573,1 = 12.94 kJ/mol (1)
emulsion phase, and undergoes decomposition. Transfer of
ammonium nitrate vapor from the emulsion to the bubble phase 170 − 230 ° C
through gas interchange between these phases is considered. NH4NO3 ⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯→ N2O + 2H 2O
Energy balance differential equations have been derived for the ΔG573,1 = −288.84 kJ/mol
bed phases to include the heat of reaction in the fluidized-bed (2)
thermal denitration model. All hydrodynamics- and heat- > 230 ° C 3 1
transfer-related parameters of a bubbling fluidized bed were NH4NO3 ⎯⎯⎯⎯⎯⎯⎯⎯→ N2 + NO2 + H 2O
4 2
estimated using the equations listed in Table 1. An increase in
bubble size due to atomizing air and vapor generation was taken ΔG573,1 = −379.39 kJ/mol (3)
into account by considering the superficial gas velocity as the
total volume of the fluidizing air, the atomizing air, and the vapor > 260 ° C 1
NH4NO3 ⎯⎯⎯⎯⎯⎯⎯⎯→ N2 + O2 + 2H 2O
divided by the cross-sectional area of the bed. The bubble size can 2
be determined by the equation given in Table 1. The transition ΔG573,1 = −413.63 kJ/mol (4)
from the bubbling to the slugging regime is taken into account by
checking whether the bubble size is greater than 0.7Dt, where Dt Gibbs free energy changes of all four reactions were determined
is the column diameter. It was estimated that slugging should set at 300 °C and 1 atm using the chemical thermodynamics
8395 dx.doi.org/10.1021/ie202018t | Ind. Eng. Chem. Res. 2012, 51, 8394−8403
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software FactSage 6.1. Reaction 4 has the most negative Gibbs place is called the reaction zone. An infinitesimally small
free energy change. Hence, according to thermodynamic laws, representative zone, Δz, of the fluidized bed was considered,
this is the most probable reaction. Reaction 4 is first-order with and mass and energy balance differential equations were
an activation energy of E = 102.6 kJ/mol, a frequency factor of formulated for the bubble and emulsion phases. For the
K0 = 4.55 × 107/s, and a heat of reaction of Hreaction = 118.86 kJ/mol. emulsion phase, two energy balance equations were set up, one
2.1. Assumptions on the Interactions between the each for the emulsion gas and particles. Profiles of the axial
Spray and the Fluidized Bed. Okasha and Miccio studied the concentration of ammonium nitrate and temperature were
pneumatic feeding of liquid fuel into a fluidized-bed combustor obtained by solving these equations.
operating at 850 °C.21 Their model predicted that part of the 2.3. Fluidized-Bed Denitrator Model. The following
liquid fuel is released as vapor inside the jet as a result of aspects for modeling the mass balance in the reaction zone
vaporization of the fuel droplets. This vapor was assumed to were considered:
contribute to the jet bubbles that periodically detached from the (1) Decomposition of ammonium nitrate takes place in both
jet. The remaining part of the injected liquid fuel reached the jet the bubble and emulsion phases.
boundaries, was deposited on the particles in the emulsion phase, (2) Ammonium nitrate is exchanged between the bubble and
and vaporized. Interaction between the spray and fluidized bed emulsion phases.
was found to be a combined effect of several microprocesses.
Because of the disruptive action of high-velocity atomizing air, The mass balance of ammonium nitrate in the emulsion phase
the liquid stream disintegrated into liquid drops. The mixture of was modeled as follows:
atomizing air and droplets had a very high velocity at nozzle
(disappearance of ammonium nitrate from the emulsion
outlet, so the mixture emerged as a jet from the twin fluid nozzle
with enough kinetic energy to even pierce the bed. Particles were phase) = (decomposition of ammonium nitrate in the
sucked into the jet stream, and a small fraction of total droplets
was deposited on the entrained particles. Atomizing air detached emulsion phase) + (transfer of ammonium
from the jet as jet bubbles. The operating temperature of the nitrate to the bubble phase)
thermal denitration process (∼350 °C) is quite low compared to
the fuel combustion process. At this operating temperature,
−[(1 − δ)AbΔz]ΔCeAN
radiative heat transfer from the fluidized bed to the solution
Δz
droplets can be neglected. All of the heat has to be transferred = K 0e−E / RTeg CeAN[(1 − δ)εmf AbΔz]
through the jet surface and by the entrained solid particles. The umf
sublimation point of ammonium nitrate is 210 °C. Vaporization Δz
+ Kbe(CeAN − C bAN)(δAbΔz)
of ammonium nitrate inside the jet is therefore quite unlikely umf
because of the very small residence time of the droplets.
dCeAN ⎛ε ⎞ δKbe
Evaporation of water, however, does take place in the jet. Jet = −⎜ mf ⎟K 0e−E / RTeg CeAN +
bubbles thus do not contain any ammonium nitrate vapor and dz ⎝ umf ⎠ umf (1 − δ)
can be treated the same as distributor bubbles. Most of the × (C bAN − CeAN) (5)
droplets follow the jet stream and get deposited on hot particle
surface in the emulsion phase. Precipitation of droplets on The mass balance of ammonium nitrate in the bubble phase was
emulsion particles and variation of drop concentration with modeled as follows:
distance from the jet outlet have been described in the
literature.22,23 Liquid droplets depositing on an emulsion particle (disappearance of ammonium nitrate from the bubble phase)
are assumed to form a uniform shell. The rates of evaporation of = (decomposition of ammonium nitrate in the bubble phase)
water and ammonium nitrate from particle surface depend on the
heat-transfer area and the heat-transfer coefficient between the + (transfer of ammonium nitrate to the emulsion phase)
particle and the liquid film. As drops are deposited over a large
surface provided by the particles, the area of heat transfer is large. −(δAbΔz)ΔC bAN
To the boiling point of the liquid, the particle-to-liquid film heat- Δz
transfer coefficient is the same as the particle-to-gas heat-transfer = K 0e−E / RTbC bAN(δAbΔz) + Kbe(C bAN − CeAN)
ub
coefficient. At the boiling point, the particle-to-liquid film heat- Δz
transfer coefficient is equal to the film boiling heat-transfer × (δAbΔz)
coefficient. Because of the rapid evaporation of the liquid film, ub
the vaporization process was almost completed in the spray zone, ⎛1⎞
dC bAN K
and the exchange of only dry particles was assumed to occur = −⎜ ⎟K 0e−E / RTbC bAN + be (CeAN − C bAN)
between the spray zone and the rest of the fluidized bed. dz ⎝ b⎠
u ub
Ammonium nitrate vapor is released into the emulsion phase, (6)
and its initial concentration in the emulsion phase is CeAN,0 =
Considerations for the energy balance over a small
mAN/(MANumfAb). The initial concentration of ammonium
representative section of reaction zone are schematically shown
nitrate vapor in the bubble phase is zero. Because of the in Figure 1. They include
continuous wetting and liquid evaporation, the spray zone
temperature is lower than the bed operating temperature (by 5− (1) heat generation due to the exothermic decomposition of
7 °C). Decomposition of ammonium nitrate in the spray zone is ammonium nitrate,
neglected. (2) heat transfer between the bubble and emulsion phases,
2.2. Reaction Zone. The bed available above the droplet (3) heat transfer between the emulsion gas and emulsion
deposition zone where ammonium nitrate decomposition takes particles,
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Δz
mbg Cpg ΔTb = K 0e−E / RTbC bANHreactionVbg
ub
Δz
− hbeS(Tb − Tep)
ub
dTb ⎡ 1
= ⎢ K 0e−E / RTbC bANHreactionVbg
dz ⎣ ub
1 ⎤
+ hbeS(Tep − Tb)⎥ (mbg Cpg)
ub ⎦ (10)
3. MODEL RESULTS
The differential equations for the mass and energy balances were
solved numerically using a fourth-order Runge−Kutta method.
Model inputs are presented in Table 2.
(meg C pg)
(7)
The energy balance for the emulsion particles was modeled as follows:
(energy accumulation in the emulsion particles)
= (transfer of energy from the emulsion gas)
+ (transfer of energy from the gas bubbles)
+ (transfer of energy from the wall)
emulsion is equal to the minimum fluidization velocity. The particles along the axial direction. The fraction of ammonium
residence time of the emulsion gas in the bed is relatively higher than nitrate decomposed in the bubble phase is negligibly small.
that of the gas bubbles. Therefore, decomposition of ammonium Consequently, no increase in gas-bubble temperature is
nitrate takes place predominantly in the emulsion phase. In observed.
principle, the initial concentration of ammonium nitrate in the 3.2. Ammonium Nitrate Conversion. Steady-state para-
bubble phase is zero. Because the rate of mass exchange between metric studies were conducted to assess the effects of operating
the emulsion and bubble phases is relatively low, a small fraction variables on the conversion of ammonium nitrate. One operating
of ammonium nitrate vapor could be transferred to the bubble parameter was varied while others were kept constant at specific
phase from the emulsion phase. The residence time of gas conditions.
bubbles in the bed is very short as compared to the residence time Effect of Bed Temperature. The influence of bed temperature
of the emulsion gas. These factors lead to negligible decomposi- on conversion along the bed height is shown in Figure 4. It is
tion of ammonium nitrate in the bubble phase. Ammonium
nitrate that enters into the bubble phase escapes from the bed
unconverted. Figure 3 presents the axial temperature profiles of
Figure 3. Model predictions of the axial temperature profiles of bubble clear that the conversion increases with increasing bed operating
gas, emulsion gas, and emulsion particles. temperature. The decomposition rate constant is a strong func-
tion of temperature and increases exponentially with temper-
ature. The magnitudes of the rate constant at 623 and 663 K are
the emulsion gas, gas bubbles, and emulsion particles. An overall 0.114 and 0.375 s−1, respectively. A 40 K increase in bed operat-
energy balance for the spray zone was carried out to estimate the ing temperature causes a factor of 3.3 increase in reaction rate
temperature in the spray zone, which is lower than the operating constant. Hence, the results appear to be quite reasonable.
temperature in the bed (623 K). The spray-zone temperature is a Effect of Bed Height. In Figure 5, the ammonium nitrate
function of the liquid feed rate, the quality of the dispersion, and vapor concentration in the emulsion phase is plotted against the
the interaction of the dispersion with the fluidized bed. In the
beginning of the reaction zone, the temperature of the emulsion
gas and emulsion particles is equal to the spray-zone temper-
ature. The ammonium nitrate decomposition reaction is exo-
thermic. In the front end of the reaction zone, the rate of decom-
position of ammonium nitrate is high, and the rate of heat
generation is also high. An initial sharp increase in the emulsion-
gas temperature indicates this fact. At the upper region of the
reaction zone, the rate of reaction is low because of the low
concentration of ammonium nitrate in the emulsion phase. The
emulsion-gas temperature passes through a maximum and then
decreases and approaches the particle temperature. In the upper
region of the reaction zone, the heat-transfer rate from the
emulsion gas to the particles is higher than the heat-generation
rate. Hence, the temperature gradient between the emulsion gas
and particles is reduced. On the other hand, considering the
temperature profiles of the emulsion particles and gas bubbles,
it is noted that there is almost no increase in temperature along
the bed height. The parameter ρCp of the solid particles is much Figure 5. Axial concentration profile of ammonium nitrate vapor in the
larger than ρCp of the gas. Therefore, when reaction heat is emulsion phase for different bed temperatures.
transferred to the emulsion particles from the emulsion gas, the
increase in particle temperature is negligible. Also, effective particle dimensionless bed height for different bed temperatures. When
mixing maintains a uniform temperature among the emulsion the bed operating temperature is 623 K (350 °C), a significant
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Figure 6. Effect of fluidization velocity on conversion for different bed 623 K compared to 598 K. A lower fluidization velocity reduces
temperatures. the heat-transfer coefficient between the particles and the gas.
The reaction heat released directly into the emulsion gas is
In the present study, model calculations were carried out only for dissipated to the emulsion particles at a lower rate at lower
the reaction zone assuming that ammonium nitrate vapor enters fluidization velocity. Hence, the increase in the emulsion-gas
mainly into the reaction zone and that its temperature is the same temperature is higher at lower u/umf. Additionally, this rise in
as the emulsion-gas temperature. It has already been established the emulsion-gas temperature enhances the rate of reaction.
that a high fluidizing air velocity leads to larger gas bubbles. The Because of this phenomenon, slightly higher conversion is obtained
gas interchange coefficient between the emulsion and bubble at lower u/umf.
phases and the residence time of gas bubbles inside the bed for u/umf is known to have a significant effect on heat transfer. It
larger bubbles are small. Therefore, the possibility of ammonium should be noted that the effect of u/umf on the spray−fluidized
nitrate vapor being transferred from the emulsion phase to the bed interaction was not considered in the above analysis. The
bubble phase and unconverted ammonium nitrate vapor effect of u/umf is expected to be significant in the spray deposition
escaping through the bubble phase is reduced. Hence, con- zone, where the heat transfer from the particles to the liquid film
version increases very slowly with fluidizing air velocity at a bed is important. However, there is an upper limit on the operating
temperature of 598 K (325 °C). As the gas exchange between value of u/umf to avoid slugging flow.
the emulsion and bubble phases is a very slow process, no pro- Effect of Feed Concentration. Figure 9 depicts the effect of
nounced effect is observed. The reverse trend when bed tem- the concentration of ammonium nitrate in the feed solution on
perature is at or above 623 K (350 °C) can be explained by the conversion for different bed temperatures. It is noted that
referring to Figures 7 and 8. Comparison of the two figures in- conversion is greater at higher feed concentrations. Axial
dicates that a significant increase in the emulsion-gas tempera- temperature profiles of the emulsion gas for different feed con-
ture occurs at a bed temperature of 623 K. This difference is centrations were estimated considering a constant bed
quite realistic because the reaction rate is significantly higher at temperature of 643 K. These theoretical results are shown
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Figure 10. Axial temperature profile of the emulsion gas for different
feed concentrations. Limited data are available on the experimental conditions
and corresponding measured conversions (see Table 3). Using
the experimental conditions as inputs to the model, the
emulsion-gas temperature. Thus, the feed concentration has to ammonium nitrate conversion was estimated. The model results
be appropriately selected to obtain maximum conversion while are presented along with the experimental data for comparison.
restricting the rise of emulsion-gas temperature to within accept- Also, comparisons between the experimental data and model
able limits. predictions for the bed temperature and bed height as process
3.3. Comparison with Experimental Data. A series of variables are presented in Figures 12 and 13, respectively. It can be
experiments was carried out to study the effects of various observed that the model-predicted percentage conversion was
process parameters on the conversion of ammonium nitrate. To always slightly lower than the value determined experimentally. In
investigate the influence of a particular process parameter, this the experimental setup, the freeboard of the denitrator and the
parameter was varied over a range keeping other process off-gas lines to the heat exchanger were heat traced to avoid
parameters constant. In the fluidized-bed denitrator, the feed deposition of unconverted ammonium nitrate. Decomposition of
nozzle was located 500 mm above distributor, inclined down- ammonium nitrate in the freeboard and off-gas lines, which is not
ward (Figure 11). In this configuration, it was estimated that the considered in the model, might be the reason for obtaining
deposition of the droplets was almost completed below the slightly higher conversions experimentally. As the concentration
location of the spray nozzle. The rate of heat transfer from the of ammonium nitrate vapor in the off-gas is very small, the rate of
particles to the deposited droplets was so high that water evapora- decomposition of ammonium nitrate is very low. Hence, the
tion and volatilization of ammonium nitrate were completed in the difference between the model calculations and experimental
spray zone. For such a nozzle arrangement, the bed available above results is quite low.
the spray nozzle can be considered as the reaction zone. With Rigorous validation of the model would require axial con-
reasonable approximation, it was assumed that the reaction-zone centration and temperature data along the bed height, which
length was equal to the height of the fluidized bed (in millimeters) − were not measured in the experiments. Such experiments are
500 mm. recommended for further extensive validation of the model.
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■
predictions for the bed height.
AUTHOR INFORMATION
4. CONCLUSIONS Corresponding Author
*E-mail: sandipb@barc.gov.in.
A mathematical model that simulates the decomposition of
aqueous solutions of ammonium nitrate in bubbling fluidized Notes
beds has been developed. The model is based on the two-phase The authors declare no competing financial interest.
theory of fluidization. From the theoretical and experimental
investigations reported herein, the following conclusions were
drawn:
■ NOMENCLATURE
Ab = cross-sectional area of fluidized-bed denitrator, m2
(1) The proposed model is able to predict the axial variation of ALR = air-to-liquid ratio
the vapor-phase concentration of ammonium nitrate and Ar = Archimedes number = [dp3ρg(ρp − ρg)g]/μg2
8401 dx.doi.org/10.1021/ie202018t | Ind. Eng. Chem. Res. 2012, 51, 8394−8403
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a* = contact area between the emulsion gas and the emulsion γp = solid volume fraction in the bubble phase, 1%
particles, m2 δ = fraction of the bed in the bubble phase
CbAN = concentration of ammonium nitrate in the bubble εmf = void fraction at minimum fluidizing conditions
phase, mol/m3 μg = viscosity of the gas, kg/(m s)
CeAN = concentration of ammonium nitrate in the emulsion ρg = gas density, kg/m3
phase, mol/m3 ρp = particle density, kg/m3
Cpg = specific heat of the gas, J/(kg K) τ = average residence time of the particles in the vicinity of the
Cpp = specific heat of the particles, J/(kg K) wall, s
D = molecular diffusion coefficient of the gas, m2/s τb = residence time of particles in the bubble phase, s
■
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