Chemical Engineering Science 169 (2017) 140–150

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Chemical Engineering Science

journal homepage: www.elsevier.com/locate/ces

Process intensification writ large with microchannel absorption in nitric

acid production
Jessy J.L. Lee, Brian S. Haynes ⇑
School of Chemical and Biomolecular Engineering, University of Sydney, NSW 2006, Australia

h i g h l i g h t s

Process microfluidics coupled with process innovation.

Steam ballast in nitric acid production from ammonia provides profound process intensification.

Annular flow model shows condensation of steam in microchannels is extremely rapid.

Residual gas-phase NO in O2 is rapidly oxidised and absorbed to form acid.

Experiments show 1000-fold process intensification with 99% absorption.

a r t i c l e i n f o a b s t r a c t

Article history: This paper presents experimental studies on the absorption of nitrous gas in microchannels. Liquid and
Received 18 June 2016 gas phase products have been analysed for a wide range of nominal residence times (0.03–1.4 s), gas
Received in revised form 25 October 2016 compositions (5–10% NO, 5–49% O2, 46–82% H2O, balance argon), system pressures (2.0–10.0 bar), mass
Accepted 9 January 2017
fluxes (1.5–30 kg m2 s1), and coolant temperatures (23–51 °C) in circular tubes with internal diameters
Available online 11 January 2017
of 1.4 and 3.9 mm.
Condensation of water vapour is very rapid in the microchannel, thereby enhancing the concentrations
Keywords:
of NO and O2 and leading to highly intensified production of nitric acid. The presence of inerts inhibits the
Nitric acid
Process intensification
degree of enhancement. A simple model of condensing two-phase annular flow, in which vapour-liquid
Narrow passage interface is assumed to be smooth, describes the main features of the observations. The interfacial area
Microreactor between the phases is the single most sensitive parameter in the model.
Microchannel Under the best conditions studied experimentally, an absorption efficiency of 99% was achieved at
2 bar, with an intensification factor relative to a conventional tower absorber of the order of 1000. The
NOx concentration in the tail gas is of the order of a few percent under these conditions but the tail
gas flow is very small. While further work remains to develop a complete process with acceptable emis-
sions, these results indicate that a microstructured system employing passages 1 m long could replace
the 70 m absorption tower in a conventional nitric acid plant.
Ó 2017 Elsevier Ltd. All rights reserved.

1. Introduction whereby the microfluidic benefits of miniaturised devices can be

The development of microreactor technology for chemical pro-
cessing has been an active topic of research for 20 years and there
are many examples of fine chemical syntheses that achieve greatly
improved conversion and selectivity as a result of the mixing and
heat and mass transfer performance achieved with this approach
(Ehrfeld et al., 2000; Hessel et al., 2005; Dietrich, 2009; Boodhoo
and Harvey, 2013). It has long been recognised that microreactor
concepts can be implemented at scale through microstructuring,
⇑ Corresponding author.
E-mail address: brian.haynes@sydney.edu.au (B.S. Haynes).
brought to bear on large production capacities – ‘‘microreactors”
could in fact be very large. However, there are relatively few pub-
lished articles that deal with application of microstructured sys-
tems to large-scale chemical production despite the fact that
these would enable process intensification and process integration
that would bring enormous benefits in energy efficiency (Johnston,
1986) as well as opening the door for distributed chemical manu-
facturing (Benson and Ponton, 1993). Examples include the cat-
alytic production of propene oxide (Markowz et al., 2005),
Fischer-Tropsch liquids (Deshmukh et al., 2010), hydrogen
(Haynes and Johnston, 2011) and hydrogen peroxide

http://dx.doi.org/10.1016/j.ces.2017.01.015
0009-2509/Ó 2017 Elsevier Ltd. All rights reserved.
 J.J.L. Lee, B.S. Haynes / Chemical Engineering Science 169 (2017) 140–150 141

Nomenclature
3
~r rate of production [mol m s1 ]
1
List of symbols R ideal gas constant; tube radius [J mol K1 ; m]
a area density [m1 ] Re Reynolds number [–]
A area [m2 ] Sc Schmidt number [–]
B surface suction rate, GG!L =GG [–] St Stanton number [–]
3 T temperature [K]
c concentration [mol m ]
D tube diameter [m] t time [s]
Dh hydraulic mean diameter [m] u velocity [m s1 ]
D mass diffusivity [m2 s1 ] U overall heat transfer coefficient [W m2 K1 ]
f fanning friction factor [–] V volume [m3 ]
2 x distance [m]
G mass flux based on superficial area [kg m s1 ]
2 X yield; conversion [–]
G0 mass flux based on phase area [kg m s1 ]
a heat transfer coefficient [W m2 K1 ]
Gz Graetz number, ðL=Dh ÞReSc [–]
1 b mass transfer coefficient [m s1 ]
H enthalpy [J mol ] d film thickness [m]
1 1
H Henry law constant [mol kg bar ] h area multiplier [–]
2 1
j diffusive mole flux [mol m s ] l viscosity [Pa s]
k thermal conductivity [W m1 K1 ] q density [kg m ]
3
~
k forward rate constant for reaction j s shear stress [Pa]
j;f
Kj equilibrium constant for reaction j
L length [m] Location subscripts
1
m mass flow [kg s ] C cooling medium
1
n mole flow [mol s ] G gas
2
N mole flux [mol m s1 ] I interface
p pressure [bar] L liquid
r radius [m] W tube wall

(Pennemann et al., 2004), as well as the synthesis of pigments and
polymers (Wille et al., 2004; Iwasaki et al., 2006).
The benefits of microstructured systems in gas-liquid process-
ing are especially attractive due to the high rates of interfacial heat
and mass transfer that can be achieved (Vankayala et al., 2007;
Lam et al., 2013; Ghiaasiaan, 2007) and it is perhaps surprising that
this has not been exploited more in practice. One of the largest ton-
nage gas-liquid reaction processes in industry is that of the oxida-
tion and absorption of nitrous gases (principally NO from the
combustion of ammonia in air) to make nitric acid. The overall
reaction is
2NOðgÞ þ O2 ðgÞ ! 2NO2 ðgÞ
3HNO2 ðaqÞ ! HNO3 ðaqÞ þ 2NOðgÞ þ H2 OðlÞ
The industrial operation (Thiemann et al., 2012; Andrew, 1985)
has hardly changed in 100 years, using large stage-wise absorption
towers that provide sufficient volume to enable the slow, recursive
third-order gas-phase oxidation of NO to proceed sufficiently to
bring about, typically, about 99% absorption of the nitrous gas feed.
The process is enhanced by operating at pressure (up to 13 bar)
and sometimes by injecting oxygen into the absorber to increase
its partial pressure (Kankani et al., 2015). Use of ozone injection
has been suggested to enhance oxidation of nitrous acid which is
carried out in the bleacher section of the absorption train
(Chacuk et al., 2007).
In general, it would not be appropriate to use a microstructured
volume for a slow reaction because creating large volumes of this
kind is unnecessarily difficult and expensive. In the case of nitric
acid production, it could only be contemplated if the reactions
could be accelerated far beyond what is currently achieved
through raising the pressure or adding some oxygen. The main
impediment to raising the concentrations of NO and O2 is the pres-
ence of a large N2 fraction (typically  80%) that is carried over
from the air feed to the ammonia combustor. However, although
this N2 is a nuisance in the absorber, it has a useful function in
the combustor where it serves as a ballast gas to moderate the
temperature such that this lies in the optimal range for NO selec-
tivity (750–950 °C).
Substitution of N2 with steam offers a resolution to the dilemma
since steam may act as ballast in the combustor and be removed by
condensation in the absorber. Indeed, this has been practised in the
past to produce NO for the production of high strength nitric acid
(typically >90 wt%, Caro et al., 1935; Manning, 1943) and for
hydroxylamine and caprolactam manufacture (Krauss and
Diekmann, 1963). In these processes, ammonia was combusted
in minimal excess of oxygen in steam – condensation of the steam
produced a weak acid and a highly concentrated stream of NO for
further processing. This provides the motivation for the present
work, to investigate the production of nitric acid through the com-
plete absorption of the nitrous gas (as the mixture of nitrogen oxi-
des formed in the combustor is known) from the combustor into
the condensed steam ballast. Specifically, we investigate the pro-
cess microfluidics of a microchannel condenser-absorber, on the
basis that the 5-fold concentrating effect of condensing the steam
ballast provides a factor of approximately 53 enhancement in the
rate of the termolecular oxidation of NO.
2. Experimental method
Experiments were conducted to study the oxidation and
absorption behaviour of nitrogen oxides in microchannels over a
wide range of conditions. The supply of oxygen is always sufficient
for the complete conversion of NO to nitric acid, which has a
stoichiometric requirement of 0.75 mol oxygen per mol NO.
3 1
NOðgÞ þ O2 ðgÞ þ H2 OðlÞ ! HNO3 ðaqÞ
4 2
The total extent of absorption and the composition of the pro-
duct were characterised. The experimental apparatus is depicted
in Fig. 1. Most experiments were performed with the absorber
142 J.J.L. Lee, B.S. Haynes / Chemical Engineering Science 169 (2017) 140–150
tubes oriented horizontally but a downflow orientation was also
examined. For the experiments with downflow, only the first
straight absorber section was employed.
Reactant (99.9% NO, Linde and 99.999% O2, Coregas) and diluent
(99.999% Ar, Coregas) gas flows were controlled using calibrated
mass flow controllers. A High Performance Liquid Chromatography
(HPLC) pump (Waters 515) was used to deliver de-ionised and
degassed water to a mixing point where it was combined with
the O2 stream. The resulting two-phase stream was passed into a
heated line (M&C TechGroup Type 5-M) where the water was
evaporated completely. NO and Ar were preheated separately
using 2.0 X/m resistance wires encased in PTFE tubes and coiled
around the stainless steel gas line. The O2/steam and NO/Ar
streams were combined and entered the absorber as a single-
phase, superheated gas at a temperature in the range 150–180 °C.
Pressure gauges (Swagelok, Model: PGI-63B-BG16-LAQX) and
calibrated pressure transducers (Swagelok, Model: PTI-S-AA16-
26AQ) were used to indicate pressures at the inlet and outlet of
the absorber. The absorber outlet was fed into a separator compris-
ing a 1 L stainless steel sample cylinder (Swagelok, Model: 304L-
HDF4-1000) to allow the liquid phase to collect at the bottom of
the vessel and separate from the gaseous products. A backpressure
regulator (Swagelok, Model: KBP1G0A4B5A20000) was used to
control the system pressure while the liquid level in the separator
was controlled manually by releasing liquid to maintain the liquid
level in the separator at approximately half full. The measured
pressure drop across the length of the absorber was generally small
(<7  10–3 bar).
The absorber consisted of three straight lengths of stainless
steel tubing with an internal diameter (ID) of either 1.4 mm
(3.2 mm OD) or 3.9 mm (6.4 mm OD) as shown in Fig. 2. Tubes of
equal diameter were connected in series via tube bends of the
same material and diameters, using Swagelok fittings to give a
total length of up to 1.47 m. The first straight section was located
within a cooling jacket in the form of a coaxial stainless steel tube
with ID = 10.2 mm. Cooling water from a temperature-controlled
bath (Thermoline BTC-9090, 21–50 °C) was pumped counter-
currently into the annulus between the two tubes. The inlet and
outlet temperatures of both the absorber and the cooling jacket
were measured using type-K thermocouples with an accuracy of
±1 K. Water jackets were not used on the subsequent downstream
Gas to Vent
FTIR
Valve
Ar GMFC
NO GMFC
PCV
Ar GMFC
P in each sample were measured by ion chromatography (Dionex
P
O2 GMFC PRV
T T
Filter
H2O Absorber
HPLC Heater
Pump Separator
Titration/I.C.
Fig. 1. Schematic of the experimental setup. GMFC = Gas Mass Flow Controller,
PCV = Pressure Control Valve; PRV = Pressure Relief Valve; FTIR = Fourier Transform
Infrared Spectrometer; I.C. = Ion Chromatography.
lengths as the intensity of heat release (due to water condensation
and nitrous gas oxidation and absorption) after the first section
was low, as confirmed by type-K thermocouples (±1 K accuracy)
mounted at various points downstream of the cooling section.
The process gas typically enters the absorber at 180 °C and exits
at 25 °C, while the inlet and outlet temperatures of the cooling
jacket were generally 20.5 °C and 21.5 °C respectively. Data from
the thermocouples and pressure transducers were retrieved by a
data acquisition unit (Agilent 34970A).
Circular holes with a diameter of 1 mm were drilled at regular
intervals along the length of the second and third straight sections
to enable liquid samples to be withdrawn for analysis. The holes
were drilled only through one side of the wall and placed along
the same axial line on each tube. Swagelok tee pieces allowed
the liquid passing through the holes to be directed into stainless
steel capillary tubing (ID = 140 lm, OD 1.6 mm). The lengths of
the capillary (2–12 m) were chosen to control the sampling flows
(typically  0.02 ml/min, or 5% of the condensed liquid flow in
the absorber tube). Since the flow pattern in the absorber under
the prevailing conditions is annular (Triplett et al., 1999), with
the liquid flowing as a film along the wall, it was possible to extract
liquid only, without allowing any significant amount of gas into the
sample. It was essential to avoid such gas flow in order to ensure
that the composition of the acid sample did not change in passing
through the sampling capillary.
Because the liquid product may contain significant quantities of
nitrous acid HNO2, as well as the desired nitric acid HNO3, it is
important also to eliminate composition changes due to decompo-
sition of HNO2 during sampling and prior to analysis. Nitrous acid
undergoes disproportionation as
3HNO2 ðaqÞ
HNO3 ðaqÞ þ 2 NOðgÞ þ H2 OðlÞ
which can not only distort the relative nitrous/nitric acid yields, but
can also lead to significant loss of total acid product (Lee, 2012).
Although this reaction does equilibrate in the sampling capillary
prior to discharge, the loss to NO here (equivalent to the dissolved
gas with an equilibrium partial pressure of 1 bar) is negligible (Lee,
2012). However, if the sample were to be exposed to atmosphere,
the loss (as NO) would become significant. Therefore, the liquid
samples exit the capillary tubes into containers pre-filled with deio-
nised water, with the outlet of the sampling lines immersed below
the water surface. Since the rate of disproportionation is fourth-
order in the concentration of HNO2 (Abel and Schmid, 1928a,
1928b), the reaction can be arrested by dilution. A further benefit
of this dilution derives from the concomitant reduction in the pro-
ton concentration, which favours more extensive dissociation of
HNO2 to relatively stable nitrite ions:
HNO2 ðaqÞ
Hþ ðaqÞ þ NO2 ðaqÞ
In order to obtain absolute concentrations, the incremental
mass due to the liquid products was measured. After further dilu-
tion to <100 mg L1, the concentrations of nitrite and nitrate ions
ICS-2000). The carrier for this determination was 4.5–15 mM
KOH (Thermo Scientific Dionex EluGenÒ EGC III KOH Cartridge,
Model: 074532) which ensured complete dissociation of the acids
in the anion-exchange column (Dionex IonPac AS11-HC). A sup-
pressor (Dionex 2 mm ASRS 300) was used to reduce background
conductance of the eluent and enhance detection of sample ions
in the conductivity cell detector.
The gaseous products leaving the separator were diluted with
argon before being passed through the gas cell of a calibrated Four-
ier Transform Infrared Spectrometer (Bio-Rad FTS6000) for NO,
NO2, N2O and H2O analyses. Measurements were made using 64
scans at a resolution of 0.25 cm1. Since the NO supply contained
 J.J.L. Lee, B.S. Haynes / Chemical Engineering Science 169 (2017) 140–150 143

Water Chiller

Water Bath
Cooling Water

Thermocouple
Cooling Jacket
Inflow
0.25 m
Absorber Tube
0.5 m

0.5 m
Outflow

Capillary Sampling Tubes

Fig. 2. Schematic of the absorber reactor.

N2O (2.11 vol%), which is neither formed nor destroyed in the sys- Table 1
tem, the N2O was used as a gas tracer to determine the total volu- The range of experimental parameters studied for nitrous gas absorption.

metric flow rate of the product gas. Parameter Range

Assuming that essentially all the water in the incoming mixture Tube internal diameter 1.4, 3.9 mm
is condensed very rapidly (as occurs in the BASF process (Krauss Absorber length 0.23–1.4 m
and Diekmann, 1963), and as found also in the modelling to be Inlet gas mole fraction 5–10% NO
described below), apparent yields of the acids (including both dis- 5–49% O2
46–82% H2O
sociated and undissociated forms) obtained at different locations
Bal. Ar
in the absorption tube are: Inlet system pressure, ðP T Þin 2–10 bar (abs)


Inlet mass flux, Gin 1.5–30 kg m2 s1
cHNO3
L cHNO2
L 0.2–8.5 m s1
X HNO3 ¼
; X HNO2 ¼
ð1Þ Inlet velocity, uG;in
cHNO
3 1
cHNO

3 1
Nominal residence time, t res;nom 0.03–1.4 s
Coolant mass flux, Gc 66, 341 kg m2 s1


where cHNO3
1 is the molar concentration of nitric acid that would Coolant temperature, T c 23–51 °C

be achieved if all the NO were to be converted to nitric acid and dis-

solved in all the condensed water. The overall absorption efficiency
is simply the sum X HNO3 þ X HNO2 .
The nominal residence time tres;nom at a given distance x based 1968; Hoftyzer and Kwanten, 1972; Carta and Pigford, 1983;
on the inlet flow conditions is: Sherwood et al., 1975; Miller, 1987; Hüpen and Kenig, 2005;
q  Pradhan et al., 1997) – here, we adopt accepted chemistry and
x develop a model for microchannel condensation, absorption and
t res;nom ¼ ¼x G
ð2Þ
uG;in G in reaction which takes into account the specific features of the small
length scales encountered.
where qG is the gas density.
The nominal residence time carries no fundamental significance
and is used only as a comparative indicator of run conditions 3.1. Reaction chemistry and kinetics
because the fluid density changes as a result of physical and chem-
ical changes through the absorber. A more meaningful two-phase In the gas phase, the reactive species are NO, NO2, N2O3, N2O4,
residence time will be defined later in this paper. and O2. The gas-phase reaction mechanism is assumed to be
The ranges of experimental conditions used in this study are
2NO þ O2
2NO2 ðR1Þ
summarised in Table 1. The flow conditions in both phases are
laminar throughout.
2NO2
N2 O4 ðR2Þ

3. Modelling
The absorption of nitrogen oxides in water is a highly complex
process, with reactions taking place in both gas and liquid phases,
and simultaneous mass transfer interchange occurring between
the phases (Thiemann et al., 2012; Andrew, 1985). Modelling of
nitrous gas absorption towers in conventional nitric acid produc-
tion has been studied over many years (Miles, 1961; Chilton,
NO þ NO2
N2 O3 ðR3Þ
Although oxidation of NO (R1) proceeds essentially to comple-
tion at equilibrium, the reaction is slow, especially at low concen-
trations of NO and O2. On the other hand, equilibrium is rapidly
established in the forward and backward directions for reactions
(R2) and (R3) (Pradhan et al., 1997), with the reaction rate con-
stants being several orders of magnitude higher than that for the
144 J.J.L. Lee, B.S. Haynes / Chemical Engineering Science 169 (2017) 140–150

oxidation of NO. In these circumstances, the governing equations The partial pressure of water at the interface is assumed to be
become stiff. Therefore, a partial-equilibrium approximation its saturation pressure at the interface conditions.
(PEA) was used, with (R1) being kinetically controlled while (R2) Table 2 reports the kinetic and equilibrium constants employed
and (R3) are assumed always to be in equilibrium. The concentra- in this work.
tions of N2O3 and N2O4 are therefore determined algebraically as
3.2. Condenser/absorber model
pN2 O4 ¼ K 2 p2NO2 ð3Þ
The structure of gas-liquid flows in microchannels has been
pN2 O3 ¼ K 3 pNO pNO2 ð4Þ studied in great depth in recent years (Ghiaasiaan, 2007; Triplett
where K 2 and K 3 are the equilibrium constants for reactions (R2) et al., 1999; Ide et al., 2007). Flow regime maps indicate that, for
and (R3) respectively. total mass fluxes G < 500 kg m2 s1, the annular regime prevails
The PEA has negligible effect on the accuracy of the calculated for almost the entire quality regime down to 10% by mass of
concentrations if the establishment of the reaction equilibria is fast vapour (Triplett et al., 1999), below which slug-annular and even-
compared to the time-step of the integration, as discussed by Rein tually slug flow arises. Baird et al. (2003) developed a model for
(1992) and Mott (1999) and confirmed specifically for the present shear-driven condensation in microchannels, based on a vapour
model (Lee, 2012). Following Ramshaw (1980), the chemical spe- core and an annular liquid film with a smooth interface. The model
cies involved in the equilibrium reactions are now assigned to was validated against an experimental data set of >2000 points
two pools based on their nitrogen oxidation states of either +2 or from 0 to >90% extent of condensation. The assumption of annular
+4. Taking note that N2O3 can be written as NO.NO2, and that flow driven by shear (and augmented by gravity in downflow
one mole of N2O4 contains two moles of N(+4) species, the concen- arrangements) was therefore adopted here also to model the con-
trations of the pools are defined as follows: densation and absorption behaviour of nitrous gases in
microchannels.
pNðþ2Þ ¼ pNO þ pN2 O3 ð5Þ Condensation was assumed to start immediately at the inlet of
the absorber (Baird et al., 2003), where the internal wall surface
pNðþ4Þ ¼ pNO2 þ pN2 O3 þ 2pN2 O4 ð6Þ has been pre-coated with a thin layer of liquid water correspond-
ing to 0.1% of the inlet mass flux. This assumption allows the
Eqs. (3)–(6) constitute a nonlinear system of four algebraic equa-
core-annular model description to be applied throughout the
tions that determines the four species concentrations from the pool
domain without having to model explicitly the first liquid forma-
concentrations. The gas phase mass balance is then written for the
tion – there is no loss of accuracy overall with this initialisation
two pools rather than for each individual species.

(Baird et al., 2003). The liquid film grows in thickness as vapour
The chemical rates of production of the pools, ~r Nðþ2Þ
G and

condenses and gases are absorbed along the length of the absorber.
~rNðþ4Þ
are given by:
G The problem is solved at steady state and is assumed to be locally
! 1D, i.e. the rate of change of film thickness along the tube is slow.


1 p2NO2
~ p2 p
~r Nðþ2Þ
G ¼ ~r Nðþ4Þ
G ¼ 2k1;f NO O2 1  ð7Þ At a distance x along the tube, the liquid phase occupies an
K 1 p2NO pO2
annular region of physical thickness dL. Chemical reactions occur
In the liquid phase, the relevant irreversible reactions are the in the gas and liquid phases, and there is transfer of heat and mass
hydration of N2O3 and N2O4 and the disproportionation of HNO2. between the phases. Heat is lost from the cooled section by con-
Nitric and nitrous acid dissociation is equilibrated but dissociation duction through the tube wall to the coolant stream which is
of HNO2 can in fact be neglected because the mixture is very acidic assumed to remain isothermal at a specified temperature. The
(except perhaps at the earliest stages of condensation). gas-liquid interface is assumed to be smooth.
The differential mole balances for the gas phase components
N2 O4 ðaqÞ þ H2 OðlÞ ! HNO2 ðaqÞ þ HNO3 ðaqÞ ðR4Þ ði ¼ Nð2þÞ; Nð4þÞ; HNO2 ; HNO3 ; H2 OÞ are:
 
N2 O3 ðaqÞ þ H2 OðlÞ ! 2HNO2 ðaqÞ ðR5Þ dni jG d½pðR  dL Þ2 Ni jG  dAI
¼ ¼ jj þ ~ri jG ð10Þ
dV G dV G dV G i G!L
3HNO2 ðaqÞ ! HNO3 ðaqÞ þ 2NOðaqÞ þ H2 OðlÞ ðR6Þ
Neglecting the derivative of the film thickness, therefore
HNO3 ðaqÞ þ H2 OðlÞ
NO3 ðaqÞ þ
þ H3 O ðaqÞ ðR7Þ dNi jG 2
¼ jj þ ~r i jG ð11Þ
dx ðR  dL Þ i G!L
Reactions (R4) and (R5) are very fast and occur within the mass
transfer boundary layer (Hoftyzer and Kwanten, 1972). The rate Similarly for the liquid phase ði ¼ NO;NO2 ; N2 O3 ; N2 O4 ;
constant for absorption from the gas phase is then given by the HNO2 ; HNO3 ; H2 OÞ:
qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
species specific value of H k ~
hydration DL (Hoftyzer and Kwanten, dNi jL 2ðR  dL Þ
¼ 2 ji jG!L þ ~r i jL ð12Þ
1972). The disproportionation of HNO2 represented by (R6) is not dx R  ðR  dL Þ2
an elementary reaction – its rate is given (Abel and Schmid,
1928b; Wendel and Pigford, 1958) by For laminar film flow, the film thickness is determined

4 (Henstock and Hanratty, 1976) as
cHNO2
sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
~
~r 6 ¼ k L
ð8Þ mtot jL lL
6;eff
p2NO dL ¼ ð13Þ
pRqL sc
Chemical equilibrium is assumed at the interface between the
gas and liquid phases, expressed in terms of Henry Law constants where sc is a characteristic shear stress that includes the effect of
for the nitrous gas species. vapour shear and gravity
   
ci jL ¼ Hi qL pi at equilibrium ð9Þ 1 dL 1 1 dp
sc ¼ sw 1   qL  þ g dL ð14Þ
3 R 3 qL dz
 J.J.L. Lee, B.S. Haynes / Chemical Engineering Science 169 (2017) 140–150 145

Table 2
Values of parameters employed in the model.

Parameter Value Units Ref

~ þ530 2
k 1;f
1:73105
exp bar s 1 Atkinson et al. (2004)
T2 T
ln K 1 4:27ð1  ln TÞ þ 4:49  103 T þ 2:27  107 T 2  1:04  109 T 3 þ 3:36  1013 T 4 þ 1:27  104 T 1 þ 4:35 bar
1 Burcat and Ruscic
(2005)
ln K 2 2 5 2 9 3 13 4 3 1 1 Burcat and Ruscic
4:80ð1  ln TÞ þ 1:62  10 T  1:04  10 T þ 4:54  10 T  8:94  10 T þ 6:39  10 T  0:81 bar
(2005)
ln K 3 2:32ð1  ln TÞ þ 1:01  102 T  7:78  106 T 2 þ 3:88  109 T 3  8:44  1013 T 4 þ 4:49  103 T 1  7:29 bar
1 Burcat and Ruscic
(2005)
pffiffiffiffiffiffiffi 1750 2 1
½H kDN2 O4 2:95  102 exp mol m s1 bar Hoftyzer and Kwanten
T
(1972)
pffiffiffiffiffiffiffi 2 1
½H kDN2 O3 1:57 mol m s1 bar Corriveau (1971)
 
~
k 1:62  10 11
exp 14;280 2 9
bar m mol
3
s 1 Wendel and Pigford
6;eff T
(1958)


HNO 1:90  103 exp 1500 T1  298:15
1
mol kg
1
bar
1 Schwartz and White
(1981)
HNO2 0.012 mol kg
1
bar
1 Schwartz and White
(1981)
HN2 O4 1.4 mol kg
1
bar
1 Schwartz and White
(1981)
HN2 O3 0.6 mol kg
1
bar
1 Schwartz and White
(1981)


HHNO2 49 exp 4800 1T  298:15
1
mol kg
1
bar
1 Schwartz and White
(1981)
HHNO3 2:1  105 mol kg
1
bar
1 Schwartz and White
(1981)

Here we evaluate the pressure gradient from the interfacial Viewed from the liquid side, the interphase transport of the
shear stress as absorbing species is
dp 2si

 ¼  qG g ð15Þ ji jG!L ¼ beff ;i
L ðci jLI  ci jL Þ ð20Þ
dz Ri




where the interfacial shear stress is determined as that arising only We calculate beff ;i
L ¼ Di jL =deff ;i
L , where deff ;i
L is the effective
from the gas side motion mass transfer thickness for species i. In confined laminar flow,
the flow is fully developed when the Graetz number satisfies

G02 Gz K 50, under which circumstances the diffusion length scale is
sI ¼ f eff
GI G
ð16Þ
2qG of the same order as the length scale of the confinement, i.e.


Baird et al. (2003) considered the effect of interphase mass deff ;i
L  dL . With the hydraulic mean diameter Dh ¼ 4dL for trans-
transfer (condensation of H2O) in determining the effective friction port to one face of a film, we use the model to evaluate


factor f eff
GI and showed that the effect of condensation mass trans-
16mtot jL dL
fer is correctly accounted for via (Hewitt et al., 1994): Gz ¼  ð21Þ
pDqL D L

2BG
f eff
GI ¼ ð17Þ
1  exp ð2BG =f 0 Þ and find that the fully-developed flow condition is always satisfied
where BG ¼ GG!L =G0G
is calculated from the interphase mass flux at within the first, cooled absorber stage. We therefore take the diffu-
sion thickness to be dL , unless the diffusion is enhanced by reaction
the gas-liquid interface. In the present work, the interphase mass
within the liquid film.
flux is taken to include both condensation (of H2O) and absorp-
The absorption of N2O4 and N2O3 is enhanced by their rapid
tion/desorption of the nitrous gas components, and the reference
hydration, with the result that the effective mass transfer coeffi-
(without mass transfer) friction factor f 0 is calculated for the gas
cient becomes (Wendel and Pigford, 1958):
flow in a conduit with the same diameter as the core. Following
Baird et al. (2003), a smooth conduit is assumed here. rffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi




The interphase fluxes due to absorption/desorption of the beff ;i
L ¼ ~


k Di jL ði ¼ N2 O3 ; N2 O4 Þ ð22Þ
i
hydration
nitrous gases are calculated as

 
beff
G ci j In general, the effective film thickness corresponding to absorp-
 ffi
rffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi


ji jG!L ¼ pi  LI ð18Þ

~


RT I Hi qL tion with fast reaction drxn;i
L ¼ Di jL =k i is much less
hydration
where equilibrium between the gas and liquid phases is assumed to than the physical film thickness. However, at the earliest stages


occur at the interface. The effective mass transfer coefficient beff
G in the condensation process, when the liquid film is extremely thin,
includes the effect of interphase mass transfer (Hewitt et al., 1994): the calculated film thickness for fast reaction is found to exceed the



physical thickness ðdL < drxn;i
L Þ. In order to ensure that the mass
BG
St eff
G ¼ ð19Þ transfer coefficient is calculated approximately correctly through-
1  expðBG =St 0 Þ
out the range, we simply add mass-transfer coefficients calculated
The reference (without mass transfer) Stanton number St 0 is for diffusion only and diffusion with reaction. While this is not
that calculated for the gas flow in a conduit with the same diame- strictly accurate, it provides a smooth interpolation from the very
ter as the core. For laminar flow, the augmentation of the Stanton early stages of the condensation through to the region where
number is the same for heat and mass transfer. reaction enhancement determines the rate of absorption of these
146 J.J.L. Lee, B.S. Haynes / Chemical Engineering Science 169 (2017) 140–150

species. Because the region where dL K drxn;i
L is very limited, the
accuracy of the final solution is not significantly affected by the
details of this smoothing.
In order to determine the interphase mass flux due to conden-
sation of water, the energy balance equations for the gas and liquid
phases must be solved. For the gas phase
n

d X
X
o
 i
¼ 2
N i jG H aeff
G ðT G  T I Þ þ  i

ji jG!L H
dx G ðR  dL Þ G
For the liquid phase, the balance includes heat flow to the cool-
ing medium
d X
n X
o
 i
¼ 2ðR  dL Þ
N i jL H aL ðT I  T L Þ þ  i

ji jG!L H
dx L 2 2 G
R  ðR  dL Þ
2R
 U W ðT L  T C Þ
R2  ðR  dL Þ2
The thermodynamic properties of gaseous species are calcu-
lated using the NASA polynomials (Burcat and Ruscic, 2005).
Liquid-phase data are determined using OLI Analyzer Studio 3.1.
Once the reaction rate terms for the gas and liquid flows are


evaluated (as described above), the rate of condensation jH2 O
G!L
can be calculated and the evolution of the phase flow rates, the film
thickness and the species concentration profiles are all determined
by numerical integration. The differential equations are solved by a
forward Euler technique in Microsoft Office Excel 2007. The model
contains many implicit dependencies and these are solved itera-
tively at each step. A step size of 1 mm was shown to produce
grid-independent solutions and is used for all the model results
presented here.
4. Results and discussion
Fig. 3 shows results from the model for typical conditions,
focussing on the early stages of the absorption process in order
to reveal the rapidity of the processes of water condensation, NO
oxidation and N2O3 and N2O4 absorption that occur in the system.
Condensation of water vapour (75% mol fraction in the inlet)
begins immediately and proceeds rapidly to completion,
tres;nom  0:007 s. As a result, the concentrations of the residual
gases (nitrous gases and oxygen) rise by a factor of 4, under
which conditions the homogeneous oxidation of NO is enhanced
significantly (by 43); at the same time, the rates of formation
and absorption of N2O3 and N2O4 are promoted, resulting in an
increasing rate of acid formation (as indicated by the nitrous gas
Fig. 3. Model predictions showing course of condensation and nitrous gas reaction
and absorption in a 1.4 mm ID tube at 2.0 bar with an inlet gas composition of 10%
NO, 15% O2 and 75% H2O, and an inlet mass flux of 9.6 kg m2 s1.
Absorption Efficiency). Note that acid formation consumes water
substance in the liquid phase, which is responsible for the apparent
reduction in the degree of condensation after 0.007 s.
It is immediately apparent that the time-scale of the absorption
in Fig. 3 is vastly less than the 100 s residence time in a conven-
tional absorption tower (Gutierrez-Cañas et al., 1989). This intensi-
fication comes both from the scale of the microchannel and from
ð23Þ the process improvement whereby condensation of the ballast
gas enhances the chemical reaction rates. The condensation of
steam and the absorption of nitrous gases also lead to significant
reductions in the volumetric gas flow rate along the absorber tube:
the actual gas-phase residence time relevant to the chemical kinet-
ð24Þ ics can be calculated as
Z x Z x
dx qG
tres jG ¼ ¼ dx ð25Þ
0 uG 0 G0G
For the case in Fig. 3, the gas velocity decreases fourfold as
steam condenses and by a further factor 2 as the nitrous gas is
oxidised and absorbed – the extended gas residence time leads
to further enhancement of the extent of NO oxidation and its sub-
sequent absorption.
In the following paragraphs and associated figures, results are
presented for a number of process variables and compared with
the predictions of the model in order to understand the most
important features of the microchannel condenser/absorber. The
basic model generally gives a qualitatively correct description of
the results but, in order to improve quantitative comparisons, the
sensitivity of the model to its various parameters has been consid-
ered. This analysis shows (Lee, 2012) that the vapour-liquid inter-
facial area density aI is the most important single parameter in
controlling the kinetics of the system, as expressed in the concen-
trations of HNO2 and HNO3 produced. In the model, this parameter
is taken as that for a smooth interface between the gas core and the
annular liquid – this is clearly a conservative simplification as
interfacial waves and intermittent flow patterns often arise in
gas-liquid flows (Triplett et al., 1999). Sensitivity to the interfacial
area density may also reflect sensitivity to heat and mass transfer
rates, frictional drag and film thickness. We have therefore chosen
this parameter as the single adjustable quantity when comparing
the model predictions with the experimental results, through the
introduction of an area multiplier hI on the geometrical value.
While values of hI determined in this way should therefore not
be equated too precisely with a physical area adjustment, it is
noteworthy that the magnitude of hI for the different conditions
studied here are generally in a narrow range, 1 < hI < 3.
Fig. 4 shows results for acid formation as a function of the nom-
inal residence time in tubes at 8 bar, with 1.4 mm (filled symbols)
and 3.9 mm internal diameter (open symbols). The data for each
tube were obtained from runs over a range of inlet mass fluxes.
For the 1.4 mm tube, the grey filled symbols show results obtained
with horizontal flow using the extended absorber as shown in
Fig. 2 and with samples taken at the exit – total absorber
lengths of 0.46 m and 1.47 m were used with mass fluxes
11–23 kg m2 s1; dashed lines in the Fig. show results of the zero
gravity model for these conditions. An additional series of runs
with identical mass fluxes, but in downflow (black filled symbols),
was conducted using only the primary 0.25 m absorber with sam-
ples collected at the exit – solid lines in the figure show results of
the model with gravitational forces. The model shows negligible
effect of mass flux at a given nominal residence time (because film
thickness in these partially condensed flows depends only weakly
on the inlet mass flux), so the predictions for a given flow orienta-
tion can be represented by a single line, with the differences
between downflow predictions (solid lines) and those for horizon-
tal flow (dashed) also being slight. Clearly, the model accurately
 J.J.L. Lee, B.S. Haynes / Chemical Engineering Science 169 (2017) 140–150
Fig. 4. Acid yield profiles for absorption at 8.0 bar with an inlet gas composition of
5% NO, 49% O2 and 46% H2O. Filled points show experimental results for 1.4 mm
tube diameter with mass fluxes of 11–23 kg m2 s1; black symbols are for
downflow, grey are for horizontal flow. Open points are for 3.9 mm tube with
downflow mass flux 1.5–3.0 kg m2 s1. Solid and dashed lines show predictions of
the model (hI ¼ 1) with and without gravitational effects respectively.
captures the details across the whole length of the absorber with-
out requiring any adjustment (hI ¼ 1Þ. Early rapid formation of
HNO2 and HNO3 sees the overall conversion rate exceed 90% by
t res;nom  0.2 s. The yield of HNO2 peaks at 7%, after which the
main apparent change is the gradual conversion of HNO2 to
HNO3, controlled by the diminishing rate of the disproportionation
reaction (R6) following fourth-order kinetics. The final absorption
efficiency is in excess of 99%, comparable with requirements for
a conventional tower absorber.
For the 3.9 mm tube in Fig. 4, the results, which were obtained
in downflow using inlet mass fluxes in the range of 1.5–
3.0 kg m2 s1, are very different. Absorption apparently ceases
after 68% completion with disproportionation of the nitrous acid
that is formed apparently suppressed, perhaps corresponding to
the inhibiting effect of residual NO on the kinetics of dispropor-
tionation. The mass flows in the two series of experiments are
the same and the velocities in the larger tube are therefore consid-
erably less than in the smaller tube. With the lower velocities com-
bined with the usual effects of duct size in process intensification,
the model predicts lower heat and mass transfer coefficients and
therefore a lower extent of absorption in a given nominal residence
time. However, the model does show that the absorption should go
near to completion and that HNO2 should disproportionate as
much as in the smaller tube.
We believe that the apparent cessation of absorption in the
3.9 mm tube may be due to a breakdown of the annular film flow
at the low velocity ðuL K 0:001 m s1 Þ arising in this case. Down-
ward flowing film stability has been studied in some depth because
of its relevance to falling-film contact devices and it is known that,
at sufficiently low flow rates (i.e. for sufficiently thin films), the
flow is more stable as one or more rivulets than as a thin film
(Mikielewicz and Moszynskl, 1976; El-Genk and Saber, 2001).
The minimum stable film flow depends on the fluid properties
and on the contact angle of the fluid with the wall (Mikielewicz
and Moszynskl, 1976; El-Genk and Saber, 2001). Hughes and Bott
(1991) considered the effect in tube flow where the curvature
extends the range of stable film flow; co-flowing vapour shear also
promotes film stability (Saber and El-Genk, 2004; Wilson et al.,
2011). Applying the method of Hughes and Bott (1991) to account
for curvature effects for the conditions in Fig. 4, we calculate
(assuming the properties of water at 25 °C and a contact angle of
60° (Li et al., 2012)) that the minimum stable film flow in the
3.9 mm tube corresponds to a condensed liquid mass flux
147
GL;min = 70 kg m2 s1, approximately 100 times greater than could
have arisen in the experiment. This comparison is sensitive to
properties (notably the contact angle which, if taken as 40°, gives
a reduction in minimum stable flow by a factor of 10) but it is
apparent that film flow in this larger tube is unlikely to be the con-
figuration with minimum energy. However, while water is still
condensing from the gas phase, it can be expected that the film
flow conditions will prevail and that breakdown of the film can
only occur further downstream – formation of a single rivulet at
this point would reduce the interfacial area for mass transfer by
a factor 50, after which the rate of absorption of nitrous gases
would effectively cease.
A similar comparison for the 1.4 mm tube is less conclusive,
with the predicted minimum stable film flow for an assumed
contact angle 60° now about 30 kg m2 s1 (compared with
7 kg m2 s1 for 40° contact angle and an actual condensed water
flow of 5 kg m2 s1). However, the observed gas absorption goes
smoothly to completion in this and all other experiments reported
here for the 1.4 mm tube and there is no evidence of a sudden
change in absorption rate. Two-phase horizontal flow regime maps
for narrow passages (Shao et al., 2009) barely extend to the low
values of superficial liquid velocity encountered here
(0.003 m s1) but, based either on velocity or Weber number plots,
the prevailing flow condition is expected to be in the Taylor-
annular to annular flow regime, consistent with the application
of the annular flow model.
In the following discussion, emphasis is placed on the perfor-
mance of the 1.4 mm microchannel absorber in the earlier phases
of the absorption where mass transfer effects and process intensi-
fication are greatest. Fig. 5 presents results for the yields of HNO3
and HNO2 as a function of pressure for fixed nominal residence
time (t res;nom = 0.08 s) – the inlet mass flux in these runs
therefore increases with pressure, from 4.3 kg m2 s1 at 2 bar to
22 kg m2 s–1 at 10.0 bar. The experimental results show a strong
enhancing effect of pressure up to 6.0 bar, above which the total
acid yield barely changes. The results of the model are qualitatively
similar, but now with the maximum acid yield at this residence
time being achieved at 5.0 bar, and with the yield passing through
the maximum and falling significantly at higher pressures. Interro-
gation of the model results (Lee, 2012) reveals that the increased
thermal load (greater mass fluxes) at the higher pressures means
that the water condensation process is increasingly delayed. For
Fig. 5. Effects of system pressure on product yields for downflow absorption in a
1.4 mm ID tube with an inlet gas composition of 5% NO, 24% O2, 25% Ar and 46%
H2O, inlet mass fluxes of 4.3–22 kg m2 s1 (t res;nom = 0.08 s). Points show experi-
mental results while lines show predictions of the model with hI ¼ 1; -and-line
symbols are for different values of area multiplier (hI ¼ 2 and hI ¼ 3).
148 J.J.L. Lee, B.S. Haynes / Chemical Engineering Science 169 (2017) 140–150

the same reason, the gas core temperatures remain >100 °C (high
enough to suppress the formation of the acid precursors N2O3
and N2O4) until further into the tube (<0.005 s at 2.0 bar; 0.05 s
at 10.0 bar). The reason for the failure of the model to capture
the turning point in the yield curves is not known – however,
the results are very sensitive to the balance between the cooling
rate and the rate of N2O4 absorption. In terms of the adjustment
parameter, changing from hI ¼ 1 as in Fig. 5 to hI ¼ 2 brings the
prediction of HNO3 yield at 5.0 bar from 29% to 48%, thus bracket-
ing the experimentally observed value.
Direct evidence for the importance of O2 concentration is shown
in Fig. 6 which compares the course of the absorption processes for
10% NO with either 10% or 24% O2. In these experiments, at 2.0 bar
in a 1.4 mm ID tube, the water vapour mole fraction is maintained
constant at 66%, with argon making up the difference (14% or 0%, Fig. 7. Effects of NO partial pressure on product yields for downflow absorption in a
respectively) – the overall mass flux is the same in both cases, 1.4 mm ID tube with an inlet gas composition of 5–10% NO, 24% O2, 20–25% Ar and
G = 10 kg m2 s1. The concentrating effect of steam condensation 46% H2O, inlet mass fluxes of 4.3–22 kg m2 s1 (tres;nom = 0.08 s) and hI ¼ 1. Filled
is the same in the two experiments, as is the flow of noncondensi- points show experimental results for 5% NO; open points are for 10% NO. Point-and-
line symbols show predictions of the model described in the text.
ble gas (O2 + Ar). The formation of acid is clearly accelerated at the
higher O2 concentration (O2:NO = 2.4 versus 1.0) – the model
reproduces these effects with hI ¼ 3 and confirms that the effect
of oxygen is simply to accelerate the oxidation of NO in the gas
phase.
The oxidation of NO is second order in the NO concentration
and is expected to proceed faster at higher NO concentrations.
Fig. 7 confirms this effect by comparing results for acid yield from
10% NO with that from 5% NO, under conditions close to those in
Fig. 6. For the run with 10% NO, the argon fraction was reduced
to 20% in order to maintain comparable inlet velocities. The results
show that the yields of HNO3 are significantly higher with 10% NO
than with 5% NO, as expected from the kinetics of reaction (R1). At
the same time the yield of HNO2 is slightly reduced, this effect
being more pronounced when the ratio HNO2:HNO3 is considered
– this is also a kinetic effect, reflecting now the greater rate of dis-
proportionation of HNO2 at the higher concentration in the solu-
tion formed from 10% NO. These trends are reproduced by the
model with hI ¼ 1 but, as discussed in relation to Fig. 5, the model Fig. 8. Product yields (left axis) and calculated true residence times (dotted line,
right axis) for horizontal absorption in a 1.4 mm ID tube at 2.0 bar with an inlet gas
predictions appear not to capture temperature effects at these composition of 10% NO, 10% O2, 66–80% H2O, and balance Ar (14–0%). The inlet
higher pressures. mass flux is maintained at 10 kg m2 s1 (t res;nom = 0.16 s). Points show experimental
Given the importance of NO oxidation, especially at later stages results while solid lines show predictions of the model with hI ¼ 3.
of the absorption process, it is clear that the actual residence time
of the gas in the absorber impacts the extent of oxidation and
absorption. Fig. 8 shows results for absorption of 10% NO at to 0% in order to maintain the overall mass flux constant at
2.0 bar in a 1.4 mm ID tube with 10% O2 and varying amounts of 10 kg m2 s1. The extent of absorption increases as the argon is
steam (66–80%). Argon was added in amounts ranging from 14% progressively replaced by steam. Two main factors contribute to
this effect of reducing argon content – the concentrating effect of
steam condensation is enhanced; and the actual residence time
in the reactor increases, by approximately the same factor. Both
effects favour oxidation of NO and the production of acid. In addi-
tion, the longer residence time of the liquid phase allows a greater
extent of disproportionation of HNO2. The model captures these
trends accurately with an area enhancement factor hI ¼ 3.
The stoichiometric oxygen requirement for conversion of NO to
HNO3 is 0.75 mol mol1, corresponding to H2O:NO = 8.25 in Fig. 8.
Any oxygen in excess of stoichiometric is itself a noncondensible
diluent and it might be expected that further enhancement of
the process could be achieved by operating closer to the stoichio-
metric requirement. However, reducing the oxygen concentration
also reduces the rate of NO oxidation, as shown above. Therefore,
there is likely to be an optimal O2 excess that takes advantage of
the increased residence time while also providing adequate oxygen
for rapid oxidation of NO. This remains a topic for further
Fig. 6. Effects of oxygen partial pressure on product yields for horizontal absorption investigation.
in a 1.4 mm ID tube at 2.0 bar with an inlet gas composition of 10% NO + 66% H2O
+ 24% (Ar + O2) and a total inlet mass flux of 10 kg m2 s1. The filled symbols are
Fig. 9 shows the effects of cooling water temperature on the
for experimental data with Ar = 0% (O2 = 24%); open symbols for Ar = 14% performance of the absorber at short residence times
(O2 = 10%). Lines show predictions of the model with hI ¼ 3. (tres;nom = 0.03 s) when operating at 2.0 bar with a small excess of
 J.J.L. Lee, B.S. Haynes / Chemical Engineering Science 169 (2017) 140–150
Fig. 9. Effects of cooling water temperature on product yields for horizontal
absorption in a 1.4 mm ID tube at 2.0 bar with an inlet gas composition of 10% NO,
8% O2 and 82% H2O, and inlet mass flux of 9.2 kg m2 s1 (tres;nom = 0.03 s). Points
show experimental results while lines show predictions of the model with hI ¼ 3.
oxygen (O2:NO = 0.80). The yields of both acids are clearly reduced
when the cooling temperature is raised, with the trends being cap-
tured by the model. Overall, there is a reduction in the condensa-
tion rate and the persistence of higher gas temperatures – as a
result, the rate of oxidation of NO and the concentrations of the
acid-forming intermediates N2O3 and N2O4 are suppressed. The
yield of HNO2 is additionally reduced because its disproportiona-
tion is enhanced when the liquid film temperature is increased.
In summary, this work has demonstrated that very high levels
of process intensification in the production of nitric acid can be
achieved through a combination of process modification and the
use of a microchannel condenser/absorber. For the conditions of
Fig. 8 with molar feed rate ratios H2O:NO = 8 and O2:NO = 1, 99%
acid yield is achieved within a tube length of 0.85 m, correspond-
ing to a volumetric intensity of 13 tonne HNO3 h1 m3. This is
approximately three orders of magnitude greater than for conven-
tional plate columns achieving 99% absorption at 2 bar, for which
values of 0.005 tonne HNO3 h1 m3 (Andrew, 1985) and
0.014 tonne HNO3 h1 m3 (Hoftyzer and Kwanten, 1972) are esti-
mated. While operation of a plate column at higher pressure
increases its productivity / p2:5 , the intensity achievable at
10 bar is still vastly less than for low-pressure absorption in the
steam-ballasted microchannel process. However, there are some
significant differences between the products obtained from the
conditions in the microchannel example and those from the con-
ventional operations.
Firstly, the NOx concentration remaining after 99% absorption in
the microchannel is 37,000 ppm whereas the conventional plant
has 1000 ppm, even though the actual flow of NOx is the same
in the two cases. To bring the microchannel absorber tail gas down
to 1000 ppm by absorption would require a tower not much smal-
ler than a conventional tower because the volumetric requirement
at the lower concentrations is determined entirely by the kinetics
of NO oxidation. Therefore, other tail gas treatment options would
need to be considered, for which the small gas volume and high
concentrations would offer many advantages.
The second important difference between the microchannel and
conventional products is that the acid concentration in the former
is 32 wt% whereas it is standard industry practice to produce 55–
65 wt%. To the extent that the concentrated form is actually
required, the tower, typically 70 m tall, may still be needed. In
other respects, however, the <1 m ‘‘height” of the microchannel
system is a very attractive alternative when coupled with ammo-
nia combustion in a steam ballast. The visual aspects of eliminating
the tower are obvious but there are process benefits also – for
149
example, the intensification achieved at relatively low pressures
(2 bar) is such that high-pressure absorption might be
unnecessary.
5. Conclusions
Absorption of nitrous gases in a 1.4 mm tube allows profound
process intensification relative to typical absorption towers
employed in conventional nitric acid plants. Intensification factors
of the order of 1000 are achievable when the nitrous gas is pro-
duced in a steam ballast – condensation of the steam is extremely
rapid in the microchannel, thereby leading to significant increases
in the concentration and rates of reaction and absorption of the
nitrous gases and oxygen. Overall, the intensification demon-
strated in this work derives from a combination of process modifi-
cation and the inherent intensification of heat and mass transfer
rates in microchannel systems.
While the interactions between reaction kinetics and heat and
mass transfer effects are complex, a simple model of microchannel
condensation in annular flow, augmented to account for chemical
reactions in the gas and liquid phases, describes the qualitative fea-
tures of the system over a wide range of conditions. Quantitative
comparisons can generally be made upon adjustment of a single
parameter, the interfacial area between the phases, by a factor
1 K hI 6 3.
Acknowledgements
The authors acknowledge the financial support and permission
to publish provided by Orica Limited. Jessy Lee thanks the Aus-
tralian Government for an Australian Postgraduate Award.
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