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CEP - Modeling Reactive Absorption
CEP - Modeling Reactive Absorption
Modeling
R
eactive absorption i.e., the absorption of gases in Equilibrium stage model
liquid solutions accompanied by chemical reactions Modeling and design of reactive absorption processes
is an important industrial operation for the produc- are usually based on the equilibrium stage model, which
tion of basic chemicals (e.g., sulfuric or nitric acid) and for the assumes that each gas stream leaving a tray or a packing
removal of harmful substances (e.g., H2S) from gas streams. segment (stage) is in thermodynamic equilibrium with the
In recent decades, this process has become especially impor- corresponding liquid stream leaving the same tray or seg-
tant for the purification of gases to high purities. Unlike physi- ment. For reactive absorption, the chemical reaction must
cal absorption (without reactions), reactive absorption is able also be taken into account.
to provide high throughput at moderate partial pressures and With very fast reactions, the reactive separation
without requiring large amounts of solvent. process can be satisfactorily described assuming reaction
The advantages of combining chemical reactions with equilibrium. A proper modeling approach is based on the
absorption are realized only in the region of low gas-phase nonreactive equilibrium stage model, which is extended
concentrations due to the liquid-load limitations imposed by simultaneously considering the chemical equilibrium
by the reaction stoichiometry or equilibrium. Other factors relationship and the tray or stage efficiency. If the reac-
that may limit the efficiency of reactive absorption are the tion rate is slower than the mass-transfer rate, the influ-
heat liberated by exothermal reactions and the difficulty of ence of the reaction kinetics increases and becomes a
solvent regeneration. Most reactive absorption processes dominating factor. This tendency is taken into account by
are steady-state operations involving reactions in the liquid integrating the reaction kinetics into the mass and energy
phase, although some applications involve both liquid- balances. This approach is widely used today.
phase and gas-phase reactions. In real reactive absorption processes, thermodynamic
Reactive absorption is a complex rate-controlled process equilibrium is seldom reached. Therefore, correlation
that occurs far from thermodynamic equilibrium. Therefore, parameters such as tray efficiencies or height equivalent to
the equilibrium concept is often insufficient to describe it, a theoretical stage (HETS) values are introduced to adjust
and instead, accurate and reliable models involving the the equilibrium-based theoretical description to real column
process kinetics (rate-based models) are required. The effec- conditions. However, reactive absorption occurs in multi-
tiveness of online model-based applications, such as process component mixtures, for which this simplified concept
control and optimization, depends strongly on the quality of often fails (1).
the available model predictions. The acceleration of mass transfer due to chemical reac-
Two-Film Model
Multicomponent diffusion in the films can be described The volumetric liquid hold-up, L, depends on the gas
by the Maxwell-Stefan equations that relate components and liquid flowrates in the column and is calculated by
diffusion fluxes to their chemical potential gradients. In a empirical correlations. To determine axial temperature pro-
generalized form, the Maxwell-Stefan equations can be files, differential energy balances that include the product
used for the description of real gases and liquids (1). For of the liquid molar hold-up and the specific enthalpy as
the liquid phase: energy capacity are formulated. The energy balances for
n x N x N continuous systems are:
xi d i
=
i Lj j Li
di = i =1 n (1) U LB
RT dz j =1 cLt Dij
t
=
l
( ) ( )
LhLB + QLB a I Ac - qLloss (5)
industrial and experimental columns. 1, a gas stream containing 20 mol% nitrogen oxides is
Chemical reactions are important in NOx absorption absorbed by an aqueous solution containing 5 mol%
because they enhance the absorption of components that nitric acid. The inlet gas stream of Column 2 contains
are otherwise insoluble in water (e.g., NO) through their 10.2 mol% nitrogen oxides and is treated by an aqueous
chemical transformation to more soluble components (e.g., solution containing 2.65 mol% nitric acid.
NO2). Nitric acid is produced through the complex reaction Figure 3 compares the simulated axial profiles of the
mechanism detailed in Table 1 (2022). The oxidation of total NOx concentration in the gas phase for Columns 1
NO to NO2 (RR1) is the slowest reaction, and thus is the and 2 with reported experimental measurements (shown
limiting step (21). Diffusion coefficients in the gas phase with 5% error bars). For Column 1, the calculated total
were estimated using the Chapman-Enskog-Wilke-Lee NOx concentration at the top of the column shows good
model (7) and in the liquid phase using the method pro- agreement with the experiments, as the maximum deviation
posed in Ref. 23. The liquid-phase activity coefficients is less than 5%. Figure 4 presents the simulated axial pro-
were calculated using the NRTL activity model, and all files of the liquid-phase temperature and measured values
other necessary thermodynamic calculations were based on for both columns. The liquid temperature profiles reveal a
the Soave-Redlich-Kwong equation of state. maximum in the lower section of each column, which is
Validation for a packed column. The model was imple- typical for NOx absorption processes (24). The absolute
mented using the commercial simulator Aspen Custom deviation between the simulated and measured liquid tem-
Modeler (www.aspentech.com), which utilizes Aspen peratures is 4.5C for Column 1 and 3.8C for Column 2,
Properties to calculate the required physical properties. which can be attributed to heat losses through the column
Validation was performed by comparing simulation wall because the experimental column was not insulated.
results with experimental data for three pilot-scale Validation for a tray column. The design details of a
columns connected countercurrently (22). Simulations for tray column are given in Table 2. A gas stream containing
two of these columns are presented here. 0.77 mol% nitrogen oxides is treated with an aqueous solu-
The simulated units have a simple configuration, with tion containing 0.68 mol% nitric acid. To maintain a fairly
one liquid inlet stream at the top and one gas inlet constant temperature profile, seven trays in the lower part
stream at the bottom. Both columns have a diameter of
0.254 m and are filled with a random packing (16-mm
5
steel Pall rings) to a packing height of 6 m. In Column Column 1
Simulation
4 Experiment
Packing Height, m
5 Column 2
Simulation
Column 1 3
Experiment
Packing Height, m
4 NOx, Simulation
NOx, Experiment
3 2
Column 2
2 NOx, Simulation
1
NOx, Experiment
1
0
0 20 25 30 35 40 45 50 55
0.04 0.06 0.08 0.10 0.12 0.14 0.18 0.22
Molar Fraction Temperature, C
Figure 3. An axial profile of the total gas-phase NOx Figure 4. An axial profile of the liquid temperature of
concentration of Columns 1 and 2 and their measured values. Columns 1 and 2 and their measured values.
HNO3, Experiment
12
10 NO 21.83 mol/s H2O 4.55 mol/s
8 NO2 58.08 mol/s T 293 K
6
N2O4 20.11 mol/s
O2 82.74 mol/s Side Feed Stream
4
N2 1016.44 mol/s
2 H2O 34.62 mol/s
T 332 K
0 HNO3 6.02 mol/s
P 5.6 bar
0.00 0.01 0.1 1 NO2 0.41 mol/s
Molar Fraction T 306 K
Figure 5. An axial profile of the total NOx concentration in Recycle Stream Flowrate 4.55 mol/s
the gas phase, the nitric acid concentration in the liquid phase,
and the measured values. for better control of the HNO3 concentration in the product
stream, which is subject to quality constraints. Similarly,
of the column are equipped with cooling coils fed with the concentration of NOx components in the gas stream at
152 m3/h water at an average temperature of 23.6C. the top of the column is subject to composition constraints
The resulting rate-based model was solved using due to environmental regulations. Inlet stream data for the
gPROMS, an integrated process modeling environment column are provided in Table 3.
(www.psenterprise.com). Figure 5 shows the calculated Applying the OCFE model formulation, the absorption
axial profiles of the total NOx concentration in the gas column is partitioned into three sections with boundaries
phase and the nitric acid concentration in the liquid phase, defined by the location of the side feed and draw streams
as well as the measured inlet and outlet values (with a attached to the column (15). Each column section is further
measurement error of 15%). The experimental and simulat- partitioned into a number of finite elements. However, the
ed values of the total NOx reveal a maximum deviation of six oxidation stages at the bottom of the column are treated
8.5%, and the deviation of the simulated HNO3 concentra- as discrete stages. The resulting model is only one-third the
tion from the experimental value is within 10%. Thus, the size of the respective tray-by-tray model.
agreement is good, as all deviations lie within the measure- Control of the total NOx composition in the fluegas
ment error margins. The simulated outlet temperature of stream is achieved by adjusting the temperature profile in
the cooling water is 24.8C. This agrees very well with the the column. Three PID controllers use temperature meas-
measured value of 24.9C (deviation <1%). From the urements at selected stages, which act as inferential vari-
results of both pilot plant and industrial applications, it can ables of NOx
be concluded that the suggested model demonstrates good composition at H2 O
accuracy for the highly complex NOx absorption process. the effluent gas
AC
Improving column operation through design optimiza- stream, to Fluegas
NOx Specifications
tion and control. A similar example involves an industrial manipulate the
column that comprises 44 trays with an internal diameter of cooling water
3.6 m. Tray spacing is 0.9 m, except at the bottom of the flowrate in the
column. The oxidation reaction (RR1) takes place mainly stage coils. Cooling System
over the bottom six trays, where larger spacing is used for Another PID H2O, HNO3
TC
higher gas-phase hold-up to enhance the NO oxidation. controller
Three independent water-cooling systems control the col- directly controls
TC
umn temperature. In general, low column temperatures the NOx compo-
favor both the NO oxidation reaction and the absorption of sition at the
NO2 in water. Empirical correlations were used for pres- fluegas stream TC
sure drop, liquid-phase hold-up, film thickness, and stage through the
interfacial area for sieve plate calculations (15). manipulation of LC
In the column configuration shown in Figure 6, a gas the solvent
stream with a high concentration of NOx enters the bottom (water) flowrate Air, NOx
of the reactive absorption column, a liquid water stream at the top of the
enters at the top, and a weak solution of nitric acid enters column.
as a side feed stream. The bottom liquid stream, an aque- Dynamic simu- Figure 6. A schematic representation
of a NO absorption column with its
ous nitric acid solution, is partially recycled in the column lation runs using control xsystem.
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