Thermal Denitration of Ammonium Nitrate Solution in A Fluidized-Bed Reactor

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Thermal Denitration of Ammonium Nitrate Solution in a


Fluidized-Bed Reactor
Sandip Bhowmick,*,† Hanmanth Rao, and D. Sathiyamoorthy‡

Chemical Engineering Division and ‡Powder Metallurgy Division, Bhabha Atomic Research Centre, Mumbai-400085, India

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.

1. INTRODUCTION model has been developed for the thermal decomposition of


A generic production process for natural uranium conversion ammonium nitrate in a bubbling fluidized bed to study the effects
normally begins with yellowcake dissolution in nitric acid, of various operating parameters on conversion. The model was
followed by a solvent extraction process. The nuclear-pure uranyl validated by comparing the measured conversions during campaign
nitrate solution, received after solvent extraction, is contacted runs with the model predictions. Optimum values of process
with ammonia to precipitate uranium as ammonium diuranate. parameters to maximize the conversion were derived. Details of
The slurry is then filtered to separate precipitated ammonium the experimental work in the bench-scale plant are not included
diuranate (ADU). ADU filtrate contains ammonium nitrate in this article.
along with small quantities of radioactive impurities. This waste
liquid stream poses a disposal problem because of its high nitrate
2. MODEL FORMULATION
content and associated residual radioactivity. Fluidized-bed The present model is based on the two-phase theory of
thermal denitration has been considered as an advance tech- fluidization.7 According to the two-phase theory of fluidization,
nology to treat such waste nitrate streams generated in the a fluidized bed is assumed to consist of two phases: a bubble
nuclear fuel cycle. This chemical-free treatment option is environ- phase and an emulsion phase. All of the gas in excess of minimum
mentally benign for the disposal of aqueous waste nitrate streams. In fluidization flows through the bed as bubbles, whereas the
the thermal denitration process, the nitrate stream is sprayed into a emulsion stays at minimum fluidizing conditions. Gases in all bed
hot fluidized bed. The bed is maintained at the desired temperature phases including the emulsion are assumed to be in plug flow.
by an induction heating system. In this process, ammonium nitrate Exchange of gas occurring between the bubble and emulsion
decomposes predominantly into nitrogen, oxygen, and water vapor, phases is taken into account. Particles in the emulsion phase are
with the formation of a small amount of NOx. The radioactive fully back-mixed. Mass and energy conservation equations have
impurities in the ADU filtrate are trapped in a small quantity of seed been derived for the two bed phases. Okasha developed a
material in the fluidized-bed reactor. mathematical model to simulate the combustion of liquid fuel in
Several experimental works, including plant-scale applications, a bubbling fluidized bed.8 In this model, mass balance differential
have been reported in the literature on fluidized-bed thermal equations are presented for the considered species in the differ-
denitration technology.1−6 Using a synthetic solution of ent bed phases. For the modeling of the fluidized-bed thermal
ammonium nitrate as a simulant of ADU filtrate, the thermal denitration process, some relevant ideas with respect to the mass
denitration of ammonium nitrate solution has been carried out at balance of ammonium nitrate vapor in the bubble and emulsion
the Chemical Engineering Division of Bhabha Atomic Research
Centre in a bench-scale fluidized-bed reactor of 150-mm diameter. Received: September 5, 2011
Regarding the thermal denitration of ammonium nitrate solution in Revised: May 23, 2012
a fluidized-bed reactor, no works have been published, and a Accepted: June 1, 2012
systematic investigation is still lacking. In this work, a mathematical Published: June 1, 2012

© 2012 American Chemical Society 8394 dx.doi.org/10.1021/ie202018t | Ind. Eng. Chem. Res. 2012, 51, 8394−8403
Industrial & Engineering Chemistry Research Article

Table 1. Correlations and Equations Used in the Model


parameter equation(s) ref
minimum fluidization velocity at elevated temperature Ar Subramani et al.11
Remf =
1650
d p3ρg (ρp − ρg )g d pρg umf
Ar = 2
, Remf =
μg μg

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 ⎥⎦

1/Kbe = 1/Kbc + 1/Kce


solids circulation flux ⎛ 1 ⎞ Werther15
J = 0.67(1 − εmf )ρp ⎜ − 1⎟(u0 − umf )
⎝ Øb ⎠
Øb = {1 − 0.3 exp[−8(u0 − umf )]}e−ωz
ω = 7.2(u0 − umf ) exp[− 4.1(u0 − umf )]
particle-to-gas heat-transfer coefficient Nup = 0.0282Rep1.4Prg 0.33 0.1 ≤ Rep ≤ 50 Chen and Chen16

Nup = 1.01Rep0.48Prg 0.33 50 ≤ Rep ≤ 104

hpg d p d pu0ρg Cpgμg


Nu p = , Rep = , Prg =
Kg μg Kg

wall-to-bed heat-transfer coefficient 0


hwb = (1 − δ)/(1/(2Kew /d p + αwc pgρg u0) Kunii and Levenspiel7

+ 1/{1.13[Ke0ρp (1 − εmf )c pp/τ ]0.5 })

⎡ 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
Industrial & Engineering Chemistry Research Article

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,
8396 dx.doi.org/10.1021/ie202018t | Ind. Eng. Chem. Res. 2012, 51, 8394−8403
Industrial & Engineering Chemistry Research Article

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.

Table 2. Data Used for Numerical Calculations


Figure 1. Block diagram of various modes of energy transfer in the parameter value(s)
reaction zone. bed temperature (°C) 300−380
bed material silica sand
(4) heat transfer between the wall and the emulsion particles, mean sand size (μm) 300
and sand density (kg/m3) 2600
(5) heat transfer due to solids circulation. fluidized-bed height (mm) 600−800
The energy balance for the emulsion gas was modeled as follows: fluidizing air flow 2−5umf
feed flow rate (L/h) 6
(energy accumulation in the emulsion gas) ALR 1.2
ammonium nitrate concentration in the feed solution (g/L) 75−200
= (energy generated in the reaction)
+ (energy transferred to the emulsion particles) 3.1. Profiles of the Axial Concentration of Ammonium
Nitrate and Temperature. Variations of the axial concen-
Δz trations of ammonium nitrate in the different phases were esti-
meg C pg ΔTeg = K 0e−E / RTeg CeANHreactionVeg
umf mated under specific conditions: u/umf = 3, Tbed = 623 K (350 °C),
Δz feed rate = 6 L/h, ALR = 1.2 (air-to-liquid ratio in an external mix-
− hpg a*(Teg − Tep)
umf type nozzle, mass flow rate of air/mass flow rate of liquid), and
dTeg ⎡ 1 ⎤ NH4NO3 concentration in the feed = 150 g/L. Model calculations
1
=⎢ K 0e−E / RTeg CeANHreactionVeg + hpg a*(Tep − Teg)⎥ considering specific conditions are presented in Figure 2. As liquid
dz ⎣ umf umf ⎦

(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)

Ṁ pCppΔTep = hpg a*(Teg − Tep) + hbeS(Tb − Tep)


+ hwb(1 − δ)(πDt Δz)(Tw − Tep) (8)

Ṁ p = JAb (9) Figure 2. Model predictions of the axial concentration profile of


ammonium nitrate in the bubble and emulsion phases.
The energy balance for the bubble gas was modeled as follows:
droplets in the spray are assumed to be deposited on the hot
(energy accumulation in the bubble gas) surface of emulsion particles and vaporized, ammonium nitrate
= (energy generated in the reaction) vapor is released into the emulsion phase. Hence, the initial
concentration of ammonium nitrate vapor in the emulsion phase
− (energy transferred to the emulsion particles) of the reaction zone can be high. The gas velocity through the

8397 dx.doi.org/10.1021/ie202018t | Ind. Eng. Chem. Res. 2012, 51, 8394−8403


Industrial & Engineering Chemistry Research Article

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 4. Influence of bed temperature on ammonium nitrate


conversion.

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
8398 dx.doi.org/10.1021/ie202018t | Ind. Eng. Chem. Res. 2012, 51, 8394−8403
Industrial & Engineering Chemistry Research Article

portion of the unconverted ammonium nitrate within the emul-


sion phase reaches the bed surface. Hence, a low conversion is
obtained. Ammonium nitrate in the emulsion phase is almost
completely decomposed when the bed temperature is at or
above 643 K (370 °C). Complete conversion is not obtained
because of the escape of a small amount of ammonium nitrate
through the bubble phase. It is noted that, at a bed operating
temperature of 370 °C, nearly a unit bed height (∼0.9Dt) is
required for almost complete decomposition of ammonium
nitrate vapor in the emulsion phase. The required bed height
above the spray zone depends on various factors, including
nozzle location, nozzle orientation, feed rate, and bed operating
temperature. Model calculations were done for a constant
nozzle location (500 mm above the distributor), nozzle orienta-
tion (inclined downward as per the experimental setup), and
feed rate (6 L/h). The bed height required for good conversion
Figure 7. Axial temperature profile of the emulsion gas for different
was found to be completely dependent on these parameters. values of u/umf (Tbed = 598 K).
Therefore, an optimum bed height can be determined only if
these parameters are fixed.
Effect of Operating Velocity Ratio (u/umf). The effects of
u/umf on conversion for different bed temperatures are presented
in Figure 6. No marked effect of u/umf on conversion can be seen.

Figure 8. Axial temperature profile of the emulsion gas for different


values of u/umf (Tbed = 623 K).

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
8399 dx.doi.org/10.1021/ie202018t | Ind. Eng. Chem. Res. 2012, 51, 8394−8403
Industrial & Engineering Chemistry Research Article

Figure 9. Influence of feed concentration on conversion for different


bed temperatures.

in Figure 10, where it can be observed that the increase


in feed concentration also contributes to a local rise of

Figure 11. Schematic sketch of the fluidized-bed denitrator.

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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Table 3. Comparison between Experimental Data and Model Predictionsa


run
1 2 3 4 5 6
feed concentration (g/L) 150 75
fluidized-bed height (mm) 800 700 600 800
reaction-zone length (mm) 300 200 100 300
h/Dt 2 1.3 0.67 2
bed temperature (°C) 300 325 350
conversion of ammonium nitrate (%) experimental measurement 40 46 60 50 35 55
model prediction 35.32 41.70 55.33 47.76 31.80 50.10
a
For all runs, the following conditions were used: u/umf = 7, feed flow rate = 6 L/h, air-to-liquid ratio (mass flow rate of air/mass flow rate of
solution) = 1.2, active nozzle orientation downward (α = −45°) at an elevation of 500 mm (from the distributor), average size of bed particles =
300 μm.

the temperature distributions in the bubble and emulsion


phases. The model predictions exhibit good agreement
with the experimental results.
(2) It was verified with the model that both higher bed
temperature and higher feed concentration improve the
decomposition of ammonium nitrate. No significant effect
of operating velocity ratio (u/umf) on the conversion of
ammonium nitrate was observed.
(3) The required reaction-zone length for complete con-
version of ammonium nitrate vapor in the emulsion phase
is an inverse function of bed temperature.
(4) The model test results suggest that a small fraction of
ammonium nitrate vapor is transferred by gas inter-
change to the bubble phase from the emulsion phase and
then escapes from the bed unconverted. Hence, complete
Figure 12. Comparison between experimental data and model decomposition of ammonium nitrate was found not to be
predictions for the bed operating temperature. possible.
(5) Higher feed concentration contributes to an appreciable
local rise in the temperature gradient between the emul-
sion gas and particles.
(6) The model predicts that about 85−90% conversion of
ammonium nitrate can be achieved by adjusting the
experimental parameters. The recommended operating
conditions based on the model results are as follows:
Tbed = 633−643 K (360−370 °C), u/umf = 3−4, feed
concentration = 175−200 g/L. However, these recom-
mendations need to be confirmed by further exper-
imental work.
(7) Development of a comprehensive model for the spray
deposition zone based on momentum and energy
exchange between the gas−liquid spray and the bubbling
fluidized bed and integration of this model with the
reaction-zone model developed in this work will improve
the predictive capability of the overall performance of
Figure 13. Comparison between experimental data and model fluidized-bed denitrators.


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
Industrial & Engineering Chemistry Research Article

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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