N02 Penetration (Fraction)
+- T=373K T=423K ~b~ T=473K
Figure 4-18. N02 penetration versus bed exposure time ([NO2]in=:100 ppm, [O2]=10%).
Mutasher, E. L; Khan, A. R.; and Bowen, J. H., "Communications: Reversible, Noncatalytic
Reactions Between Gases and Solids in Fixed Beds," Industrial Engineering Chemistry
Research. 28(10): 1550-1553, 1989.
Nelson, B.W.; Nelson, S.G.; and Higgins, M.O., A New Catalyst for NO.. Control.
ESL-TR-89-11, HQ AFESC, Tyndall AFB, Florida, 1989.
Nelson, B.W.; Van Stone, D.A.; and Nelson, S.G., Development and Demonstration of a
New Filter System to Control Emissions During Jet Engine Testing. CEL-TR-92-49, HQ
AFCESA, Tyndall AFB, Florida, 1992.
Nelson, S.G; Van Stone, D.A.; Little, R.C.; and Peterson, K.A., Laboratory Evaluation of a
Reactive Baffle Approach to NO.. Control. Final Report, Contract Number FO8635-90-C-
0053, HQ AFCESA, Tyndall AFB, Florida, 1993.
Nelson, S.G., (Sanitech, Inc.), U.S. Patent 4,721,582 (Jan. 26, 1988).
Nelson, S.G.; Nelson, B.W.; and Higgins, M.O., Study of the Regenerabilitv of a Unique New
Sorbent that Removes S02-N0.. from Flue Gases. Phase II Final Report, EPA SBIR
Contract 68-D80066, Sanitech, Inc., Twinsburg, Ohio, 1990.
Newton, G. H.; Chen, S. L.; and Kramlich, J. C., "Role of Porosity Loss in Limiting S02
Capture by Calcium Based Sorbents," AIChE Journal. 35(6):988-994, 1989.
NTIS Tech Notes, "Process Eliminates 99% of NOx from Exhaust in Lab Tests," DOE
Technology Application, July 1987.
Organization for Economic Cooperation and Development (OECD), Control Technology for
Nitrogen Oxide Emissions from Stationary Sources. Paris. France, 1983.
Pakrasi, A., "Kinetic Studies on the Removal of Hydrogen Chloride from Flue Gas by
Hydrated Lime Powders in a Bench Scale Fixed Bed Reactor," Ph.D. Dissertation; University
of Tennessee, Knoxville, Tennessee, 1992.
Perry, R. A. and Siebers, D. L., "Rapid Reduction of Nitrogen Oxides in Exhaust Gas
Streams," Nature. 324 (18):657-658, 1986.
Petrik, M.A., Use of Metal Oxide Electrocatalvsts to Control NO..Emissions from Fixed
Sources. ESL-TR-89-29, HQ AFESC, Tyndall AFB, Florida, 1991.
Pigford, R. L. and Sliger, G., "Rate of Diffusion-Controlled Reaction Between a Gas and a
Porous Solid Sphere," Industrial Engineering Chemistry Process Design and Development.
T=373 K, [O2]=0%). [ y = O.OOlx + 0.06, rM).99, Fit Std Error = 0.001, F-724.0],
+ Experimental Predicted
Figure 4-47. Experimental versus predicted N02 concentration ([N02]in=170.0 ppm, T=473 K, [O2]=0%, Gas samples collected
from middle of bed).
provided from exhaust-gas augmentation may accomplish some of this oxidation.
2. More MgO-vermiculite surface studies are necessary to better understand the
nature of the surface and the role it plays in the removal of N02 from a flowing gas stream.
Pore size distributions and associated structural implications may be very useful in further
explaining the rate-limiting processes involved in this reaction. The measurement of
additional physical parameters is required for the strict mathematical interpretation of
shrinking unreacted-core model results. Real-time surface analyses would allow for following
the progress of reaction, which could be combined with post-sorption analyses for the
quantification of solid conversion and product formation. A modified reactor design that
would allow for the removal of all used sorbent after a run (without any loss) would be an
improvement in this regard.
3. More traditional sorption studies, where the progress of reaction is followed
using thermogravimetric methods and single sorbent pellets, may also assist in the application
of the shrinking unreacted-core model to this reaction. This research is actually a step ahead
in that regard, since the basic research on the reaction between N02 and MgO powder
(without vermiculite substrate) has not yet been conducted or reported. The use of pressed
pellets of MgO would also be useful in this regard. Dispersing small quantities of MgO in an
inert bed of quartz sand is another method that may allow for the collection of this type of
4. The range of experimental conditions studied should be extended to evaluate
the application of this sorbent material to other combustion sources. The use of NOx
concentrations from one to two orders of magnitude greater than used here for the collection
surface is still being converted into an inert product layer after the same period of exposure
From Figure 4-9, at a reaction temperature of 423 K, initial N02 penetration is
lowest for the two lower inlet concentrations. Since there is less energy being supplied via
heat energy to overcome the activation energy barrier, it may be that only a limited number
of molecules can be removed. After approximately 25 minutes of bed exposure time have
elapsed, the overall penetration numbers again converged toward a value between
approximately 30 and 40 percent. At a reaction temperature of 373 K (Figure 4-10), there
was no discernible pattern observe for the initial penetration values, although the value for an
inlet N02 concentration of 20 ppm remained the lowest. Toward the end of the bed exposure
time period, however, N02 penetrations were lowest for the two highest concentrations. This
may be an indication of the higher concentration gradient serving to facilitate N02 removal
in promoting diffusion of the N02 molecules toward available MgO interior reaction surfaces.
Intrinsic first-order rate constants for these data are shown in Table 4-2.
Effects of Oxygen
Like NO removal, initial N02 removal efficiencies were improved when oxygen was
present. Since some NO, present as impurity in the N02 gas supplied, is oxidized to N02,
the actual N02 removal rate may be higher than observed, particularly at lower temperatures.
It is possible that NO, which is physisorbed on the sorbent surface, is eventually oxidized to
N02 before being sorbed to form a nitrite or nitrate compound. Since 02 concentrations
were at the percent level, they are considered to be in great excess relative to N02
acids, they were ultimately collected in the coalescing filter or condensed out in the sampling
manifold prior to analysis.
Similarly, the presence of water vapor itself can interfere with NOx measurements
directly by N02 absorption, as well as via third-body quenching of chemiluminescence
(Trdona et al., 1988; Campbell et al., 1982). Therefore, it is important to minimize contact
time of the gas with water vapor in sampling lines. Any N02 removed by gas humidification
is accounted for by the fact that bed inlet gases were sampled after this point in the system.
The analyzer reaction chamber is maintained at a vacuum of approximately 29 inches of
mercury (98 kPa) to minimize third-body quenching effects. Another common interference
with NOx measurements in the atmosphere is caused by the presence of such other nitrogen-
containing compounds as peroxyacetyl nitrate (PAN), which can be converted into NO in the
thermal converter. Again, these species are not suspected to be present in the experimental
procedures used in this study.
To prevent particulate matter contamination of the chemiluminescent analyzer, a 0.5
pm pore size Teflon filter (Gelman Sciences, Ann Arbor, Michigan) was placed in the
sample line at the analyzer sample inlet. This filter was found to be essentially non-reactive
to NOx. Without such a filter, it is quite easy to experience blockage of internal capillary
tubing. Deposits could also form on the glass filter that separates the reaction chamber from
the photomultiplier tube, causing a loss in instrument sensitivity (Klapheck and Winkler,
A continuous gas analyzer (Model IR-2100, Infrared Industries, Inc., Santa Barbara,
California) was used to electrochemically measure 02 concentrations. The principle of
Initial studies found that the sorbent material could be successfully regenerated with
minor reduction in adsorption capacity of the regenerated material. Ruch et al. (1990)
confirmed that the MgOvermiculite/NOx reaction is most likely due to chemisorption and
that the vermiculite/NOx sorption is a result of physical adsorption based upon hysteresis
during limited adsorption/desorption tests. This observed hysteresis is most probably the
result of the forces of chemisorption, generally involving electron transfer between the solid
(adsorbent) and gas (adsorbate) molecules held at the surface. These forces are typically
much stronger than the intermolecular van der Waals forces associated with physical
adsorption (Kovach, 1978; Szekely et al., 1976). They also evaluated the surface areas of
these products using N2 and water adsorption and Brunauer-Emmett-Teller (BET) theory
and found the sorbent surface areas to be larger than would be expected from the collective
surface areas of the vermiculite and MgO. This suggests that the vermiculite support
effectively enhances the surface area development of the MgO. Reported nitrogen isotherm
surface areas ranged from 16 to 55 m2/g for sorbents prepared at 550 C. Sieved samples had
a maximum surface area of 36 m2/g. Fourier transform infrared (FTIR) solid spectra indicated
the presence of Mg(OH)2, which disappeared as conditioning temperature increased. Nitrite
was found in some samples exposed to low-concentration flue gases by FTIR solid and
solution spectra, but results were determined to be inconclusive. X-ray diffraction interplanar
spacings showed that Mg(N03)2 was present.
CONTROL OF NOx THROUGH GAS-SOLID INTERACTION
Exhaust-Gas Treatment Methods
A significant amount of research has been conducted over the past two decades to
determine a means of treating flue gases to reduce nitrogen oxide emissions. Some of the
most extensive research has been conducted in Japan, which was one of the first countries to
enact strict NOx emission regulations. In general, three classes of catalytic methods have been
evaluated. The first class involves mixing the waste gas with methane (CH4) or other gaseous
fuels/reducing agents before exposing the mixture to a catalyst; the second involves mixing
the effluent with ammonia before exposure to a catalyst; and the third involves exposure to
a catalyst or adsorbent with or without methane (or other fuel) or ammonia additions.
Numerous materials have been proposed as catalysts, and a number of these have been
patented, however, those receiving the most attention have been platinum or other precious
metals or metallic oxides from the alkaline earth group (Nelson et al., 1989; Klimisch and
Larson, 1975;Meubus, 1977).
chemical reactions can have substantial activation energies, operating at lower temperatures
should lead to control by chemical kinetics, making intrinsic kinetic data collected in this
range more valid. The effects of gas film mass transfer resistance were evaluated by varying
flow rate through the bed at the highest reaction temperature and graphically evaluating its
effect on initial reaction rate. Figure 4-1 is an example of this type of study. The definition
ofN02 penetration is the fraction of inlet N02 concentration that exits the bed at a given time,
i.e., C(JCm. While superficial gas velocity was varied by an order of magnitude, this did not
greatly affect the initial rates. The absolute variation in associated rate constants determined
during this type of evaluation was generally less than ten percent. Because increasing flow
rate through the packed-bed by an order of magnitude did not significantly affect the reaction
rate, the lowest flow rate was used for the majority of experimental runs to conserve cylinder
It will be shown later that, in most cases, the initial chemical kinetics were affected by
an increase in temperature, providing more evidence that gas film mass transfer was not rate
limiting. Using the mass-transfer correlation of Ruthven (1968), the ratio of superficial
velocity to sorbent particle diameter is sufficient to minimize mass-transfer resistance, within
the temperature range evaluated. Because flow through a packed-bed is a highly complex
phenomenon and the intricate details relative to the gas-solid reaction mechanism and the
physical characteristics of the solid sorbent are not fully understood, it is possible that some
gas-film resistance to reaction exists. However, based upon the preceding discussion, it does
appear that this resistance has been effectively minimized in this experimental research study.
Figure 4-34. Shrinking unreacted-core chemical-reaction-control-equation evaluation, xr=205 minutes ([NCy^SO ppm,
T=423 K, [OJ=0%). [ y = 0.005x + 0.0002, rMJ.98, Fit Std Error = 0.003, F=812.9].
100ppm s 50ppm 20ppm
Figure 4-11. N02 penetration vs bed exposure time (T=473 K, [O2]=10%).
quantity of material reacting is proportional to the available surface area of the unreacted core
(which at the beginning of the reaction would be the exterior surface of the particle as there
is no inert product layer formed) and can be expressed in the same manner as equation 4-4:
4 ti r 2 dt
4 7i r] &
Here ks represents the intrinsic first-order rate coefficient for the surface reaction (cm/s).
Writing Nb in terms of the shrinking radius by analogy to equation 4-7:
4 2 c
This may be rearranged and integrated to derive an expression describing how the unreacted
core shrinks with time:
-apB f*c drc bks[A]g dt (445)
After integration, t may be isolated by rearrangement:
The time for complete conversion of the solid under chemical reaction control, defined as rn
occurs when r= 0:
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operation upon which this instrument is based is a simple coulometric process in which
oxygen in the sample gas stream is reduced in an electrochemical cell. The gas stream enters
the cathode cavity, with any oxygen being metered to the cathode through a diffusion barrier.
At the cathode, oxygen is electrochemically reduced via the reaction
02 + 2H20 + 4e' 40H- (3-3)
An electrolyte solution in the cathode cavity contains potassium hydroxide (KOH), which
facilitates migration of the generated hydroxyl ions to an anode, where they are oxidized back
to oxygen. This occurs following the reaction
40H- 02 + 2H20 + 4e* (3-4)
The resulting cell current is directly proportional to the oxygen concentration in the sample
gas stream. This current is measured electronically and is converted into an indicated
concentration value. The instrument measures oxygen concentration between zero and 25%,
with a manufacturer-reported accuracy of 2% of full-scale on all ranges. When using this
instrument, one must keep the sample inlet pressure and flow rate within the specified limits
to ensure accuracy of the measurement.
Multiple-point calibrations were performed on all instruments following procedures
outlined in the appropriate instrument manuals. Certified standard gases were used as transfer
standards whose composition is traceable to the National Institute of Standards and
Technology, and appropriate calibration curves were determined by challenging the
instruments with known standard mixtures. Typical calibration curves for the NOx and 02
analyzers are shown in Figures 3-7 and 3-8, respectively. Daily zero and span checks were
performed on each analyzer, and quality control charts were produced. Running sample
There is some deviation outside the confidence intervals in the middle of the run, most
probably the result of a transition from one mechanism to another. Both the combination of
controlling-mechanism and increased-molar-volume equations predicted x values between
approximately 400 to 500 minutes. To evaluate the predictability of sorption behavior at this
(relatively) high concentration and temperature scenario, the empirical relationship between
1 Ik and bed exposure time was used to produce the plot shown in Figure 4-47. Since this
relationship is most predictable after an exposure time greater than approximately 30 to 40
minutes, it is likely that the rate coefficients predicted are for the slow-rate-diffusion process.
For this reason, the model does not predict early sorption behavior well, leaving a gap
between the experimental and predicted curves.
Figure 4-48 is a plot of cumulative N02 mass removed versus bed exposure time,
which clearly shows the decreased mass removal rate as reaction progressed and diftusional
resistance increased. While a larger mass of N02 was collected in this case, MgO utilization
was still less than one percent. An interesting finding related to this slowdown in mass
removal is depicted in Figure 4-49, which shows N02 and NO concentrations as a function
of time as measured at the middle of the bed. It can be seen that as the N02 concentration
increased toward the equilibrium product layer diffusion control situation at approximately
40 minutes, NO production was increasing toward a maximum. As N02 removal rate
decreased due to the diftusional resistance, the rate of product formation (including NO) also
decreased. After 300 minutes, N02 removal was approximately 5% and the NO
concentration had almost reached its initial value. It is expected that when N02 was no longer
conversion in gassolid reactions to the effective closure of a narrow size range of small
surface pores, leaving larger pores of smaller surface area available for reaction at a greatly
reduced rate. Bhatia and Perlmutter (1981b) presented a correlation that allows for the
calculation of maximum conversion based upon initial porosity (ea) and Z:
= (Z-l)(l-e; (4-36)
Assuming an initial porosity value of 0.3, based upon values used for CaO by the authors, the
calculated value for Xmax is approximately 16%. High initial sorbent porosity (and associated
high surface area) can create the potential for internal diffusion limitations to chemical
reaction. Marsh and Ulrichson (1985) found that grains of CaO obtained by calcining
Ca(OH)2 contained significant quantities of micropores, many of them around 22 in radius.
Effective pore closure occurs when this radius decreases to approximately 5 A. If intrapellet
diffusional resistance is appreciable, pore closure may occur at the surface, significantly
limiting diffusion into the particle interior and reducing ultimate MgO conversion within the
sorbent. In micropore diffusion, the diffusing molecules are "trapped" by the attractive forces
near the pore walls in a process similar to surface diffusion, but steric effects are more
important. Small differences in molecular size or shape can produce large differences in
diffiisivity (Ruthven, 1988). The simple grain model cannot realistically simulate porosities
less than 26%, whereas initial porosities of calcined limestones can be greater than 50%
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RESULTS AND DISCUSSION
Intrinsic Kinetic Studies
Experiments were conducted to collect data that provide insights into relevant
parameters controlling NOx removal efficiencies, potential reaction mechanism(s) and
reaction kinetics. Duplicate runs were conducted for every set of conditions to generate the
data necessary for the determination of kinetic parameters. A comparison of results between
duplicate runs under similar conditions showed remarkable reproducibility (statistical error
< 5%). To determine intrinsic reaction kinetics, NOx concentrations were followed with
increasing bed exposure time from a selected sampling valve, which represented a specific bed
residence time. This was necessary because of a system artifact that created a lag-time of
approximately 3-4 minutes to allow for line flushing until a stable instrument reading was
reached after a sampling valve was selected. To explain further, for a given set of conditions,
four separate runs would be necessary to collect data for all five sampling points; bed inlet,
three points within the bed, and bed outlet. Bed inlet values were checked on all runs, before
and after the other data were collected. Every 10 seconds, the three NOx analyzer channels
displayed 10-second average NO, N02, and NOx concentration values ([N02] calculated by
difference). Data were collected every minute throughout the run. From these data,
1 (1-x)1/3 1 3(1-X)2/3 2(1-X)
+ 473K-R 473K-D
Figure 4-44. Shrinking unreacted-core model evaluation ([N02]in=200 ppm, T=473 K, [O2]=0%).
T=373K T=423K -b- T=473K
Figure 4-19. N02 penetration versus bed exposure time ([NO2]in=50 ppm, [O2]=10%).
forming a sharp front which moves inward with increasing exposure time. Larger samples
with varying (CaO) thickness may lead to significant intraparticle difrusional limitations,
which may intensify as the solid product forms particle agglomerations (Zarkanitis et al.,
1990). While dynamic equilibrium conditions are achieved at a time equal to x, and effective
conversion approaches a fairly constant value, N02 is still being removed from the gas stream
at a rate dependent upon its effective diffiisivity through the product layer and/or porous
structure of the sorbent. There remains a significant residual N02 removal capacity, which
continues at significant levels for extended periods of time.
The molar volume ratios of Mg(N03)2 products to Mg(OH)2 reactants are
approximately 50% smaller than the ratio to MgO reactants, which may partially account for
the improved performance of hydrated sorbents. This results in more available surface area
through unblocked pore-surface area on a normalized time basis. The shrinking unreacted-
core model was used to interpret results under these conditions and, in genera}, x values were
approximately twice as large. This means that hydrated sorbents can remove approximately
twice as much mass from a gas stream with a given mass flow rate. Due to the inherent
complications involved in the study of gas-solid reactions, chemical kinetics or the shrinking
unreacted-core model alone can not completely describe the molecular processes that are
occurring. A structural investigation of reactants and products may be helpful for this
purpose. The crystalline structure of MgO is the same as that of NaCl, while Mg(OH)2
crystallizes with the Cdl2 layer structure, in which every Mg atom is surrounded by six OH.
Every OH forms three bonds to Mg atoms in its own layer, while contacting three OH of an
adjacent layer (Wells, 1952). A larger bulk reactant would be comprised of relatively thin,
apparently very sensitive to the presence of water vapor, which reduces porosity (Borgwardt,
1989). A graphic representation of the shrinking unreacted-core model was depicted in a
series of energy dispersive X-ray analysis micrographs of calcined limestone chalk and S02
(Dam-Johansen and Ostergaard, 1991a). The associated data were fitted with a grain model
of the shrinking unreacted-core mechanism (Dam-Johansen, 1991b). Bjerle et al. (1992)
reported useful experimental techniques for describing this reaction as well. They were able
to use the shrinking unreacted-core model to describe the various stages of reaction as
conversion progressed. Sotirchos and Zarkanitis (1992) found that the sulfation rates of MgO
were comparable to those for CaO. A simple grain model was also used to interpret data
describing a furnace sorbent slurry injection process, in which a limestone slurry was calcined
for use in S02 removal (Damle, 1994).
S02-Calcium Hydroxide Reaction
Flue-gas desulfurization through spray drying of a Ca(OH)2 slurry has recently become
an important alternative to the traditional wet lime or limestone scrubbing techniques. In
spray drying, S02-containing flue gases are contacted in a dryer with finely atomized lime
slurry that absorbs the S02. As water evaporates from the slurry droplets, reacted solids and
unreacted Ca(OH)2 remain and are collected on bag filters. This accumulated residual
Ca(OH)2 serves to remove considerable quantities of unreacted S02 from the inside of the
bags as well as in the ducts. Ruiz-Alsop and Rochelle (1988) used a bench-scale fixed-bed
reactor to study this reaction. The shrinking unreacted-core model was applied to their
results. Among the many factors evaluated, relative humidity of the gas was determined to
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LIST OF FIGURES
2-1. Schematic representation of a jet engine test cell (JETC) 24
2-2. Schematic representation of the shrinking unreacted-core model 38
2-3. Schematic representation of the grain model 40
3-1. Experimental arrangment for packed-bed studies 59
3-2. Example low-flow-rate rotameter calibration curves
(Omega N042-15ST Tube) 61
3-3. Example high-flow-rate rotameter calibration curves
(Omega NO92-04G Tube) 62
3-4. Schematic representation of 316 stainless steel packed-bed reactor 64
3-5. Schematic representation of internal sampling tube location and appearance ... 65
3-6. Schematic representation of 316 stainless steel mixing or sampling manifold ... 66
3-7. Typical chemiluminescent NOx analyzer calibration curve (for NO channel) ... 74
3-8. Typical IR-2100 oxygen analyzer calibration curve 75
4-1. Gas-film-mass-transfer resistance evaluation N02 penetration (C^/C^
versus bed exposure time ([N02]in=200 ppm, T=473 K, [O2]=0%) 81
4-2. Log-probability plot of MgOvermiculite sorbent particle size distribution .... 84
4-3. Log-probability plot of Akrochem Elastomag 170 MgO powder particle size
distribution (manufacturer-provided data) 85
variation, as well as for comparison with data from the Sorbtech samples to ensure that the
sorbent was properly prepared.
The sorbent material was incorporated into a packed-bed arrangement in a
non-reactive 316 stainless steel tubular reactor in a controlled temperature (tube furnace)
environment, which will be described later. A single batch of material was used for all
experiments. Limited surface area/composition analyses of the material were performed to
establish baseline values. Comparative experiments were conducted using sorbent samples
provided by Sorbtech.
Reaction temperatures were controlled using a tube furnace (Model 421135,
Thermolyne, Dubuque, Iowa) to contain the reaction vessel. Sorption study temperatures of
373, 423, and 473 K were used. These temperatures were chosen because they represent a
reasonable range expected for augmented/cooled exhaust gases. Gases were preheated
before entering the furnace to ensure that they were at or above reaction temperature (+ 20
0 C) when they entered the bed, so they would not need additional heating.
All runs were conducted at atmospheric pressure. The bed outlet gases were
exhausted to the atmosphere through a laboratory ventilation system. Pressure drop versus
exposure time was evaluated through the bed, using a U-tube manometer connected to ports
at the bed inlet and outlet. Pressure drop versus gas velocity was evaluated via an empirical
removed, NO would no longer be produced and would indeed reach its initial bed inlet
General Applicability of the Shrinking Unreacted-Core Model
It appears from the cases just presented that the shrinking unreacted-core model
provides a basis for chemically and physically describing the sorption behavior occurring
during the removal of N02 by the MgOvermiculite sorbent. Combined with the classical
chemical kinetics evaluations performed, these results allow for the prediction of sorption
behavior with time under a variety of conditions. The use of the local-equilibrium theory to
describe the transition from packed-bed theories to the shrinking unreacted-core model was
a key step in the process. While the local-equilibrium theory allowed for the determination
of solid conversion as it relates to N02 penetration, it is apparent that this conversion is
relative rather than absolute, based upon the low sorbent utilization rates found. These low
utilization rates are certainly a complex function of many factors, however, such as the low
N02 concentrations evaluated, as well as probable low porosities, which may produce
intraparticle diffusional resistances, are key parameters. The high solid-product-to-reactant
molar volume ratio is another mitigating factor in this situation. Dam-Johansen and
Ostergaard (1991b) attributed the rapid decrease in reaction rate during the sulfation of
limestone particles to filling of micropores. The macroporous structure remaining may allow
some sulfation to continue at a very slow rate. The degree of conversion decreases linearly
from the particle surface inward to a certain distance from the surface where it goes to zero,
The combustion of carbonaceous jet fuels during jet engine testing produces
significant quantities of nitrogen oxides (NOx). Besides direct negative impacts on human
health, nitrogen oxides have been linked to other detrimental effects on air quality and the
environment. The latter include interactions with hydrocarbons to produce photochemical
oxidants and smog, and contribution to the phenomenon of acid precipitation through nitric
acid formation. Nitric oxide emissions may also contribute to the degradation of visibility and
aesthetics by direct emission of high NO levels in elevated plumes followed by atmospheric
oxidation to N02 and fine particulate aerosols resulting from by-products of N02 reactions
(Wark and Warner, 1981).
Properties and Health Effects of Nitrogen Oxides
There are seven possible forms of nitrogen oxides (NxOy). Two of the most abundant
of these gaseous oxides of nitrogen, nitric oxide (NO) and nitrogen dioxide (N02), are the
predominant air pollutants of environmental and health concern. These two forms, however,
are rapidly interchangeable in the atmosphere and are often grouped together and collectively
2 2.1 2.2 2.3 2.4 2.5 2.6 2.
Bed Exposure Time
^ 5 minutes 10 minutes -b 15 minutes 20 minutes
Figure 4-22. Arrhenius plot of In k versus 1000/T (T between 473 and 373 K, [NO2]in=20 ppm, [O2]=0%).
4-4. NO removal by humidified MgOvermicuilite sorbent ([NOJ^^IO ppm,
T=423 K, =11%, 3% H20 vapor) 88
4-5. N02 removal versus residence time (T=473 K, =9.9%) 90
4-6. First-order kinetic plot ([NOJ^lOO ppm, T=473 K, [O2]=10%) 92
4-7. First-order kinetic plot ([NO2]fa=100 ppm, T=473 K, [O2]=10.5%) 93
4-8. N02 penetration vs bed exposure time (T=473 K, [O2]=0%) 95
4-9. N02 penetration vs bed exposure time (T=423 K, [O2]=0%) 96
4-10. N02 penetration vs bed exposure time (T=373 K, [O2]=0%) 97
4-11. NQ2 penetration vs bed exposure time (T=473 K, [O2]=10%) 102
4-12. N02 penetration vs bed exposure time (T=423 K, [O2]=10%) 103
4-13. N02 penetration vs bed exposure time (T=373 K, [O2]=10%) 104
4-14. N02 penetration vs bed exposure time ([N02]in=200 ppm, [O2]=0%) 108
4-15. N02 penetration vs bed exposure time ([N02]in:= 100 ppm, [O2]=0%) 109
4-16. N02 penetration vs bed exposure time ([NOJ^SO ppm, [O2]=0%) 110
4-17. N02 penetration vs bed exposure time ([NO2]in=20 ppm, [O2]=0%) Ill
4-18. N02 penetration vs bed exposure time ([N02]Â¡=100 ppm, [O2]=10%) 113
4-19. N02 penetration vs bed exposure time ([NOJ^SO ppm, =10%) 114
4-20. N02 penetration vs bed exposure time ([NO2]i=20 ppm, =10%) 115
4-21. Arrhenius plot of In k versus 1000/T (T between 473 and 423 K,
([NO2]m=100 ppm, [O2]=0%) 116
4-22. Arrhenius plot of In k versus 1000/T (T between 473 and 373 K,
([NO2L=20 ppm, [O2]=0%) 117
4-23. N02 penetration versus bed exposure time (20 ml H20 added to 7 g
MgOvermiculite sorbent, [NO2]in=100 ppm, [O2]=0% T=473 K) 121
and its variations, as well as empirically. These models provided a chemico-physical basis for
explaining sorbent performance and probable reaction mechanisms.
MgOVermiculite Reactive Sorbent Material.
This material (approximately 45% MgO to 55% vermiculite substrate by weight) was
prepared according to a process patented by the inventor (U.S. Patent 4,721,582, Sorbent
Technologies Corporation, (Sorbtech), Twinsburg, Ohio, 1988). Commercial-grade
magnesium oxide was used (98% volatile-free MgO) with a manufacturer-reported surface
area of 170 m2/g (Elastomag 170, Akrochem Corporation, Akron, Ohio). While the
process of preparing the sorbent is described in detail in the patent, a more general descriptive
process is presented here for informative and comparative purposes. Sorbent was prepared
in small batches, by necessity, in stainless steel pans in the laboratory. A quantity of coarse
vermiculite was weighed out in the pan, to which a 4:1 mass ratio of deionized water was
added. This is the maximum ratio allowed in the patent, but is greater than the 2:1 ratio
reported by Sorbtech in the preparation of a sample provided by them for experimental use.
Trial-and-error practice in the laboratory indicated that sufficient water was necessary to
attach the majority of the MgO particles to the surface of the vermiculite. Since the
vermiculite is highly hydrophilic, it readily absorbs the extra water. The sorbent is
subsequently heat-treated, during which process any excess water will be driven off. The
water and vermiculite were mixed to ensure complete absorption.
compared and averaged to determine actual experimental reaction temperature. This reaction
temperature was used to calculate the actual flow rate through the bed, which could then be
used to determine residence time at any given sampling point within the bed. It was assumed
that the sorbent bed was at the same temperature as the reactor surface after sufficient
When gas humidification was used, a secondary preheating heat tape was used before
the gases entered the humidification vessel, which consisted of an impinger apparatus
mounted inside a modified 3-liter Pyrex flask (Southern Scientific, Inc., Micanopy, Florida)
containing deionized water The flask was placed in a heated flask mantle connected to a
separate voltage controller. Various temperature/flow rate combinations were evaluated to
allow for 3-5% water vapor to be picked up by the flowing gas stream. The humidified gases
were then reheated to ensure that they were approximately 20 C above reaction temperature.
The actual water vapor content of the gases was determined by weighing collected condensed
water from a stainless steel coalescing filter (Model 41S6, Balston, Inc., Haverhill,
Massachusetts) at the bed outlet. Water vapor was removed from the sample gas stream
before analysis through condensation in the sampling manifold. Gas flow rate was always
corrected for the presence of water vapor. The effect of moisture on reaction was sometimes
evaluated simply by adding sufficient deionized water to a virgin bed to convert all MgO into
Mg(OH)2. This was verified by the presence of water vapor at the bed outlet. Once
converted, Mg(OH)2 is stable over the range of temperatures evaluated (Sidgwick, 1952).
While initial N02 penetration was lowest for an inlet N02 concentration of 20 ppm, it rapidly
increased and reached a value of approximately 50%. This short initial period of efficient
removal may represent the small quantity of N02 molecules initially physically adsorbed on
the surface of the sorbent, or a chemical reaction induction period which occurs before
dynamic equilibrium conditions are achieved.
From all of these data, it seems apparent that the range of reaction temperatures
evaluated encompass a transition region where sorbent N02 removal characteristics in the
presence of oxygen are changing. The significance of the effects of temperature variation on
N02 penetration and the difficulty in distinguishing between these effects at the two lower
temperatures will be examined in a later section. Table 4-3 contains intrinsic first-order rate
coefficient data obtained with 02 present, which can be compared to the values displayed in
Table 4-2 as a means of estimating the significance of oxygen in its effect on N02 removal by
Effects of Bed Temperature
There appeared to be a N02 reaction rate dependence on bed temperature when
temperatures exceeded 423 K. In the range from 373 to 423 K, initial first-order N02
removal rate coefficients were often approximately the same. When temperatures greater
than 423 K were used, there was a much greater difference in first-order rate coefficient
values. As expected, with all other variables kept constant, higher bed temperatures produced
higher rate coefficient values. Additionally, as temperature increases, theoretically, more
adsorbate molecules with sufficient activation energy for reaction to occur will strike the
a a dNb
S dt 4nR2 dt
in which kg is the mass transfer coefficient between the gas phase and the sorbent particle.
Letting pB represent the molar density of B in the solid, and Fbe the particle volume,
the number of moles of B present in the particle is:
N pBr (4-5)
The decrease in the volume or radius of the shrinking unreacted core as a result of the
reaction of adNB moles of solid and (or with) bdNA moles of gas is given by the equation
-adNB = -bdNA = -apBdV = -apBd(4/3 nr)3 = -a\npJf]drc (4-6)
Substituting equation 4-6 in equation 4-4 produces an expression for the rate of reaction in
terms of the shrinking radius or unreacted core:
a?/c dr c
By rearranging and integrating, an expression for how the unreacted core shrinks with time
sorption behavior over a variety of conditions, in particular showing a transition from
chemical reaction control to product layer diffusion control. In some cases it appeared that
both processes were simultaneously rate-limiting. It is evident that the range of
concentrations and temperatures evaluated represented a transition region, which made it
difficult to conclusively determine rate-limiting mechanisms. The possibility of simultaneous
and sequential surface reactions makes modeling the N02 removal a challenging problem.
12. An empirical equation was developed that allows for the prediction of N02
removal over extended periods of time. MgO utilization rates are far below stoichiometrically
predicted values, most probably the result of some combination of lost surface area due to
pore blockage or reduced surface area due to coverage of available reactant by a higher-
molar-volume product, and an insufficient concentration-gradient driving force for continued
Recommendations for Further Research
Based upon the conclusions presented above and the experiences gained during the
conduct of this experimental study, a number of recommendations for further research in the
area have become evident:
1. The oxidation of NO to N02 is critical to the effective employment of this
sorbent medium in the control of total NOx. Options for the accomplishment of this oxidation
should be investigated. This oxidation could be accomplished prior to entering the bed or
within the bed, although residence times there may be too short. Contact with oxidizing
agents like peroxide solutions, for example, may be a starting point. In practicality, oxygen
Air Flow (mL/min)
Omega Data I Lab Calibration
Figure 3-2. Example low-flow-rate rotameter calibration curves (Omega N042-15ST Tube).
CONCLUSIONS AND RECOMMENDATIONS
The gassolid reactions between N02 and NO and MgO-vermicuite sorbent were
studied using a bench-scale packed-bed reactor and simulated operating conditions
representative of jet engine test cells. The effects of primary variables including gas-phase
concentrations, reaction temperature, moisture, and gas velocity were evaluated. The design
of the packed-bed reactor allowed for the collection of gas samples from various points within
the bed, which is an improvement over the common use of inlet and outlet measurements in
the determination of intrinsic chemical kinetic parameters in packed-bed studies. First-order
rate coefficients were determined for use in the determination of activation energies
associated with this reaction using the Arrhenius relationship. Sorption behavior over time
was interpreted using the shrinking unreacted-core model, as well as an empirical model,
which described the chemical and physical processes occurring during the course of the
reaction. It should be emphasized that the conclusions reached from this research study are
specific to the sorbent studied and the operating conditions used. Based upon the results of
the experiments conducted and the interpretation of data collected during the course of this
study, the following conclusions can be drawn:
Cum Mass NO 2 Removed (mg)
Figure 4-36. Cumulative mass N02 removed
collected from center of bed).
I NOx Analyzer Data
versus bed exposure time ([NO2]in=50
ppm, T=423 K, [O2]=0%, Gas samples
Davini (1988) studied the reduction of nitrogen oxide with ammonia in the presence of
carbonaceous soots from industrial boilers. Lee and Kline [U.S. Patent 3,864,451 (1975)]
describe a method for removing NO in the presence of sulfur dioxide by mixing ammonia with
the flue gas in the presence of a catalyst selected from the group of platinum and transition
metals and oxides and mixtures of these. Andersen and Keith [U.S. Patent 3,008,796 (1961)]
have described the use of NH3 in combination with cobalt, nickel, or iron supported on
alumina, silica, silica gel, or diatomaceous earth. Lyon (1987) describes an improved method
using ammonium injection in a tightly controlled noncatalytic process. A problem with this
method is the formation of ammonium salt particulate matter. Other patents relating to the
use of ammonia and precious metal or other catalysts for the removal of oxides of nitrogen
from a waste or tail gas include those of Cohn, Steele, and Andersen [U.S. Patent 2,975,025
(1961)] and Keith and Kenah [U.S. Patents 3,245,920 (1966); and 3,328,155 (1967)] (Nelson
et al., 1989).
Control of nitrogen oxides is also attainable by several processes that do not utilize
methane or ammonia, because the latter may be difficult to control. Additionally, the desired
ammonia reaction occurs only within a narrow range of temperatures. One process that
received great attention was the "RAPRENOx" selective reduction reaction first developed
by Perry and Siebers (1986). In this process, cyanuric acid (non-toxic) is mixed with Ma
intaining exhaust gases from which the NOx concentration (as NO) is significantly reduced
(NTIS Tech Notes, 1987). Heap et al. (1988) combined this technology with combustion
modification techniques to further improve the reduction of NOx. Unfortunately, it appears
that this reaction is negatively affected by the presence of free oxygen (Wicke et al., 1989).
Before integrating equation 4-23, one of the variables must be eliminated. As in gas-film
diffusion, Na can be eliminated by writing it in terms of rc. Substituting again from equation
4-6, and rearranging produces an integrable form:
- apB /r'(- Wcdre bDt[A] f dt (4-24)
Jr.-R r R Jo
Defining rd as the time to complete conversion (r= 0) of the solid particle under product-
This leads to an expression for the progress of the reaction in terms of rd\
= 1 3(f 2()3
x, R R
This may also be expressed in terms of fractional solid conversion from equation 4-11:
p(X) = 1 3(1-Z)m + 2(1-X)
(JETCs) is regulated for soot opacity, JETCs currently operate under implicit exemption from
NOx regulations, although they qualify as stationary sources. If jet engine testing operations
are conducted in an ozone non-attainment area or where photochemical smog is already a
significant problem, they become obvious targets for environmental regulation. Mobile
sources are regulated under Title II of the Clean Air Act Amendments of 1990. Part B of
these amendments addresses aircraft emission standards. A jet engine in a test cell could be
considered to be a stationary source under Title I, and may be included for regulation under
Title IV, Acid Deposition Control (Quarles and Lewis, 1990). In anticipation of these
possibilities, the Administrator of the EPA and the Secretary of Transportation, in concert
with the Secretary of Defense, have commissioned an investigation into the implications of
regulating jet engine test cells. Some of the issues studied included the impacts of not
controlling nitrogen oxides, the existence of appropriate control technologies, costs
associated with these technologies and their effects on safety, design, structure, and operation
or performance of aircraft engines and performance tests in test cells (EPA-453/R-94-068).
After the recommendations of this study are evaluated, NOx emission standards for jet engine
test cells may be promulgated and enforced in the near future. A review of the most common
NOx control methods for stationary sources is useful for the consideration of their
applicability to JETC exhaust control.
An expression for the decrease in the radius of the shrinking core or the increase in fractional
conversion of the solid particle surface then follows, including a substitution from equation
*(*)' 7'1 R '1 (4-18)
A linear plot of the right-hand side of the equation versus bed exposure time would allow for
the prediction of rr, and identify chemical-reaction kinetics as the rate-controlling process.
This analysis is somewhat more complicated since it requires a two-step process, first
considering diffusion flux in a partially reacted particle, then letting the size of the unreacted
core change with time. From Figure 4-30, both reactant A and the unreacted core radius
move inward with time; however, the unreacted core shrinkage is slower than the flow rate
of A toward the unreacted core by approximately three orders of magnitude (the order of the
ratio of solid density to gas density), so a steady-state assumption regarding the dimension
of the unreacted core is valid. This assumption greatly simplifies the mathematics, because
it can now be assumed that the rate of reaction of A is equal to its rate of diffusion to the
surface of the unreacted core:
- = 4tir2QA = A%R 2Q^ = 4tir^QAC = Constant
associated resistance to reaction or is simply a result of cumulative experimental error. Since
the rate of reaction becomes very slow toward the end of the run, small errors in the
determination of rate constants would become exaggerated in this range. It is also possible
that there is more than one process controlling the reaction, or multiple reactions could be
simultaneously taking place, obscuring the apparent activation energies measured.
Effects of Water
Water vapor carried by humidified gases greatly improved N02 removal efficiency and
overall sorption capacity. It is possible that this effect is due to the conversion of MgO into
the more-reactive Mg(OH)2, which is thermally stable over the range of temperatures
evaluated. Additionally, since N02 is somewhat soluble in water, a small quantity may be
removed in this way. This may cause the formation of nitrous and/or nitric acids, which are
probably more reactive than N02 and should be immediately neutralized by the basic sorbent,
preventing any potential for corrosion problems.
Intrinsic first-order rate coefficients (and N02 removal rates) for these experiments
were generally comparable in the early stages of reaction, however, N02 removal efficiency
remained higher for an extended period of time when water was present in the system. Figure
4-23 is a typical example of an N02 concentration versus bed exposure time profile utilizing
moistened sorbent. The possible reasons for this effect include the increased reactivity of
Mg(OH)2 compared to MgO, the solubility of N02 in water, and the lower molar volume ratio
of Mg(N03)2 to Mg(OH)2 compared to the molar volume ratio of Mg(N03)2 to MgO. N02
solubility was avoided in experiments where the sorbent was wetted prior to exposure to
flowing gases to convert the MgO on the surface into Mg(OH)2, leaving little free water.
concentration versus bed residence time curves could be plotted. Values for the same bed
exposure time were used to plot concentration of interest versus residence time, which was
a function of sampling point location and, thus, reaction time.
Limitation of Gas Film Mass Transfer Resistance
In the conduct of intrinsic chemical kinetic studies of gassolid reactions in packed-
bed reactor systems, it is critical that gas film mass transfer resistance to reaction be
minimized. The following description of the limitation of this resistance is based upon the
work of Fogler (1992) and Szekely et al. (1976). The mass flux from a fluid to a solid
surface is the product of a mass transfer coefficient and the concentration driving force.
When gas film mass transfer is rate-limiting, the extent of reaction or fractional solid
conversion is linear with respect to time. In a packed-bed system, the concentration driving
force is the difference between reactant concentration at the void space at a point in the bed
and the concentration at the surface of the sorbent particle adjacent to this point. Gas film
mass transfer resistance can generally be minimized by using small sorbent particles and high
superficial gas velocities. At low velocities, the stagnant gas film boundary layer thickness
is large at high velocities this thickness is decreased, reducing the mass transfer limitation
through increased convective mass transfer.
Operating at lower reaction temperatures also helps to reduce gas film mass transfer
limitations. When a reaction is gas film mass transfer limited, it will generally be insensitive
to increases in temperature. Since gas film mass transfer is not an activated process, while
Modifications to Operating Conditions
Several modifications to stationary and mobile source operating conditions have been
developed that can be used to reduce NOx formation from combustion. These include 1) low-
excess-air firing; 2) off-stoichiometric combustion; 3) flue gas recirculation; 4) reduced air
preheat; 5) reduced firing rates; and 6) water injection. Excess air is the amount of air that
is in excess of the amount stoichiometrically required for 100 percent combustion of the fuel.
Due to imperfect mixing of air and fuel in the combustion zone, there must be some excess
air present at all times to reduce fuel waste and to prevent smoke formation. As excess air
decreases, NOx follows, while using less fuel. Off-stoichiometric combustion (also called
staged-combustion) burns the fuel in two or more steps. The initial flame zone is fuel-rich,
and the following zone(s) is (are) fuel-lean. Combustion with remaining air in the resulting
fuel-rich regions in the primary flame zone are controlled by heat transfer. Although the
overall air/fuel ratio is near stoichiometric, the primary NOx formation zone of the flame is
operated in a low-NOx condition.
Rerouting some of the flue gas back to the burner primary combustion zone is called
flue gas recirculation. This process not only reduces the peak flame temperature, but also
lowers the partial pressure of available oxygen at the burner, thereby decreasing NOx
formation. Reducing the amount of combustion-air preheat lowers the peak temperature in
the primary combustion zone, decreasing thermal NOx production. Since JETCs operate
using ambient air as combustion air, this technique is obviously not applicable to these
operations. Likewise, reduced firing rates to reduce heat release per unit volume cannot be
1. NO is not readily removed by MgOvermiculite. Any removal probably
occurs through limited physisorption and/or conversion into nitrogen dioxide by oxygen
present in the augmented exhaust gas. The oxidation of NO to N02 is crucial to the
successful employment of this medium.
2. Nitrogen dioxide removal efficiencies greatly exceed nitric oxide removal
efficiencies, with maximum values greater than 90 percent. N02 continues to be removed by
the sorbent at a greatly reduced rate for extended periods of time.
3. High concentrations of N02 were readily removed from the gas stream, rapidly
converting MgO into Mg(N03)2. The formation of a solid product layer slowed the reaction
down as it progressed from control by chemical-reaction kinetics to diffusion control, a much
slower process. The higher concentration gradients provided the larger driving forces for the
continued removal of N02 through diffusion.
4. The reaction between N02 and MgOvermiculite is first-order with respect
to N02. The temperature dependence of the first-order rate coefficients is evidence that data
were collected in the region of chemical reaction control. Activation energies associated with
this reaction were in the range from approximately 20 to 36 kJ/g-mol in the absence of
oxygen and 15 to 25 kJ/g-mol when oxygen was present in the system. These values are
indicative of a low-energy chemisorption process.
5. Wetted sorbent or humidified gases promote N02 removal, possibly by the
conversion of MgO into Mg(OH)2, which appears to be more reactive and is thermally stable
over the range of temperatures studied. Since the molar volume ratio of magnesium nitrate
to magnesium hydroxide is lower than when compared to MgO, there is less potential for
It is also possible that the transformed surface catalyzes the continued oxidation (or
reduction) of N02. A more descriptive discussion of sorbent lifetime within the context of
the shrinking unreacted core model will be presented later.
Beds regenerated through heating to approximately 550 K can be reused with little
loss of performance. Obviously, regenerating solely through heating serves to release NOx
from the solid surface into the gas phase. This might defeat the purpose of using the sorbent
to control NOx. Introduction of a reducing gas (CO appears to be the reductant of choice)
when regenerating the sorbent can alleviate this problem (Nelson et al., 1990).
Proposed Reaction Mechanism
While the exact reaction mechanism in this gas-phase interaction is unknown, the
experimental data provide information that may be used to describe a possible mechanism.
While the NQ2 removal greatly exceeded NO removal, some NO was removed initially,
presumably via a physisorption mechanism, as previously discussed. The finding of NO
production during N02 sorption led to an investigation of possible reaction mechanisms that
would ultimately produce NO. A stepwise mechanism was envisioned, in which N02
molecules are sequentially incorporated into intermediate products, ultimately forming
A simplified mechanism is proposed as follows:
1) N02 + MgO MgN03
2) N02 + MgN03 MgN2Q5
It has been determined that various alkali metal oxides and silicate materials can reduce
nitrogen oxides without additional methane or ammonia. Harris, Morello, and Peters [U.S.
Patent 3,459,494 (1969)] have successfully evaluated CaO, SrO, BaO, K20, Na20 and others
supported on Alundum cement, porcelain, silica, extended alumina, or alumina beads. Heavy-
metal catalysts (copper, silver, nickel, molybdenum, palladium, and cobalt), supported on
alumina were patented by Ryason [U.S. Patent 3,454,355 (1969)]. The catalytic properties
of copper for the reduction of NOx without added methane or ammonia are described by
various investigators, including Gehri and Frevel [U.S. Patent 3,718,733 (1973)] and Kressley
[U.S. Patent 3,682,585 (1972)]. Kranc and Lutchko [U.S. Patent 3,576,596 (1971)]
employed a combination of copper and chromium impregnated on carbon supports to remove
both NO and CO from a waste gas.
Many problems associated with catalytic control methods often make the use of
non-catalytic methods more appealing. The most common problems with catalytic techniques
include catalyst fouling or poisoning, and a narrow range of operating temperatures. These
problems can be avoided by using non-catalytic controls. A number of dry sorption
techniques that do not employ catalysts have also been evaluated as they apply to the control
of nitrogen oxides. Ganz (1958) evaluated activated carbon, aluminosilicate, silica gel,
manganese dioxide, copper dioxide, and coke for the removal of high concentrations of N02
and found aluminosilicate to be the most suitable sorbent. Kyollen [U.S. Patent 3,498,743
(1970)] described a process employing either sodium carbonate, calcium carbonate, or
I 5 min
Bed Exposure Time
Figure 4-5. N02 removal versus residence time (T=473 K, =9.9%).
features in the local area. At an emission source, the concentration of nitrogen oxides is much
higher than ambient background levels. Emission rates vary widely depending on the type of
source and type of fiiel used, as well as on the type and quality of pollution control equipment
employed. This variation in NOx production rates for uncontrolled sources is quite evident
in Table 1-2.
From Table 1-2, it can be seen that an individual aircraft appears to emit negligible
amounts of nitrogen oxides when compared to much larger combustion sources. However,
recent studies by Johnson et al. (1992) indicate that aircraft emissions into the troposphere
at an altitude above 10 km produce increased concentrations of ozone, off-setting ozone
depletion, but contributing to increased surface temperatures ("global warming"). Modeling
suggests that the radiative forcing of surface temperature is about 30 times more sensitive to
aircraft emissions of nitrogen oxides than surface emissions. In the vicinity of an airport or
Air Force base, where ground operations (taxiing, take-offs, landings, and maintenance in
engine test cells) are combined with flight operations for a large number of aircraft, the
contribution of pollutants in the local area due to nitrogen oxides can be significant. NOx
standards have traditionally not been enforced for jet engine test cells, which qualify for
regulation as stationary sources. Gas turbine engines operating as mobile sources also have
not been regulated in the past. Evolving regulations including the 1990 Clean Air Act
Amendments, the failure of existing controls on stationary industrial processes to significantly
lower urban ozone concentrations, and a demonstrated correlation between ozone levels and
on the particles are a function of particle surface area. The MgO particle surface median
diameter can be calculated from the log-probability distribution using the well-known Hatch-
Choate equations (Hinds, 1982). A calculated count median diameter of approximately 0.1
pm led to the determination of a value of approximately 0.6 pm for the surface median
diameter using these equations.
NO.. Removal by MgfNO,V,-coated Vermiculite
Results for Mg(N03)2-coated vermiculite were similar to those for the plain heat-
treated vermiculite. Removals of N02 were less than five percent over the range of
temperatures (373 to 473 K) and concentrations (20 to 200 ppm) evaluated. NO removal
efficiencies were much lower, and approached zero. The results of these tests were useful in
verifying that if magnesium nitrate is formed on the solid surface during the course of the
MgO (Mg(OH)2) reaction with N02, and all the remaining MgO (or Mg(OH)2) is utilized or
is otherwise unavailable for reaction, then these results preclude the further removal of NOx
from the gases supplied to the bed, and reaction/removal should cease.
NO.. Removal by Sorbent Material
It was found to be more difficult to remove NO than N02 by reaction with MgO, the
former being generally less reactive than the latter. The removal of each species was
independently affected by the experimental variables evaluated. Specific results are described
in the following paragraphs.
Sorbtech-Supplied Sample Results
Experimental results for samples of sorbent provided by Sorbtech were generally
comparable to those for laboratory-prepared sorbent. Initial removal rates were greater than
99% for all cases evaluated; however, N02 penetration remained lower at the end of the run
for these samples. Intrinsic first-order rate constants were approximately the same early in
the reaction, but the decrease with extended bed exposure time was not as great. As
discussed earlier, the Sorbtech samples actually showed lower average BET surface areas
than the laboratory prepared sorbent. This difference in available surface area would
generally indicate less activity for the Sorbtech samples in the removal of N02, which
apparently was not the case. It may be that the laboratory-prepared sorbent had higher
porosity, which would contribute to a higher total surface area. The physical appearance of
the Sorbtech sorbent was darker, with a more brown to tan color than the cleaner white
appearance of the laboratory-prepared sorbent.
One distinct difference between the samples was that the Sorbtech sorbent was
significantly more dense than the laboratory prepared sorbent, a bed volume of the Sorbtech
sorbent weighed approximately 40% more than the laboratory sorbent. It was thought that
the higher mass might be the result of the presence of water in the Sorbtech sorbent, which
would also help to explain the improved N02 removal efficiency with time. Preweighed
samples of both sorbents were heated in a muffle furnace to a temperature of 623 K for one
hour to evaluate weight loss from dehydration. This proved to be insignificant, with the
T=373K T=423K -a- T=473K
Figure 4-20. N02 penetration versus bed exposure time ([NO2]in=20 ppm, [O2]=10%).
I am extremely grateful for the support of my doctoral committee chairman, Dr. Eric
R. Allen, for his wealth of knowledge in academic research, for sharing in the excitement of
discovery, as well as for providing encouragement when problems arose. I will always fondly
remember our enlightening discussions about my research, as well as life in general, as high
points in my research. I also appreciate the sage advice of Dr. Dale A. Lundgren, whose
practical and applied approach to engineering goes a long way beyond what can be learned
in a textbook. I am thankful to both professors and to my fellow air pollution graduate
students, for their friendship and comradery during my time as a graduate student at UF.
Special thanks to Dr. Joseph D. Wander, whose belief in the value of academic
research is unparalleled, for providing the idea for this project, as well as for his help,
friendship and advice all along the way. I am also thankful to Dr. W. Emmett Bolch, Jr.,
whose letter years ago convinced me to come to the University of Florida, and to Dr. Robert
J. Hanrahan, to whom I credit the excellent performance of the experimental system.
I would like to acknowledge Colonel Robert A. Capell, USAF, BSC, who saw the
need for a bioenvironmental engineer with a Ph.D. in air pollution. Finally, I would like to
thank the Armstrong Laboratory/OL-EQS, Tyndall AFB, Florida for providing funding for
this research project, and the U.S. Air Force and the Air Force Institute of Technology, for
their confidence in selecting me for advanced education and for the financial support.
N02 Penetration (Fraction)
0 10 20 30 40 50 60
Bed Exposure Time (min)
100ppm ~13 50ppm x_ 20ppm
Figure 4-13. N02 penetration vs bed exposure time (T=373 K, [O2]=10%).
Residence time (sec)
1 hour 1 1.5 hours 2 hours
Figure 4-4. NO removal by humidified MgOvermiculite sorbent ([NO]in=210 ppm, T=423 K, =11%, 3% H20 vapor).
I [N02] [NO]
Figure 4-49. Comparative bed N02 and NO concentrations versus bed exposure time during long-term run showing NO
production ([NO2]in=170 ppm, T=473 K, [O2]=0%, Gas samples collected from middle of bed)).
2. Evaluate saturation characteristics (lifetime) of the material. Develop a model
to predict sorbent performance with time.
3. Evaluate the desorption and regeneration efficiencies of NOx on
4. Evaluate the pressure-drop characteristics of the material over time as gas
N02 Penetration (Fraction)
+- T=373K T=423K -b- T=473K
Figure 4-16. N02 penetration versus bed exposure time ([NO2]in=50 ppm, [O2]=0%).
HETEROGENEOUS-PHASE REACTIONS OF NITROGEN DIOXIDE WITH
VERM3CULITE-SUPPORTED MAGNESIUM OXIDE
LARRY THOMAS KIMM
A DISSERTATION PRESENTED TO THE GRADUATE SCHOOL
OF THE UNIVERSITY OF FLORIDA IN PARTIAL FULFILLMENT
OF THE REQUIREMENTS FOR THE DEGREE OF
DOCTOR OF PHILOSOPHY
UNIVERSITY OF FLORIDA
resistance to diffusion. A mathematically simple model, that was developed by Yagi and
Kunii in 1955, is often used to describe non-catalytic gas-solid reactions. This model, often
called the shrinking unreacted-core model, is based upon the visualization that the reaction
occurs first at the outer surface of an idealized spherical reactant particle (Yagi and Kunii,
1961). As reaction progresses, the reaction front (or zone) moves radially into the solid,
often leaving behind completely converted material in the form of an inert solid product called
"ash." A graphical representation of this model is shown in Figure 2-2.
The reaction steps in this model are the same as those previously described for a
generalized non-catalytic gas-solid reaction, occurring sequentially, although in any given
reaction, some steps may not occur. Effective diffusivity of the adsorbate through the solid
product is assumed to be a constant. Various equations relating the radial position of the
reaction zone (a measure of solid conversion) with reaction time have been developed. These
equations will be described in following sections before they are applied to the present study.
Although originally developed for application to non-porous solid reactants, the model has
been successfully used to describe systems utilizing porous solid sorbents. The main physical
difference between the two situations is that the reaction zone is diffuse in a porous solid as
opposed to a sharp interface in a non-porous one. A variable-diffiisivity shrinking-core-model
was developed by Krishnan and Sotirchos (1993 a). Their analysis revealed the strong effects
of reaction temperature, gas-phase concentration, and product layer thickness on effective
diffusivity of the reactant gas through the solid reactant and "inert" product layer matrix.
formation of N02 is favored at low temperatures, but N02 dissociates back to NO at higher
temperatures. The rate of equilibrium NO formation increases rapidly with increasing
temperature. As the combustion zone temperature rises above 1000 K, the formation of N02
becomes less likely under equilibrium conditions. Kinetically, however, the NO formation
reaction is a slow one, which affects the availability of reactant to form N02. NO formation
by reaction (1-1) has a very high activation energy (317 kilojoules/mole) and is most likely
the rate-controlling reaction (Ismagilov et al., 1990).
It has been observed experimentally that NO concentrations in the combustion flame
zone are significantly higher than those predicted by the Zeldovich mechanism. This "prompt"
NO formation is attributed to super-equilibrium radical concentrations that are likely in
hydrocarbon flames. It has been suggested that the intermediate, HCN, is formed when N2
reacts with a hydrocarbon radical. HCN combines with OH to form CN, and then CN is
oxidized to NO. Based upon experimental data, MacKinnon (1974) developed a model that
predicts the concentration of NO formed during combustion as a function of temperature, N2
and 02 concentrations, and time. At a total pressure of one atmosphere, the model equation
CNO 5.2 x 1017 (exp -72000/T) YN2(YG2)1/21 (1-8)
where: CNO = NO concentration (ppm),
T = absolute temperature (K),
YÂ¡ = mole fraction of component i,
and t = time (seconds).
The flux of A within the inert layer is expressed by Fick's law for equimolar
counterdifliision: (Note that 0A is positive.)
Qa D^-1 (4-20)
where De represents the effective diffusion coefficient of the gaseous reactant through the
product layer (cm2/s). Owing to variations in the properties of the inert layer, the value of
this coefficient is difficult to estimate and is generally determined experimentally. The
effective diffusion coefficient can be obtained by adjusting De in the shrinking unreacted-core
or grain model until the model predictions fit experimental data (Marsh and Ulrichson, 1985).
Equations 4-19 and 4-20 may be combined:
. 4=Z> m. C <4-2
dt e dt
Integrating through the inert layer :
- f' = 4rcD f[AV d[A] (422>
dt Jr r2 e J[A]g4A]s
(- h 4nDJAl
For a shrinking unreacted-core of given size, dN/dt is constant, but the inert layer
becomes thicker as the core shrinks, which decreases the diffusion rate of A through the layer.
subsequent product layer divisional limitation of reaction rate) may further improve the utility
of the model to describing reaction mechanism(s).
It is appropriate now to examine the equations for the three potential rate-limiting
resistances affecting heterogeneous gas-solid reactions. The detailed derivations can be
found in most standard texts on gas-solid reactions. The following is based on the
descriptions reported by Szekely et al. (1976) and Levenspiel (1972). Using the generalized
gas-solid reaction represented by equation (2-1)
aA (gas) + bB (solid) cC (solid) + dD (gas)
to identify the only process acting, we can describe the rate of reaction with respect to
conversion of the solid reactant for three idealized or limiting resistance situations: diffusion-
through-gas-film control, chemical-reaction control, and diffiision-through-inert-product-layer
Whenever the stagnant gas film layer surrounding the sorbent particle produces
significant mass transfer resistance to reaction, the gas-phase concentration profile for
reactant A is as shown in Figure 4-28. From the figure, it is evident that no gaseous reactant
is present at the solid surface, therefore, the concentration driving force [the quantity ([A]&1S
- [A]^ = ([A]g [A]J] is a constant, having the value [A]g. It is convenient to derive kinetic
expressions for gassolid reactions based on the external surface area of the sorbent particle,
S = 4kR2. From equation 2-1, we know that a(dNB) = b(dNA), where NA and NB represent
the number of moles of the reactants. Therefore, we can write
The smallest unit of a gas-solid system can be represented by the interaction between
a single solid particle and a flowing gas stream. This representation is convenient and simple,
and, in principle, may be generalized to more complex multi-particle systems, such as packed
beds. These interactions can be catalytic, in which the solid functions as a catalyst -- often
in the facilitation of a gas-phase reaction or non-catalytic, in which the surface acts to
physically or chemically remove reactants from the gas phase.
Adsorption occurs with a decrease in surface free energy and normally a decrease in
entropy; as a result, it is generally an exothermic process. In physical adsorption, sorbed
species are attracted and held at the solid surface by van der Waals dispersion forces. These
forces are much weaker than chemical bonding forces; the heat evolved is small, generally
between 1 and 10 kcal/g-mole (4-40 kJ/g-mole), approximately the heat of vapor
condensation for relatively non-polar substances. Chemisorption is primarily responsible for
gassolid reactions and catalysis on solid surfaces. In chemisorption, the forces involved are
of the same order of magnitude as those for chemical bonding, and the heat of chemisorption
is often between 10 and 150 kcal/g-mole (40-600 kJ/g-mole). The process of physical
adsorption, like condensation, has very little or no activation energy and as a result is assumed
to occur rapidly. Chemisorption often displays a higher activation energy, implying a slow
rate; however, chemisorption reactions having small activation energies are known. Unlike
physisorption, chemisorption is specific to the gases and solids involved, just like chemical
Bed Exposure Time (min)
1 3.05 alpm 6.06 alpm 29.49 alpm
Figure 4-1. Gas film mass-transfer resistance evaluation N02 penetration (C^/C^) versus bed exposure time ([NO]in=200 ppm,
T=473 K, [O2]=0%).
When product-layer diffusion is rate-controlling, a plot of the right-hand-side of equation 4-
28 versus bed exposure time allows for the determination of rd.
Derivations of the Shrinking Unreacted-Core Model
As reaction proceeds and a product layer is formed, the decreasing product layer
diffusion rate can affect the overall rate. Equation 4-19 assumes a constant value of De,
which may not be a valid assumption. Variation of the (decreasing) diffusion coefficient in
the product layer may have to be taken into account to describe a reaction in which a more
voluminous solid product forms (Krishnan and Sotirchos, 1993). More-elaborate models can
be constructed allowing for changes in the controlling mechanism with time or solid-surface
conversion. Often, a simple modification to the basic equations allows for an improved
representation of the experimental data. When product-layer-diffusion is truly the rate-
limiting process, the inclusion of the molar volume ratio (represented by Z) in equation 4-28,
as follows, may improve the fit (Szekely et al., 1976):
J_ 3[Z (Z + (1 Z)(l X))]2* 3(1 ^y/3 (4-29)
This is especially true when the product layer molar volume is significantly larger (or
smaller) than that of the solid reactant. Referring back to Table 2-1, four molar volume ratios
are of interest in this research:
The experimental arrangement for sorption and desorption/regeneration employed in
this study is shown in Figure 3-1. Nitrogen oxides (mixed in N2) were supplied from separate
certified standard cylinders (Bi-Tec Southeast, Inc., Tampa, Florida) to ensure reliability of
concentrations and to minimize contaminant concentrations. Initially, N02 mixtures were
generated using a NOx generator (Model 100, Thermo Environmental Instruments, Franklin,
Massachusetts) as a source of N02. This generator produces N02 by mixing ozone generated
from UV irradiation of air with NO. While the system could easily and efficiently convert
high concentrations of NO to N02, two major problems resulted from its use. First, it is
extremely difficult to perfectly titrate ozone with NO using this system, without leaving
excess ozone. The flow controls in the unit are insufficient for this purpose. A related but
more important variation was the ultraviolet lamp output used to generate ozone appeared
to vary from one test to the next for a given voltage setting. The presence of ozone was
unwanted in the experimental study since it could complicate data interpretation by oxidizing
NOx to other species not readily measurable with the instrumentation used.
As a result, it was necessary to use standard cylinder gas as an N02 source. Since this
is actually N204 under pressure, there is a small potential for the gas to decay with time.
While total NOx was the same as certified, some NO "contamination" is generally present in
the cylinder gas. The NO contamination in the N02 cylinders was always less than two to five
percent. Similar impurity values were noted in the NO/NO ratio in the NO cylinders. This
This work is dedicated to my family, especially my wife, Lisa, whose patience, love
and support during this effort made it all possible, and to my children, Meredyth and Wilson,
who always give me the best welcome home after a long day.
called "N0X." Some of the physical properties associated with gaseous nitrogen oxides
(NxOy) are shown in Table 1-1. Nitrous oxide (N20) is another oxide of nitrogen that is also
present in the atmosphere at appreciable concentrations. Nitrous oxide is a gas with
recognized anesthetic properties, which has also been suggested to be a product of
combustion. Its ambient concentration is approximately 0.5 parts per million (ppm), well
below the threshold concentration for biological effects. Fortunately, in the troposphere, it
is balanced atmospherically by a cycle that is independent of the other oxides of nitrogen.
Nitric oxide (NO) is a colorless gas whose ambient concentration is normally well below 0.5
ppm. At this concentration it produces minimal effects on human health. However, nitric
oxide is a precursor to the formation of N02 and is an active compound in the formation of
photochemical smog, initiating reactions that produce secondary air pollutants.
Table 1-1. Physical properties of nitrogen oxides (NxOy).
See Note 1
See Note 2
See Note 2
NOTES: 1. Reacts with H20 forming H0N02 and/or HONO
2. Liquid and solid forms are primarily N204
Sources: Nealetal., 1981.; Lange's Handbook of Chemistry, 1973.
Solid Sorbent Characterizations
Surface Area Analyses
Five samples of the composite batch of MgO-coated vermiculite were randomly
selected for BET-specific surface area analyses. The intent was to look at the variability in
surface area between smaller batches of material prepared in the laboratory. If the variation
between samples is small enough, the mean surface area and sample standard deviation can
be used to establish confidence limits for sorbent sample surface area. Results are shown in
Table 4-1. BET surface areas of selected samples of laboratory prepared
BET Surface Area (m2/g)
41.92 + 0.19
36.08 + 0.15
37.93 + 0.11
39.20 + 0.17
42.10 + 0.17
Sample Standard Deviation
Stagnant Gas Film
Figure 4-29. Graphical representation of the shrinking unreacted-core model under chemical-reaction control.
the toxicity of these heavy metals is a detriment. The seventh study, which was selected for
development, involved vermiculite and magnesium oxide (MgO)-coated vermiculite. NOx
removal rates for this medium were appealing, and the technology has many other advantages
including economics, simplicity, regenerability, and particularly, insensitivity to changes in
exhaust gas conditions or composition (Nelson et al., 1989). The USAF has sponsored
numerous studies in order to quantify emissions from jet engines. Seitchek (1985), Fagin
(1988), and Spicer et al. (1990) have published jet engine emission values for many engines
in the USAF-inventory operating on JP-4 jet fuel. Similar studies are underway for emissions
associated with the combustion of JP-8 fuels. These documents describe NOx and other
combustion by-product emission rates correlated with power setting or operational
procedures. They are very useful for determining appropriate exhaust gas concentrations in
order to simulate jet engine exhaust gas composition in the laboratory. Many lab-scale studies
have used these data in their experimental design.
Vermiculite ((Mg,Fe(n),Al)3(Al,Si)4O10(OH)2-4H2O, a thermally expanded form of a
common aluminosilicate material) has been used as a carrier for other materials including
nitrates and phosphates, in which the combinations are used as slow-release fertilizers.
Evanshen [U.S. Patent 3,757,489 (1973)] describes the treatment of flue gases with
polyvinylpyrrolidone with or without the addition of a catalyst of a nitrate or sulfate of copper
or silver. He suggested suspending these materials on a carrier such as vermiculite. Sanitech,
Inc., (now Sorbent Technologies Corporation, Twinsburg, Ohio) developed a new class of
+ Experimental Predicted
Figure 4-43. Experimental versus predicted N02 concentration ([N02]in=19.1 ppm, T=373 K, [O2]=0%, Gas samples collected
from middle of bed).
laboratory samples losing approximately two percent mass, and the Sorbtech samples losing
about three percent. The higher density material did not produce a higher surface area on a
per bed basis, because there was little difference between the surface areas of laboratory-
prepared samples and Sorbtech samples. In fact, laboratory prepared samples had, on
average, 10% more surface area, which may be attributable to more microporosity, and may
help in explaining the decreased performance since the high-surface-area micropores are
more prone to blockage or plugging as reaction progresses and the nature of the sorbent
Pressure Drop Characteristics
The arrangement of particles in packed beds produces a complex geometry that makes
the flow field difficult to define. For most practical problems, empirical relationships between
pressure drop and the flow rate and characteristics of the fluid are used. When an empirical
equation can be validated with experimental data, this is the best situation. Of numerous
correlations proposed for relating pressure drop to flow rate, the Ergun equation is most
widely accepted (Szekely et al., 1976):
c3 cp d
^ s p
presence of water are truly the result of the Mg(OH)2 formed and the change in molar
volume ratio, or are a result of an absorption process.
8. Studies similar to those reported here should be conducted using S02 as the
adsorbate gas as it is also effectively removed by this sorbent. The basic kinetic and
mechanistic data on the reaction between S02 and MgO have not yet been reported. The
simultaneous exposure of the sorbent to S02 and NOx should also be evaluated since there
is a reported synergistic effect on the combined removal when the two species are present
together. The presence of S02 may also help in the removal of NO by its reduction to
nitrogen. Steciak et al. (1995) reported that the reaction: MgO + S02 + NO MgS04 + !4N2
is thermodynamically feasible below 1030 C, but no kinetic data have been reported. An
important point to be stressed here is that there are many other potential uses for this sorbent
that could be investigated.
9. The use of high-purity N02 from a permeation tube apparatus would avoid the
problem of NO contamination in bed feed gas. This would allow for an improved evaluation
of the NO formation seen during the course of reaction in this research. If there were no NO
present in the samples that entered the bed, formation by chemical reaction on the sorbent
surface would be easier to follow.
10. The application of this sorbent medium to ambient N02 sampling should be
investigated. Since low concentrations of N02 can be effectively removed using this sorbent
it may be feasible to attempt to collect low-level concentrations of N02 from urban
atmospheres for analysis if conditions were optimized.
Goochee, 1988). In general, gas-solid reactions can be described by an ideal Langmuir
isotherm only when there is exclusive and complete monolayer sorption, all active sites on the
sorbent are equivalent and there is no interaction between adjacent adsorbate molecules
(Comes et al., 1993). Solid structural changes resulting from the chemical change in the solid
can be quite complex, but are generally classified as being either sintering (and resultant pore
closure), swelling, softening, and cracking (Szekely et al., 1976). These changes may affect
diffusivities of gaseous reactants as well. A number of mathematical models based upon these
recognized physical and chemical phenomenon have been developed and described in the
This model is a simplified, idealized model for the non-catalytic reaction of particles
with a surrounding fluid. A basic assumption of this model is that the reactant gas enters and
reacts throughout the particle at all times, although probably at different rates at different
locations within the particle. This model obviously assumes a highly porous particle structure
to allow for easy reactant diffusion with little intraparticle resistance to diffusion. With
negligible diffiisional (or mass transfer) resistance, the overall rate is controlled by chemical
kinetics, which is generally slow in this case.
Shrinking Unreacted-Core Model
Evidence from a wide variety of situations indicates that the progressive-conversion
model does not accurately approximate the behavior of real particles. Often, the reaction
produces an inert product layer of converted solid reactant which can produce significant
Figure 2-3. Schematic representation of the grain model.
Results from a long-term run are presented at Figure 4-43. It appears from this figure
that full "effective" utilization and achievement of dynamic equilibrium occurred closer to 500
minutes than to 250 minutes, indicating that the combination of resistances equation may be
best-suited for describing sorption behavior in this situation. Chemical kinetics may be
partially controlling due to the low N02 concentration and associated limited reactant
availability, and diffusion may be controlling due to the lack of concentration driving force
to promote reaction. The ratio of N02 removed to NO produced was approximately 3:1 after
7 hours exposure time. The total mass of N02 removed at this time was approximately 10
mg, resulting in a very low utilization rate.
200 ppm NO? at a Reaction Temperature of 473 K
The other extreme condition evaluated was the highest N02 concentration at the
highest reaction temperature. The shrinking unreacted-core model was used to fit these data
as well. Figure 4-44 is a comparison of the two primary equations over the course of one
hour. While the product-layer-difiusion-control equation is fairly linear over this entire
period, the chemical-reaction-control equation shows a rapid increase in equation value,
corresponding to a rapid increase in N02 penetration early in the reaction. As expected, the
product-layer-diftusion-control equation seems more appropriate for describing the entire
course of reaction over the first hour. Figures 4-45 and 4-46 depict linear least-squares fits
to the chemical-reaction-control equation and product-layer-diffusion-control equation,
respectively. From these figures, it is evident that statistically, the product-layer-difiusion-
control-equation best represents the data, based upon the statistical parameters evaluated.
Bed Exposure Time (min)
NO Analyzer Data
Figure 4-37. Cumulative mass N02 removed versus bed exposure time for a long-term run ([NO2]in=50 ppm, T=423 K, [O2]=0%,
Gas samples collected from center of bed).
sorbent surface. Figures 4-14 through 4-17 are typical plots, similar to those presented in the
previous sections, in which the effect of reaction temperature can more readily be seen.
These figures depict sorbent performance when oxygen was not present in the system.
Similar plots for those experiments where oxygen was present in the system are shown at
Figures 4-18 through 4-20.
When the N02 inlet concentration was 200 ppm (without oxygen), initial N02
penetration was lowest at a bed reaction temperature of 473 K (Figure 4-14). Penetrations
for the lower temperatures were somewhat higher initially. This separation in penetration
remained until a bed exposure time between 20 and 25 minutes had elapsed, when N02
penetration at 473 K exceeded the values at the other temperatures. If diffusion through the
inert product layer controls the reaction at high conversion levels, an increase in temperature
would increase the diffusion rate since effective diffusivity can be temperature dependent and
improved diffusivity would be expected. This would cause higher reaction rates and overall
conversion levels (Marsh and Ulrichson, 1985). While the initial rate of change in N02
penetration versus time was low, it rapidly increased before beginning to taper off toward the
end of the run. This coincides with a relative increase in N02 penetration rate for the two
lower temperatures evaluated. This delay in increasing N02 penetration most likely represents
the added time required to complete formation of the outermost product layer due to the
decreased temperatures employed.
Similar curves are seen for an N02 inlet concentration of 100 ppm (Figure 4-15). For
inlet N02 concentrations of 20 and 50 ppm (Figures 4-16 and 4-17, respectively), initial
penetrations were low for all temperatures, but it appears that a higher temperature was
application to JETCs is expensive and involved compared to other treatments. At
temperatures from 900 to 1000 C, NH3 will reduce NOx to N2 without a catalyst; however,
NOx reduction efficiencies are only 40-60 percent. If the temperature is too low, unreacted
NH3 will be emitted ("ammonia slip"), and if the temperature is too high, NH3 can be oxidized
to NO. Thus both of these situations are obvious problems. Dry sorption techniques have
the advantage of simplicity of operation and minimization of waste effluent. Relatively high
NOx reduction rates have been documented (Nelson et al., 1989; Lyon, 1991).
enormous. A unique feature of jet engine test cells is their highly variable test cycles (and
NOx production associated with varying peak flame temperature). Because of this variability,
aNOx control technology applicable to jet engine test cells must perform over a wide range
of rapidly varying operating conditions.
Research Sponsored bv the U.S. Air Force (USAF)
The Air Force (through the US AF Engineering and Services Center and USAF Civil
Engineering Support Agency, now the Human Systems Center-Armstrong Laboratory,
Tyndall AFB, Florida) has recently sponsored seven independent projects that specifically
target the control of NOx from JETCs. Johnson and Katz (1989) showed that reburning of
exhaust with extra fuel was effective, but not economical. Ham et al. (1989) reported partial
success with non-catalytic reduction using additives (ammonia, amines, and hydrazines) to
simulated exhaust. Unfortunately, as temperature increased, NOx production increased. A
dual-bed mordenite-copper catalyst did offer some improvement in sensitivity to variable
conditions over some better known selective catalysts (Kittrell, 1991). Berman et al. (1991)
evaluated the photopromotion of NO thermal decomposition by various metallic oxides. This
decomposition was very effective, but only in the absence of oxygen. Initial work reported
by Petrik (1991) also found that NOx reduction by ceramic-supported electrocatalysts was
inhibited by even trace amounts of oxygen; however, continued development of these
materials has produced catalytic ceramics that may be effective inside the jet engine (Gordon,
1994). Lyon (1991) evaluated NOx reduction at the surface of heavier Group Ila oxides, but
Cohn [U.S. Patent 3,118,727 (1964)] has been issued a patent that describes a
process for purifying waste gases containing nitrogen oxides by mixing them with a fuel (such
as CH4) and passing the mixture over a platinum- or rhodium-containing catalyst at an initial
reaction temperature of 690-780 F. Acres and Hutchings [U.S. Patent 3,806,582 (1974)]
describe a similar process. Childers, Ellis, and Ryan [U.S. Patent 2,910,343 (1959)] describe
a methane process involving two catalyst beds in series, one containing platinum or alumina
and the second containing nickel or alumina. Vanadium oxide, molybdenum oxide and/or
tungsten oxide catalysts on alumina or silicic acid substrates were used in combination with
CH4 as described by Nonnenmacher and Kartte [U.S. Patent 3,279,884 (1966)]. Such base
metal catalysts as iron, cobalt, nickel and copper dispersed on a refractory support were used
by Reitmeier [U.S. Patent 2,924,504 (I960)]. Other patents relating to the use of methane
and precious metal catalysts for the removal of NOx from waste or tail gases include those of
Andersen and Green [U.S. Patent 2,970,034 (1961)]; Romeo [U.S. Patent 3,425,803 (1969)];
Newman [U.S. Patent 3,467,492 (1969)]; Kandell and Nemes [U.S. Patent 3,567,367
(1971)]; Andersen, Romeo, and Green [U.S. Patent 3,098,712 (1963)]; and Hardison and
Barr [U.S. Patent 3,402,015 (1968)] (Nelson et al 1989; Lewis, 1975).
The use of ammonia as a reducing gas in the presence of a catalyst was described
earlier. Baiker et al. (1987a, 1987b) and Chen et al. (1990) describe the selective catalytic
reduction of nitric oxide with ammonia upon catalysts comprised of mono- and multi-layers
of vanadia supported on titania, and mono-layers of vanadia immobilized on titania-silica
Table 3-1. USAF FI 10 Turbine Engine Emissions Data (as reported)
Source: Spicer et al., 1990, page 27.
Gas Flow Ratef s')
Gas flow rate(s) were kept constant for each run. However, flow rates/gas velocities
were varied to produce two contact times of 0.5 and 1.0 second, keeping pressure drop to
a minimum. Contact times were calculated by dividing bed length by superficial gas velocity.
This is only an approximation of the true distribution of contact times since the actual gas
velocity may be based upon a more tortuous pathway through the packed bed volume,
increasing or decreasing the contact time of an individual reactant gas molecule. These
superficial velocities correspond to nominal space velocities of 3,600 and 7,200 per hour.
Since mass transfer limitations from the gas phase to the solid surface can obscure
intrinsic chemical kinetics, it is important to limit this resistance to chemical reaction. A
sufficiently high gas velocity will effectively decrease the thickness of the stagnant gas film
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Figure 4-10. N02 penetration vs bed exposure time (T=373 K, [O2]=0%).
recorded by the analyzer. These data were plotted according to the BET model to determine
the total surface area of the sample. Initial screening results were used as an indication of the
best preparation method to use in making the sorbent. Based upon these results, a large
quantity of sorbent was prepared following the procedure already described. Five additional
samples were taken and analyzed using the BET method for precision estimates.
Determination of Sorbent Particle Size
The MgOvermiculite sorbent is inherently a highly heterogeneous material. As a
result, the range of particle sizes in a given sorbent sample can be great. Samples of
MgOvermiculite sorbent were sieved using a standard ASTM sieving apparatus. Cumulative
mass collected at each stage was plotted agaihst particle diameter using a log-probability chart
to determine the mass median particle diameter. This median size was used in all calculations
for which sorbent particle diameter was required to determine flow characteristics through
the packed bed. It was noted that this value may or may not be the most accurate value, since
sieving the sorbent material likely causes a decrease in particle size through mechanical
abrasion. The true size is probably somewhat larger. Data for magnesium oxide powder
particle size was plotted similarly using a manufacturer-provided mass distribution. Once the
MgO powder has been applied to the surface of the vermiculite, any agglomeration would
tend to create larger size particles. It is not known, however, how the application of
Mg(OH)2 slurry affects particle size. Results of these determinations are presented in the
be the most important variable affecting sorption behavior. Chu and Rochelle (1989)
examined the simultaneous removal of S02 and NOx (as NO) by Ca(OH)2 and in some cases
additives, including fly ash, CaS03, and NaOH. These additives improved NOx removal.
Another bench-scale evaluation of the removal of S02 and NO by Ca(OH)2 was conducted
by Jozewicz et al. (1990). NO was not very reactive toward Ca(OH)2 relative to S02, but
adding Mg(OH)2 did improve NO removal somewhat.
SO-,Calcium Carbonate Reaction
Pigford and Sliger (1970) noted the effects of increased product layer difliisional
resistance in the reaction between S02 and CaC03. The overall reaction rate was governed
by both diffusion of S02 through a layer of solid reaction product, progressively formed on
the active solid surface, and diffusion of S02 through pores in the solid. The direct sulfation
of CaC03 was studied by Hajaligol et al. (1988) via thermogravimetric analyses and a bench-
scale fluidized bed setup. The product layer diffusion controlled shrinking unreacted-core
model was used to fitted to the experimental data, using a correction factor for product layer
volume, although chemical kinetics were still important to determining the overall reaction
rate. Snow et al. (1988) also evaluated the direct sulfation of limestone under conditions that
did not decompose CaC03 to CaO. Their results were similar to those of Hajaligol et al.
(1988). As previously mentioned, a variable diffusivity shrinking unreacted-core model was
successfully applied to the direct sulfation of CaC03 by Krishnan and Sotirchos (1993b).
Effective gas diffusivity through the solid product layer was found to be a strong function of
gas temperature and S02 concentration in the bulk gas-phase.
When gas humidification was used, since N02 concentrations were monitored directly at the
bed inlet, chemical kinetics was not a function of N02 absorbed in the humidification vessel.
Since the molar volume ratio is smaller when starting with the hydroxide, more N02 can be
removed before the exterior surface becomes covered and Mg(OH)2 is no longer readily
available for reaction. This may mean that it takes longer to form a complete inert product
layer shell when moisture is available in the system. After this layer is formed, however, the
typical shrinking core behavior with product layer diffusion control would still be expected.
Effects of Residence (Reaction) Time
Studies varying gas flow rate and the resulting NOx bed residence time showed an
effect on N02 removal efficiency, as expected. When whole-bed half-second residence time
data were compared to data from the mid-point of the bed for a one-second residence time,
they were found to be directly comparable. These results suggest that the chemical reaction
is truly first-order with respect to NO^ and is essentially zero-order with respect to the solid,
MgO "concentration." The total quantity of N02 removed, however, would be a factor that
would affect overall bed performance, particularly as surface "saturation" is approached.
Better removal efficiencies were obtained with longer residence times. A residence time of
one second produced very high initial removal efficiencies, often greater than 99%. This
situation did not appear to be gas-film-mass-transfer-limited, as already discussed.
Additionally, since longer residence times correspond to lower gas velocities, measured bed
pressure drops were lower, which is preferable for JETC applications. Pressure drop results
will be presented later.
Constraints on MgO-Vermiculite Sorbent Usage
Based upon the experimental results collected in this study, it is apparent that there
may be some practical constraints on the effective employment of the MgOvermiculite
sorbent in the control of nitrogen oxides from jet engine test cells. The widely varying
conditions produced by jet engine testing require a control medium that is effective over the
entire range. While the sorbent effectively removed N02 from a flowing gas stream, the
ability of the sorbent to remove NO was minimal. The low concentrations of total NOx
emitted from a jet engine test cell make their removal by the sorbent more difficult, especially
after a product layer has formed on the exterior surface of the sorbent particles. Depending
upon the focus of any regulations related to jet engine test cells promulgated in the future,
a 50% reduction in NOx emissions may be sufficient.
This research has shown that the sorbent can continue to remove an average of
approximately 50% of the total quantity of N02 for a significant period of time, particularly
from lower concentration gas streams (< 100 ppm). To put some of the results into
perspective, the mass of sorbent required for the removal of N02 from a larger volume source
can be calculated. Using the results from the conditions under which the bed was nearly
Cum Mass NQ2 Removed (mg)
Bed Exposure Time (min)
1 NOx Analyzer Data
Figure 4-48 Cumulative mass N02 removed versus bed exposure time for a long-term run ([NO2]in=170 ppm, T=473 K,
[O2]=0%, Gas samples collected from center of bed).
Bjerle, I.; Xu, F.; and Ye, Z., "Useful Experimental Technique for the Study of
Heterogeneous Reactions," Chemical Engineering Technology. 15:151-161, 1992.
Borgwardt, R. H., "Kinetics of the Reaction of S02 with Calcined Limestone," Environmental
Science and Technology. 4(l):59-63, 1970.
Borwardt, R. H., "Calcium Oxide Sintering in Atmospheres Containing Water and Carbon
Dioxide," Industrial Engineering Chemistry Research. 28(4):493-500, 1989.
Borgwardt, R. H. and Bruce K R, "Effect of Specific Surface Area on the Reactivity of CaO
with S02," AIChE Journal. 32(2):239-246, 1986.
Borgwardt, R. H.; Roache, N. F.; and Bruce, K. R., "Surface Area of Calcium Oxide and
Kinetics of Calcium Sulfide Formation," Environmental Progress. 3(2): 129-135, 1984.
Campbell, N.T.; Beres, G.A.; Blasko, T.J.; and Groth, R.H., "Effect of Water and Carbon
Dioxide in Chemiluminescent Measurement of Oxides of Nitrogen," Journal of the Air
Pollution Control Association. 32(5):533-535, 1982.
Chen, J. P.; Buzanowski, M. A.; Yang, R. T.; and Cichanowicz, J. E., "Deactivation of the
Vanadia Catalyst in the Selective Catalytic Reduction Process," Journal of the Air and Waste
Management Association. 40(10): 1403-1409, 1990.
Chu, P. and Rochelle, G. T., "Removal of S02 and NOx from Stack Gas by Reaction with
Calcium Hydroxide Solids," Journal of the Air Pollution Control Association. 39(2): 175-179,
Clark, A., The Theory of Adsorption and Catalysis. Academic Press, New York, 1970, pp.
Comes, P.; Gonzalez-Flesca, N.; Menard, T.; and Grimalt, J.O., "Langmuir-Derived
Equations for the Prediction of Solid Adsorbent Breakthrough Volumes of Volatile Organic
Compounds in Atmospheric Emissions Effluents," Analytical Chemistry. 65(8): 1048-1053,
Cooper, C.D. and Alley, F.C. Air Pollution Control: A Design Approach. 2nd ed., Waveland
Press, Inc.; Prospect Heights, Illinois, pp 485-513, 1994.
CRC Handbook of Chemistry and Physics, 73rd ed., CRC Press; Boca Raton, Florida, pp 4-
Dam-Johansen, K. and Ostergaard, K., "High-Temperature Reaction Between Sulphur
Dioxide and Limestone I. Comparison of Limestones in Two Laboratory Reactors and a
Pilot Plant," Chemical Engineering Science. 46(3):827-837, 1991a.
oxygen in the combustion gas. The mechanism of the conversion of fuel nitrogen is believed
to proceed via a series of intermediates. One of the most important intermediates is hydrogen
cyanide (HCN), which is fully converted from bound nitrogen in the reaction zone of the
flame. Moving away from the reaction zone, the amount of HCN decreases as a result of its
conversion into N2 and NOx. Ammonia (NH3) may be detected along with N2, HCN, and NOx
in the products of combustion of nitrogen-containing fuels in the presence of a deficiency of
atmospheric nitrogen. The conversion of fuel nitrogen into HCN is rapid, and the rate-
limiting stage in the formation of NOx is the oxidation of HCN. The yield of NOx is
influenced by the content of nitrogen in the fuel, the amount of excess air, and, to a lesser
extent, combustion temperature (Ismagilov et al., 1990; Cooper and Alley, 1994; Wark and
Due to the extremely high temperatures in the combustion zones of aircraft jet engines
(up to 2500 K), thermal nitrogen oxides are formed by the oxidation of atmospheric nitrogen.
The accepted model for the chemical reactions responsible for NOx formation in the post
combustion zone was developed by Zeldovich in 1946. The reactions in Zeldovich's model
are as follows:
N2 + 0 ^ NO + N
N + 02 ** NO + 0
and N + OH^NO + H
200ppm 1 100ppm 50ppm 20ppm
Figure 4-8. N02 penetration vs bed exposure time (T=473 K, [O2]=0%)
Tubular Fixed-bed Reactors
The reactors, and mixing and sampling manifolds were machined from 316 stainless
steel seamless pipe stock (2.54 cm ID) (T.M.R. Engineering, Micanopy, Florida). Schematic
representations of the reactors, sample lines, and mixing and sampling manifolds are shown
in Figures 3-4, 3-5, and 3-6, respectively. While it is often standard practice and may be
sufficient to use only inlet and outlet concentrations from a fixed-bed to determine overall
conversion efficiency, this is obviously inadequate for the determination of intrinsic chemical
kinetics. For this reason, the reactors were designed to allow for the collection of samples
from three points within the packed bed. Using data collected from these points, a more
accurate depiction of the concentration versus time profile within the bed can be discerned.
This leads to the calculation of valid intrinsic chemical kinetic parameters. An Arrhenius-type
expression was used to determine corresponding activation energies.
Sampling lines were connected to the reactor via permanently welded 316 stainless
steel compression fittings (Swagelok, Inc., Solon, Ohio) and could be easily removed between
runs. One-eighth inch diameter internal sampling lines were used to minimize the cross-
sectional area blocked by the lines which could disrupt flow through the bed. The fractional
area blocked by the cross-section of a sampling line was approximately 16 percent. A total
of 12 holes (0.1 cm diameter) were drilled in the sampling lines. As shown in Figure 3-5,
these holes were placed in three places, located at the centroids of two concentric circles of
equal area within the reactor diameter. Each sampling location was from three sets of two
pairs of holes, the latter offset by 90 from each other.
general, higher N02 concentrations (> 100 ppm) were removed more efficiently and more
rapidly than lower N02 concentrations, particularly at elevated temperature. This finding
validates the use of a concentration-dependent chemical reaction model. The higher
concentrations of N02 may provide more opportunity for contact with active sites on the
sorbent surface area at which the chemical reaction(s) take place. In some cases, this may
mean that the external sorbent particle surface becomes covered by an "inert" (Mg(N03)2)
product layer, leading to rate limitation by a diffusion-controlled process following the
shrinking unreacted core mechanism. A higher concentration gradient would provide a driving
force to facilitate pore diffusion and diffusion through the inert (Mg(N03)2) product layer to
available remaining reactive MgO surface area in the interior portions of the sorbent particles.
Representative N02 penetration data presented in Figure 4-8 shows that at a reaction
temperature of473 K, initial N02 penetration was low (less than one percent), suggesting that
the N02 removal efficiency was greater than 99%, for all concentrations evaluated. After an
initial conditioning period of approximately 10 minutes, there is a distinct diversion between
the curves representing 20 and 50 ppm and the curves representing 100 and 200 ppm. N02
penetration increased to approximately 45-50% for the latter, while it remained at
approximately 25% for the former. Also, the rate of change of penetration was significantly
higher for the higher N02 concentrations. Kinetically, the fast initial reaction suggested that
significantly more N02 was removed at higher concentrations in a shorter period of time than
at lower concentrations. It is possible that the decreases in N02 removal rates at
approximately 25 minutes for the two higher concentrations correspond to the completion of
the "inert" surface-product-layer shell, whereas for the two lower concentrations, the exterior
Stagnant Gas Film
Figure 4-30. Graphical representation of the shrinking unreacted-core model under diffiision-through-inert-product-layer control.
higher temperatures would be expected. N02 penetration curves with a sharp break to a flat
curve would be expected if total pore closure occurs. However, positive slopes are seen even
after a sharp drop in reaction rate (Marsh and Ulrichson, 1985). The calcination of Ca(OH)2
to CaO results in highly porous particles with a theoretical porosity of approximately 50%
(Newton et al., 1989). Depending upon the temperature used, the actual porosity can be
lower, particularly for the calcination of Ca(OH)2. Virtually all of the surface area is in the
internal pore structure. The increase in molar volume from solid reactant to product results
in the filling of the pore structure and due to rapid reaction rates and pore diffusional
resistances, may lead to plugging of the outer CaO layers, leaving the interior unreacted.
As was previously noted, the first-order kinetic rate coefficients decreased with time
as reaction progressed. An empirical relationship between the inverse values of these
coefficients and exposure time was noticed. After an initial period of adjustment to dynamic
equilibrium conditions, a linear relationship between \/k and time appeared. Figure 4-38
displays an example of this relationship. This relationship allowed for the prediction of k-
values at an extended bed exposure time, based upon the values obtained from the first hour
of the experimental run. These predicted values were used in the first-order kinetic equation
to predict N02 concentration at any given time. Predicted N02 outlet concentration values
are compared to experimental values for a long-term run, as shown in Figure 4-39.
To test the validity of t values predicted by the shrinking unreacted-core equations,
the N02 penetration (or fractional outlet concentration) versus time curves are useful. Based
upon the shrinking unreacted-core model, "complete" conversion would be predicted to occur
at approximately 180 minutes (one-half of approximately 360 minutes). Looking at Figure
N02 Penetration (Fraction)
Figure 4-12. N02 penetration vs bed exposure time (T=423 K, [O2]=10%).
The rate equations obtained from the shrinking unreacted-core model can be used
together with the fixed-bed model, but simple analytical solutions are hard to find and the
determination of rate constants by the method of least squares is not possible. Some type of
numerical procedure has to be used instead (Bjerle et al., 1992). The constant-pattern
assumption allows the use of the relationship
Substituting the quantity (C/Ca) for X in the shrinking core equations allowed for the
evaluation of their applicability to the experimental data collected. Karlegard and Bjerle
(1994) used this approach in their study of the removal of H2S by zinc ferrite. Other notable
examples where the quantity (C/CQ) was used as an indication of solid conversion are the
work of Wolff et al. (1993) who used Y-Al203-supported CaO to remove gaseous S02, and
Dam-Johansen and Ostergaard (1991a), who examined the S02-limestone reaction.
Application of Shrinking Unreacted-Core/Grain Model to Experimental Data
To determine the applicability of the shrinking unreacted-core model to the
experimental data collected in this study, the respective governing equations were evaluated
for various stages of the reaction. Three examples were chosen for presentation to show the
range of applicability of the model to the reaction between N02 and MgO. As an intermediate
situation, the removal of 50 ppm N02 at a reaction temperature of 423 K was chosen. For
1 (1-X) 1/3 1 3(1-X) 2/3 + 2(1-X)
A 20ppm-R x 20ppm-D
Figure 4-40. Shrinking unreacted-core model evaluation ([NO2]in=20 ppm, T=373 K, [O2]=0%).
MgOVermiculite Particle Size, Dp (mm)
Â¡-probability plot of MgO-vermiculite sorbent particle size distribution.
adsorption isotherms are "favorable and exhibit the non-linear Langmuir form. A favorable
isotherm can be assumed for a single adsorbate with a high adsorption capacity, whose
concentration decreases in the downstream flow direction (Frey, 1992). The asymptotic limit
is reached when the fluid-phase front matches the adsorbed-phase front, and
a C (4-32)
* o o
in which q represents moles adsorbate sorbed per mole of reactant in the sorbent, qa
represents the largest number of moles of adsorbate that can be sorbed per unit mole of
sorbent, C represents outlet gas concentration, and Ca represents inlet gas concentration.
Constant-pattern behavior is the opposite limit to "unfavorable" or "proportional-pattern"
behavior, in which the concentration front becomes diffuse and extended by mass transfer
with the solid.
The differential-concentration driving force allows for mass transfer between phases.
In the fixed-bed model, the simplified differential mass balance is represented by
P b dq
where ev represents the void fraction of the bed. Correlation of this model with the shrinking
unreacted-core model, using the assumption of constant-pattern behavior, produces
P b dg ^ dX_
e dt 0 dt
where A and B are gaseous and solid reactants, respectively, C and D are products, and a,b,c,
and d are stoichiometric coefficients. This overall reaction may actually comprise several
sequential or simultaneous steps, of which one is rate-controlling. The three basic steps in
the generalized non-catalytic gas-solid diffusion-reaction process are
1) Gas-phase mass transfer via diffusion of the gaseous reactant from the bulk gas
stream to the external surface of the solid sorbent particle.
2) Gas-solid interaction on or within the solid sorbent particle through
a) Diffusion of the gaseous reactant into the pores of the solid complex,
which could consist of a combination of solid reactants and products.
b) Adsorption of the gaseous reactant on the surface of the solid complex.
c) Chemical reaction at the surface.
d) Desorption and diffusion of gaseous products, if any, from the surface and
out of the pores of the solid complex.
3) Gas-phase mass transfer of any gaseous products from the external solid surface
into the bulk gas stream
The number of diverse processes and steps involved makes the analysis of gassolid
reactions a potentially unwieldy problem. In general, each step provides resistance to
chemical reaction, and these resistances are additive. When the processes occur in series, it
is necessary to determine which step provides the major resistance to reaction, and ultimately
controls the overall reaction rate. The resistances of the different steps can vary greatly from
each other, so the step with the highest resistance can be considered to be the rate-controlling
of intrinsic kinetic data would be extremely useful in this regard. These data would also be
useful in determining the true limits of MgO utilization by N02 in the sorbent, and would most
likely make the shrinking unreacted-core model results easier to interpret. The high
temperature limit appears to be between 523 and 573 K, at which magnesium nitrate
decomposition is significant.
5. Obviously, there are other exhaust gas components whose presence may affect
the N02 removal characteristics of this sorbent. These other components should be evaluated
to determine their respective roles in the N02 removal process. One major component
includes the combustion aerosols, which would probably accumulate on the surface of the
sorbent, possibly making MgO on the exterior surface of the particle unavailable for reaction.
Some of the carbonaceous aerosols may themselves remove N02. The effect of this added
layer on the effective diffusivity of N02 inward toward unreacted MgO inside the particle
would also need investigation.
6. More tests at all operating conditions, but at longer reaction times, should be
conducted to provide more information on reaction rates and final conversions. Fully
automated valve-switching and data-collection systems would be very useful when
performing long-term runs. The predictability of N02 penetration as it relates to MgO
conversion is useful information in the design of any application that might employ this
7. The role of water and water vapor needs further study to validate the findings
of this research. It is essential to know if the improved N02 removal capabilities found in the
- 3(1-X)2/3 + 2(1-X)
Figure 4-35. Shrinking unreacted-core product-layer-diffusion-control-equation evaluation, xd=957 minutes ([NO2]in=50 ppm,
T=423 K, [O2]=0%). [ y = O.OOlx + 0.003, r^O.98, Fit Std Error = 0.0006, F=814.8],
+ Experimental Predicted
Figure 4-39. Experimental versus predicted N02 concentration ([N02]in=47.5 ppm, T=423 K, [O2]=0%, Gas samples collected
from middle of bed).
irregularly shaped layers and may show more or less diffusional resistance as the lattice
expands with reaction, forming a complex structure. Bamford et al. (1984) noted that lattice
structure changes often associated with gas-solid reactions sometimes effectively eliminate
oxygen vacancies, which have been reported to be relevant to the chemical reactivity of MgO.
It must be emphasized that while these models seem to have some utility in providing
a chemico-physical basis for describing N02 removal by the MgO-vermiculite sorbent under
the range of experimental conditions studied, this applicability is limited by the experimental
constraints placed upon these variables. Referring to the sulfation of CaO, Wen and Ishida
(1973) stated that various kinetic studies indicate that reaction rates can vary significantly
depending upon the type of limestones used, sometimes more than an order of magnitude.
It is likely that MgO powder dispersed within a packed bed, or individual pure MgO pellets
would behave quite differently from the combined MgO-vermiculite sorbent particles studied.
The low N02 concentrations used in this study probably have obscured the distinction
between the controlling mechanisms, often making it difficult to absolutely distinguish one
rate-determining mechanism from another.
It is apparent that the processes of pore closure, product-layer diffusion, and product
sintering are important factors in this study, whose combination makes data analysis very
difficult. To obtain a better understanding of how these mechanisms ultimately affect
conversion-versus-time behavior, more information is required on the solid structure and how
it changes during the course of reaction (Marsh and Ulrichson, 1985). Because of the high
diffusional resistance of the product layer, the concentration of gaseous reactant at the
reaction interface, and consequently the reaction rate, may not be uniform even under the
EXPERIMENTAL METHODS AND MATERIALS
General Research Approach
A fixed-bed reactor system was designed, constructed and used to collect the relevant
data to meet the established research objectives. The present study systematically addressed
individual exhaust gas components, focusing primarily on NOx, under strictly controlled
conditions to delineate the nature of the sorption rates and mechanisms. Processes and rates
for removal of N02 and NO by MgO-vermiculite sorbent were independently evaluated.
Moistened sorbent and/or humidified gases were used to evaluated the NOx removal
characteristics of Mg(OH)2. A variety of test conditions were used to determine important
operating parameters and limitations. By combining gaseous components, their interactions
in the presence of the sorbent material could be evaluated. Intrinsic and overall kinetic
parameters were determined. A complete description of the kinetics of gassolid reactions
is very complicated, especially for systems involving solid products, for which the processes
at both the gas-solid interface and the reaction interface between the reactant and product
solids must be considered. Although the rate expressions can be quite complex, the reactions
between adsorbate and adsorbent can often be described by first-order kinetics (Szekely et
al., 1976). Data were mathematically interpreted using the shrinking unreacted-core model
Engineering, Inc., Stamford, Connecticut) and meter were attached to the outside of the
The packed reactor was placed inside the tube furnace with the bed centered within
the furnace and the tube element mounted vertically on the furnace control base. The vertical
arrangement was chosen to optimize gassolid contact by avoiding the potential for solid
settling and channeling of the gas stream through the bed volume. The middle 15 cm of the
furnace was reported to be completely temperature-controlled by the manufacturer, providing
a sufficient length for isothermal experimental conditions. Once the reactor was in place,
sampling lines were individually connected to two-way stainless steel valves (Model W-l 188,
Whitey Co., Highland Heights, Ohio) at the sampling manifold. Gas lines entering the tube
furnace were wrapped in high-temperature heating tapes. These had been previously
calibrated using a Type K thermocouple to measure surface temperature at various settings
on the variable voltage controller. Depending on the reaction temperature of interest, the heat
tape voltage controller was set to produce a gas preheat temperature approximately 20 C
above reaction temperature. The tube furnace was turned on and allowed to heat up for
approximately one hour to achieve temperature control, while the bed was simultaneously
being flushed with approximately 2 sLpm dry N2. After this conditioning period,
thermocouple readings for the tube furnace and independent reactor thermocouple were
Krishnan, S. V. and Sotirchos, S. V., "A Variable Diffusivity Shrinking-Core Model and its
Application to the Direct Sulfation of Limestone," The Canadian Journal of Chemical
Engineering. 71:734-745, 1993a.
Krishnan, S. V. and Sotirchos, S. V., "Sulfation of High Purity Limestones Under Simulated
PFBC Conditions," The Canadian Journal of Chemical Engineering. 71:244-255, 1993b.
Krishnan, S. V. and Sotirchos, S. V., "Experimental and Theoretical Investigation of Factors
Affecting theDirect Limestone-H2S Reaction," Industrial Engineering Chemistry Research.
33(6): 1444-1453, 1994.
Lange's Handbook of Chemistry, 11th ed., McGraw-Hill Book Company; New York, p 4-88,
LeVan, M. D., "Fixed-Bed Adsorption of Gases: Effect of Velocity Variations on Transition
Types," AIChE Journal. 34(6):996-1005, 1988.
Levenspiel, O., Chemical Reaction Engineering. 2nd ed., John Wiley and Sons, Inc., New
Lewis, W. H., Nitrogen Oxides Removal. Noyes Data Corporation; Park Ridge, New Jersey,
Lyon, R. K., "Thermal DeNOx: Controlling Nitrogen Oxides Emissions by a Noncatalytic
Process," Environmental Science and Technology. 21 (3):231-236, 1987.
Lyon, R.K., New Technology for Controlling NO., from Jet Engine Test Cells.
ESL-TR-89-16, HQ AFESC, Tyndall AFB, Florida, 1991.
Marsh, D. W. and Ulrichson, D. L., "Rate and Diusional Study of the Reaction of Calcium
Oxide with Sulfur Dioxide," Chemical Engineering Science. 40(3):423-433, 1985.
Mejias, J. A.; Marquez, A. M.; Fernandez Sanz, J.; Fernandez-Garcia, M.; Ricart, J. A.;
Sousa, C.; and Illas, F., "On modelling the interaction of CO on the MgO(lOO) Surface,"
Surface Science. 327:59-73, 1995.
Meubus, P., "Catalytic Decomposition of Nitric Oxide in the Presence of Alkaline Earth
Oxides," J. Electrochem. Soc.: Electrochemical Science and Technology. 124(l):49-58, 1977.
Neal, D. D.; Hoke, S. H; and Spencer, W. P., NO.c Sources. Properties and Analytical
Procedures. Technical Report 8907, U.S. Army Biomedical Research and Development
Laboratory, Fort Detrick, Maryland, 1981.
N02 Penetration (Fraction)
Figure 4-9. N02 penetration vs bed exposure time (T=423 K, [O2]=0%)
All reactions were monitored by selectively removing gas samples from the stainless
steel tubular reaction vessel through selected valves connected to the sampling manifold
system. NOx concentrations were analyzed using a chemiluminescent analyzer (Model 42H,
Thermo Environmental Instruments, Franklin, Massachusetts) based upon the reaction of NO
with 03, following reduction of N02 to NO. The feasibility of the commercial
chemiluminescent analyzer was established in 1970 by Fontijn et al. and the first prototype
was developed in 1972 (Steffenson and Stedman, 1974). The method is now widely used,
in fact, the use of a chemiluminescent method is required for the measurement of N02 in the
atmosphere (40 CFR, Part 50, Appendix F). The principle of operation of the
chemiluminescent analyzer is based upon the chemiluminescent reaction between NO and
ozone (03). This reaction is as follows:
NO + O3- [N02* + 02] -N02 + 02 + hv (3-1)
where hv, which represents the quantity of light energy emitted by an electronically excited
intermediary (N02), is simply Planck's constant (h) multiplied by the frequency of the
emitted radiation (v), in this case with a wavelength greater than 600 nm. A sample of gas
is drawn from a selected point in the system by an external pump. The sample is mixed with
ozone generated by an internal ozonator inside a reaction chamber. The resultant reaction
produces a characteristic luminescence with an intensity directly proportional to NO
concentration, since 03 is provided in excess, and its concentration can be considered a
active surface area coverage by the product, which improved sorption performance with
6. The presence of oxygen in the exhaust gas aided in the removal of NO by the
oxidation of NO to N02. It appeared that oxygen may have promoted the continued removal
of N02 by the sorbent.
7. Temperature affected the reaction by increasing reaction rates both initially
(chemical-reaction control) and by improvingeffective diffusivity. Reaction temperature must
be kept below 523 K, since this is the temperature at which Mg(N03)2 begins to decompose.
8. The pressure drop versus superficial velocity relationship can be described
using the Ergun equation. This equation should be used to design any system in which this
sorbent will be employed since pressure drop is a limiting factor in a jet engine test cell
9. It is possible to regenerate the sorbent by heating for reuse. The initial N02
removal efficiency of regenerated sorbent is similar to fresh sorbent, but the extended
performance decreases with time, probably the result of structural changes (i.e., reduced
porosity/surface area, sintering, etc.).
10. A reaction mechanism has been proposed to explain the production of NO
during the removal of N02. NO may be produced during the final oxidation step of mixed
nitritenitrate product to its final nitrate form. After the N02 removal rate decreases, NO
production decreases accordingly.
11 The shrinking unreacted-core model was applied to N02 penetration data using
the local-equilibrium theory to estimate solid-sorbent conversion. The model described the
Generalized Non-Catalytic Gas-Solid Reactions 33
Mathematical Models 35
Progressive-Conversion Model 36
Shrinking Unreacted-Core Model 36
Grain Model 39
Analagous Gas-Solid Reaction System Research 41
S02CaO Reaction 42
S02-Calcium Hydroxide Reaction 43
S02-CalciumCafbonate Reaction 44
Other Acid-gas-Calcium-based-solid Reactions 45
General Applicability of the Shrinking Unreacted-Core Model 46
Research Justification 47
Research Objectives 47
3. EXPERIMENTAL METHODS AND MATERIALS 49
General Research Approach 49
Experimental Variables 50
MgOVermiculite Reactive Sorbent Material 50
Gas Composition 53
Gas Flow Rate(s) 54
Gas Reaction/Sorption/Desorption 55
Fixed-Bed Reactor System 55
General Experimental Considerations 55
Experimental Arrangement 58
Tubular Fixed-bed Reactors 58
Experimental Procedures 63
Gas Analyses 70
Sorbent Surface Area Determination 76
Sorbent Particle Size Determination 77
4. RESULTS AND DISCUSSION 78
Intrinsic Kinetic Studies 78
Limitation of Gas-Film-Mass-Transfer Resistance 79
Solid Sorbent Characterizations 82
Surface Area Analyses 82
Particle Size Distributions 83
NOx Removal by Mg(N03)2-coated Vermiculite 86
NQX Removal by Sorbent Material 86
NO Removal by Sorbent Material 87
N02 Removal by Sorbent Material 89
Effects of Operational Variables 94
saturated (170 ppm N02, 473 K) the sorption capacity of the sorbent (after 5 hours) was
approximately 40 mg N02/3.5 g sorbent bed. This corresponds to a mass loading ratio of
approximately 1.14 x 10'2 g N02 per gram sorbent, at an overall rate of 2.3 x 10'3 g N02 /g
sorbent-hour. While initial N02 removal was greater than 90%, the average removal over the
five-hour period was approximately 40%. Taking as an example a 10,000-acfm source of 200
ppmN02 at 473 K, the volume of bed required to treat this source, with all other conditions
remaining the same, and taking the bed to saturation after one hour, is approximately 3 m3,
not an inordinately large size. Obviously, it is not practical to regenerate or replace the bed
every hour, and the volume of gas to be treated may be larger, so a larger bed would be used.
As was already pointed out, jet engine test cells are not steady state sources and the average
test run may be much shorter than an hour in duration. After jet engine exhaust is augmented,
the concentration of N02 would also likely be less than 200 ppm, so the bed would last longer
because it takes longer to form the product layer when reacting with lower concentrations of
gases. Lower N02 concentrations will produce lower removal rates, but the bed will last
longer. When lower-concentration gases are expected, elevated temperatures can help to
improve difftisivity through the product layer in the absence of a large concentration gradient
The effective conversion of NO to N02 is a crucial element in the eventual successful
employment of this NOx control medium. Spicer et al. (1990) noted that exhaust
augmentation can increase the NOz-to-NO ratio from 1 or 2:10 to 7 or 8:10. While they
attributed some of this oxidation to the presence of peroxy radicals in fuel-rich combustion,
oxygen oxidation can be significant as well. Obviously there are a number of other variables,
Figure 4-3. Log-probability plot of Akrochem Elastomag 170 MgO powder particle size distribution (manufacturer-provided
required to maintain a reasonable amount of N02 removal from the gas stream. When oxygen
was present in the system, it had a less noticeable effect when comparing the temperature
effects for a given inlet N02 concentration as can be seen in Figures 4-18 through 4-20.
Again, initial N02 penetration was lowest at the highest temperature for all concentrations,
but it increased more noticeably for the higher concentrations. For an inlet N02 concentration
of 20 ppm, penetration stayed below 10% for an exposure time of nearly an hour.
Activation Energy Determination
To determine experimental activation energies, Arrhenius plots of the natural
logarithm of the bed-exposure-time-specific first-order rate coefficients versus the reciprocal
of the absolute reaction temperature were prepared. The rate of removal of N02 was
sometimes less temperature-dependent between 373 and 423 K, as seen in Figure 4-21.
When this was the case, data were collected at an intermediate temperature of approximately
450 K, since the plots were often more linear over the higher temperature range. A good
example of linearity in the plot between 473 K and 373 K can be seen at Figure 4-22. From
the slopes of these Arrhenius plots, the apparent activation energies can be determined. These
were approximately 33 kJ/g-mol at 5 minutes bed exposure time and about 8 kJ/g-mol at 20
minutes bed exposure time for the example shown in Figure 4-21. The decrease in activation
energy with bed exposure time suggests that a change in N02 removal mechanism occurs with
increasing bed exposure time. It is common, however, for Arrhenius plots of heterogeneous
reaction parameters to show curvature (Clark, 1970).
Initial activation energies were often difficult to determine due to system fluctuations
during the first 1 to 2 minutes of operation. This instability probably caused some of the
chemico-physical model to adequately explain the removal of gaseous contaminants. A means
for accomplishing this correlation using local equilibrium theory and assumptions regarding
constant-pattern behavior for mass transfer in a fixed-bed will be detailed later.
The basic principles that govern chemical kinetics and diffusion phenomena in single
particles are normally unaffected by the presence of other particles in an arrangement like a
packed bed. Changes in the flow field due to the packed bed arrangement likewise do not
invalidate these principles (Szekely et al., 1976). In this way, a fixed-bed experimental
system may be used to extend the information obtainable from single particles to multiple-
particle systems. Multiple-particle systems are obviously of more interest since practical
systems must be of this type. Since the sorbent material is highly heterogeneous, data
reproducibility between samples is very important. This was evaluated by comparing results
for the same experimental conditions between different samples of sorbent material.
While the basic principles of single gas-solid interaction will still apply, the physical
characteristics of any experimental fixed-bed reactor can markedly affect chemical kinetics
and overall sorption behavior. It is critical that such a system be carefully designed, to ensure
that any experimental data collected are scientifically valid and defendable. Often, practical
constraints such as temperature and, particularly, gas velocity and its effect on pressure drop
through the bed, must be incorporated into the experimental design. Such other factors as
particle fluidization velocity and the potential for temperature and concentration gradients
must be accounted for as well. In this research, MgO will be attached to its vermiculite
substrate. Results, however, may be different from those for individual MgO particles due
to this arrangement.
The most harmful effects of NOx are primarily attributed to exposure to N02 the most
toxic of these oxides. N02 is a reddish-brown gas that is quite visible in sufficient
concentration (> 0.25 ppm). N02 is not a primary pollutant in the sense that it directly affects
human health, unless the exposure concentration is high. N02 exerts its main toxic effects on
the lungs via free-radical-mediated reactions and other mechanisms. Both NO and N02 are
free radicals that may produce lipid peroxidation reactions within human cells. The
environmental hazard of N02 is primarily associated with the pulmonary effects of the
pollutant. Exposure to concentrations ofN02 from 0.7 to 5.0 ppm for 10 to 15 minutes have
produced abnormalities in pulmonary airway resistance. Exposures to 15 ppm can cause eye
and nose irritation, and pulmonary discomfort is noted at 25 ppm for exposures of less than
The greatest danger of exposure to N02 is the delay in experiencing its full effect upon
the respiratory system. The delayed effect of N02 injury is made potentially more dangerous
by two other factors. Human perception of the odor of N02 is insufficient to warn against
injury or even death. Additionally, N02 quickly desensitizes an individual to its odor through
olfactory fatigue, and if N02 levels gradually rise, a person could unknowingly be exposed
to concentrations high enough to cause permanent injury or death. Because of the low
solubility of N02 in water, it is only slowly removed from the lungs by circulating blood and
may remain in contact with lung cells for prolonged periods of time. Given the same total
dose, short-term exposure to high concentrations of N02 is more injurious than long-term
exposure to lower concentrations. The toxic effects of N02 are often synergistic with or
3) N02 + MgN205 Mg(N03)2 + NO
It should be noted that N02 is functioning as an oxidizing agent in the final step, to complete
the formation of Mg(N03)2, in the absence of oxygen. If oxygen were present, then it may
competitively complete this last step, reducing NO formation. When Mg(OH)2 is the solid
reactant, the mechanism remains essentially the same, except that water may be liberated
during the first step in forming MgN03. This first step is presumed to be the rate-limiting step
since the other two steps are expected to be much faster.
From a comparison of the ratio of the quantity of N02 removed to NO produced as
reaction progressed, some support for this mechanism was obtained. Initially, the absolute
value of this ratio was very high, with much more N02 being removed than NO being
produced. As reaction progressed, however, this ratio often decreased to a point where 2 to
3 moles of N02 were removed for every mole of NO produced. This value is appropriate
given the proposed mechanism just shown. The time when this ratio was achieved was
normally toward the end of the one hour experimental period. It is likely that even after the
reaction becomes product-layer-diffusion-controlled, the other sequential steps are still
occurring so that N02 removal by the overall process is still apparent.
Application of the Shrinking Unreacted Core/Grain Model
The shrinking unreacted core model contains parameters that are useful for predicting
the behavior of gassolid reactions. Incorporating such physical parameters as the molar
volume ratio of products to reactants (which can affect product layer formation and
describing the observed discrepancy between theoretical and observed solid conversion is the
effective difiisivity through the product layer. Incomplete conversion, which decreases with
an increase in intrapellet diffusional resistance, is predicted using the random pore model
developed by Bhatia and Perlmutter (1981a). A unique feature of this model is that solid
pores are not assumed to be of uniform size, so smaller pores are more easily blocked when
a dense or large-volume product is formed on the surface. Dam-Johansen et al. (1991) used
physical parameters of a chalk sorbent to modify the grain model down to the micrograin
level. While this provides a physical description of the reaction occurring at the sub-grain
level, the reaction taking place still follows the shrinking unreacted-core mechanism.
Analogous Gas-Solid Reaction System Research
The most similar gassolid reaction systems discussed in current literature describe
the reactions between sulfur dioxide (S02) and lime/calcium oxide (CaO), calcium hydroxide
(Ca(OH)2), or limestone (calcium carbonate (CaC03)). Reactions of acidic gases with
calcined limestone have been closely studied because of their industrial importance. The high
porosities of various forms of CaO (nominally over 50 percent) makes them quite suitable for
tests of the numerous forms of the shrinking unreacted-core model. Although these models
have been used quite successfully, the fundamental rate-controlling processes are still not well
understood (Borgwardt et al., 1986). Data on reactions between other acid gas/acid
anhydride gases and other carbonate rocks are also available. In these processes, S02-
containing gases are contacted with lime or limestone, either as a wet slurry or dry solid. S02
is generally collected on the solid surface for reuse or disposal. Regeneration may produce
is a problem with attempting to use "pure" N02 (or NO) in gas-solid sorption studies
employing cylinder gases. These gases were diluted with dry air or prepurified N2 to the
appropriate concentration(s). Cylinder gas flow rates were measured using precision
rotameters (Omega Engineering, Inc., Stamford, Connecticut) with only glass and/or stainless
steel wetted parts. While the manufacturer provided calibration data, all rotameters (both
high- and low-flow-rate tubes) were independently calibrated in the laboratory using a primary
airflow standard (Gilibrator, Gilian Instrument Corporation, Wayne, New Jersey). These
calibrations were extremely important for accurate gas flow rate measurements, particularly
when using low-flow-rate tubes, which have non-linear calibration curves. Good agreement
was reached between the calibration curves, as can be seen in the example comparative
calibration curves, Figures 3-2 and 3-3. Laboratory calibration curves were used to measure
gas flow rates in this study.
All system components were made of either 316 stainless steel or Pyrex glass to
reduce the potential for NOx removal by system reactivity. Inert gas transfer lines were made
from Teflon tubing of minimal lengths to minimize transfer losses. Most connections were
through 316 stainless steel compression fittings (Swagelok, Inc., Solon, Ohio). Where pipe
thread connections were necessary, Teflon tape was used to prevent leakage. Before
experiments were initiated, the entire system was leak-checked and NOx decay (reactivity)
measurements were made for the system. Each system component was isolated and evaluated
separately. Overall NO and NQ2 removal as a result of system reactivity were estimated at
less than one percent. In this way, any changes in NOx concentration with time could be
attributed solely to the presence of the sorbent material in the fixed-bed reactor.
Figure 4-45. Shrinking unreacted-core chemical-reaction-control-equation evaluation, t=495 minutes ([N02]in=200 ppm,
T=473 K, [O2]=0%). [ y = 0.002x + 0.035, ^=0.94, Fit Std Error = 0.011, F=159.7],
Pilot-scale tests of this MgO-vermiculite sorbent were conducted on a JETC facility
at Tyndall AFB, Panama City, Florida, between 9-11 June, 1992 and on 18 September, 1992.
A two-stage filter bed design, consisting of four inches of virgin vermiculite in front of eight
inches of MgO-coated vermiculite, was evaluated through four approximately 20 minute runs
of subscale drone engines. An additional run was conducted through four inches of activated
carbon, followed by the eight-inch MgOvermiculite bed. NOx removal efficiencies for the
first four tests were approximately 50 percent. This increased to approximately 80 percent
with the addition of the activated carbon bed. Between June and September 1992,
approximately 150 unmonitored engine tests took place. When the September 1992 test was
conducted, NOx removal had decreased to 60 percent. Gas temperatures, velocities, and
pressure drop through the beds were also measured. The Air Force sponsor had imposed a
pressure drop limit of two inches of water on the bed, which was not exceeded. However,
approximately two-thirds of the volumetric flow was allowed to bypass the filter to prevent
overheating inside the JETC facility. Results showed that significant amounts of unburned
(non-methane) hydrocarbons (primarily ethylene) passed through the beds that did not contain
activated carbon (Nelson et al., 1992; Wander and Nelson, 1993).
More regeneration studies were conducted by Nelson et al. (1990) to attempt to
optimize the regeneration of MgOvermiculite after "saturation" with NOx (and S02). The
sorbents were alternately exposed to simulated jet engine exhaust and regenerated in reducing
atmospheres for a number of treatment cycles to evaluate NOx sorption capabilities.
uniform temperatures and concentrations in the porous network. Structural properties
depend not only on conversion, but also the relative rates of reaction (intrinsic kinetics) and
mass transport in the product layer (Sotirchos and Yu, 1985). Gullett et al. (1992) compared
the magnitude of the sum of squared errors as well as the coefficient of determination in
defining the best-fitting shrinking-core-model equation in the reaction between HC1 and CaO.
They found that often either the chemical-reaction-control model or the product-layer-
diftiision-control-model is sufficient to describe sorption, without the inclusion of both models
simultaneously. The two main governing equations for chemical-reaction-control and
product-layer-diffusion-control are themselves not uniquely distinct, particularly when the
true solid sorbent conversion level is low. Therefore, care should be taken in using these
modeling results to quantitatively derive physical parameters of the sorbent under the
conditions evaluated, or in their extrapolation to different conditions under which MgO solids
may be used to remove N02 from a flowing gas stream.
Effects of N02 Concentration 94
Effects of Oxygen 99
Effects of Bed Temperature 105
Activation Energy Determination 112
Effects of Water 120
Effects of Residence (Reaction) Time 122
Sorbtech-Supplied Sample Results 123
Pressure Drop Characteristics 124
Magnesium Nitrate Surface Decomposition 127
Sorbent "Lifetime" and Regeneration 130
Proposed Reaction Mechanism 132
Application of the Shrinking Unreacted Core/Grain Model 133
Derivations of the Shrinking Unreacted-Core Model 144
Correlation Between Gas-Phase Concentration and Solid Conversion 146
Local-Equilibrium Theory 146
Application of Shrinking Unreacted-Core/Grain Model to Experimental Data 148
50 ppm N02 at a Reaction Temperature of 423 K 149
20 ppm N02 at a Reaction Temperature of 373 K 165
200 ppm N02 at a Reaction Temperature of 473 K 169
General Applicability of the Shrinking Unreacted-Core Model 178
5. PRACTICAL CONSIDERATIONS 182
Constraints on MgO-Vermiculite Sorbent Usage 182
6. CONCLUSIONS AND RECOMMENDATIONS 185
Recommendations for Further Research 188
LIST OF REFERENCES 192
BIOGRAPHICAL SKETCH 201
the evaluation of the extreme experimental conditions, the removal of 200 ppm N02 at 473
K and the removal of 20 ppm N02 at 373 K were evaluated. These three cases contain data
collected in the absence of oxygen, using dry sorbent (no Mg(OH)2). The relevance of the
shrinking unreacted-core model to these situations will also be generally discussed. Each case
will be presented separately, with a discussion of the specific applicability and considerations.
50 ppm NO-, at a Reaction Temperature of 423 K
Figure 4-31 represents the mathematical transformation of solid sorbent conversion
data (X or N02 penetration) into the values obtained from the shrinking unreacted-core
equations. The left ordinate shows the chemical-reaction-control-equation values (Equation
4-18) and the right ordinate indicates the product layer diffusion control equation values
(Equation 4-28). If an equation is representative of the mechanism occurring, then the plot
will be linear with a slope of the inverse time to complete reaction, tr or rd, as previously
discussed. From this figure, it visually appears that over the entire course of reaction
evaluated, the reaction-control-equation line shows noticeably greater curvature than the
product-layer-diftusion-control-equation. To apply some statistical significance to the fit of
these equations at various stages of the reaction, linear least-squares regressions of the data
were performed, including the determination of 95% confidence intervals.
The two equations are separately evaluated as shown in Figures 4-32 and 4-33. From
Figure 4-32, the equation of the least-squares linear regression line for the chemical-reaction-
control-equation is y = 1 = 0.0025t + 0.0223, with an r2 value of 0.95. From this
Ln Instrument  (Percent)
+ Mid Scale High Scale
Figure 3-8. Typical IR-2100 oxygen analyzer calibration curve.
Major Larry Thomas Kimm was born in Mount Clemens, Michigan, on November 6,
1960. After graduation from Fraser High School, in Fraser, Michigan, in 1978, he attended
the U.S. Air Force Academy at Colorado Springs, Colorado, until his graduation and
commissioning as a second lieutenant in the U.S. Air Force in 1982. He received a Master
of Science degree in biology (industrial hygiene) from Old Dominion University, Norfolk,
Virginia, in 1988. He was competitively selected to continue his education under the USAF
Biomedical Sciences Corps advanced education program, and came to the University of
Florida and the Department of Environmental Engineering Sciences to begin his Ph.D. studies
in August 1991. Serving as abioenvironmental engineer in the U.S. Air Force, Major Kimm
returns to his career after receiving his degree. He has been married to the former Lisa Anne
Wilson since 1987, and is the father of two children, a daughter, Meredyth Grace, and a son,
including the presence of other exhaust gas components, that need investigation before one
can truly predict what may happen on the sorbent surface.
As was noted by Wander and Nelson (1993), bed pressure drop is a potentially
significant limiting factor in the use of the MgO-vermiculite sorbent in a packed-bed scenario.
Nelson et al. (1993) evaluated the potential for NOx removal in a variety of flow-through bed
arrangements in which the gases would make indirect contact with the sorbent at the wall of
the container rather than physically passing through it. This did not work well, so it appears
that direct contact is necessary for the removal of N02 from the gas stream. The Ergun
equation describes the pressure-drop-versus-superficial-velocity relationship, so it can be
used in the design of a packed bed in keeping pressure drop below established limits. An
empty-bed residence time of approximately one second is recommended for efficient N02
removal, as well as in the minimization of pressure drop through the bed, although reduced
times still allow for some removal of N02. The physical dimensions of a unit designed for the
control of nitrogen oxides from a jet engine test cell must be based upon these constraints in
order to effectively remove the nitrogen oxides while minimizing the negative impacts on the
jet engine testing operations that are producing the exhaust to be treated.
Most experimental work published on CaO-S02 reactions was conducted using S02
concentrations in the tenths of a percent, one to two orders of magnitude greater than N02
concentrations evaluated in this research. It is noted that Equation 4-36 does not have a gas-
phase concentration term. At a given conversion level (or product layer thickness), Marsh
and Ulrichson (1985) found that doubling the bulk gas-phase adsorbate concentration should
double the overall reaction rate, consistent with the idea of a product layer surrounding the
active surface area of the oxide. Another example is the degree of zinc ferrite utilization in
the removal of2,600 ppm H2S at 500 to 600 C, as reported by Karlegard and Bjerle (1994),
which varied from 5 to 11%.
A significant correlation between adsorbate concentration and solid conversion in the
reaction between S02 and CaO was reported by Simons (1988). Simons reported a
utilization factor of approximately 0.6 for this effect, meaning a ten-fold increase in
concentration produced a six-fold increase in effective utilization. Based upon this
correlation, a ten-fold lower concentration would predict an Xmax value of approximately 3%,
and a hundred-fold lower concentration would predict an Xmax value of approximately 0.4%.
This may partially explain the low N02 utilization rate by MgO. Since little is known about
the pore size distribution of the MgO-vermiculite sorbent, it is difficult to say what effect it
may have on sorbent utilization. However, Simons also pointed out that small-pore plugging
is dominant for 1- to 10-pm particles, while pore-mouth plugging is dominant for 100-pm
particles. Rate limitations resulting from product-layer diffusion (prior to plugging or filling)
are most evident for thick product layers occurring within the larger pores of larger particles.
If pore plugging within the grains of the particle were occurring, lower conversion levels at
sorbents originally designed for the control of S02, that were based upon MgO (an alkaline
earth [Ha] metal oxide) coated onto vermiculite or perlite [Nelson, U.S. Patents 4,721,582;
4,786,484, 1988; and 4,829,036 (1989)]. S02 reduction is believed to occur primarily by
reaction with MgO, forming complex sulfites or sulfates. It was assumed that NOx could be
removed in a similar manner, forming nitrites or nitrates. Sanitech researchers began
evaluating expanded vermiculite as a catalyst in 1987. A patent describing the use of
vermiculite as a selective reduction catalyst [US Patent 4,806,320] was granted to Sanitech
In August 1988, the Air Force awarded Sanitech a Small Business Innovation
Research (SBIR) project to further develop the new catalyst for application to jet engine test
cells. Nelson et al. (1989) reported the results of a series of tests designed to establish the
applicability and technical feasibility of using vermiculite as a catalyst to reduce NOx from
simulated jet engine exhaust. These studies, beginning as a selective-catalytic approach,
evaluated how vermiculite variables (type and size), bed size, solid additives to vermiculite,
flue gas variables (temperature, composition, flow rate) and the addition of methane or
ammonia to the exhaust gases generally affected NOx reduction.
Some initial regeneration studies were also performed. These screening studies
indicated that a MgO-coated vermiculite material showed great promise as a NOx-reducing
agent for a wider variety of conditions than encompassed by commercial catalysts. Some of
the major conclusions of this study included data indicating that vermiculite alone, without
ammonia or methane additions, demonstrates the ability to reduce NOx by 50 to 73 percent
over the temperature range of 250-850 F. The use of gaseous ammonia only marginally
1) Mg(N03)2-6H20 : MgO = 13.9 : 1
2) Mg(N03)2-2H20 : MgO = 8.1 : 1
3) Mg(N03)2-6H20 : Mg(OH)2 = 6.3 : 1
4) Mg(N03)2-2H20 : Mg(OH)2 = 3.7 : 1
As all of these values are noticeably greater than one, the use of the Z-term is expected to aid
in the interpretation of the experimental data collected in this study.
Szekely et al. (1976) also pointed out that the use of one or the other of the governing
equations may not be sufficient to best describe the experimental data. Since the two
equations are similar, it is often difficult to distinguish between chemical-reaction control and
product-layer-diffusion control. In some cases, assuming gas-film diffusion is not rate-
limiting, chemical-reaction and product-layer-diffusion may collectively control the reaction
rate. In such cases, a term (o2) representing the ratio of diffusional resistance to chemical-
reaction resistance can be defined to apply the relative importance of each resistance to the
This term is applied via the equation:
Correlation Between Gas-Phase Concentration and Solid Conversion
To use the shrinking unreacted-core model equations it is necessary to collect data
describing solid conversion with time. This is normally done using thermogravimetric
methods on single pellets, by way of real-time surface analyses, or post-sorption chemical
analyses. As was previously explained, these data were not collected since they are less
relevant to data directly indicative of the control efficiency of gaseous NOx pollutants. It is
necessary to be able to correlate these data so that they can be used in the model equations
to interpret sorption behavior. By invocation of assumptions related to constant-pattern
behavior associated with the local-equilibrium theory of fixed-bed reactors, the previously
displayed gas-penetration-versus-time data are made more amenable for this purpose.
While a detailed discussion of the local-equilibrium theory can be found in any
standard text on adsorption in fixed beds, the following brief presentation is based upon
descriptions by Sherwood et al. (1975) and Ruthven (1984). When there is efficient mass
transfer between the gas and solid phases, the reactive gas travels through the packed bed as
a wave without a significant change in concentration, other than that caused by reaction with
the sorbent surface. The wave front reaches a steady state and its width, as it moves through
the bed, attains a "constant pattern." The constant-pattern approach is based on the
assumption that the width of the concentration front tends toward a constant value as the
concentration wave moves through a packed bed. The mass-transfer zone reaches a stable
asymptotic form in this case (LeVan et al.., 1988). According to Suzuki (1990), most
Magnesium Nitrate Surface Decomposition
Solid Mg(N03)2*6H20 (Certified A.C.S. grade, Fisher Scientific, Pittsburgh,
Pennsylvania) was dissolved in deionized water and applied to heat-treated vermiculite, and
the mixture was allowed to air dry. The mass ratio applied was approximately 15%
Mg(N03)2. This material was packed inside a clean reactor and 2 sLpm dry N2 was delivered
to the bed. Bed outlet concentrations of NO and N02 were followed over time as bed
temperature was increased from ambient temperature to 373 K through 573 K in 50 K steps.
Results are plotted in Figure 4-25. From this figure, it can be seen that at temperatures used
for sorption, little NO and N02 were released compared to those emissions observed at much
higher temperatures, 523 and especially 573 K. In either case, the ratio ofN02/NO released
was approximately between 10:1 and 16:1. Heating samples of used sorbent to a temperature
of 523 K produced similar results (See Figure 4-26). This implies that N02 is the
predominant gaseous reactant in the forward reaction. Also, it is important to recognize that
the decomposition of Mg(N03)2 is not a significant source of NO. Although it is obviously
necessary to control NO emissions, these studies imply that NO production observed in N02
sorbent removal studies must occur through a mechanism other than decomposition of
Air Flow (mL/min)
Omega Data I Lab Calibration
Figure 3-3. Example high-flow-rate rotameter calibration curves (Omega NO92-04G Tube).
Table 4-2. Intrinsic first-order rate coefficients (s'1) for N02 removal by MgO-vermiculite sorbent ([O2]=0%)
Reaction Temp ( K):
Integration and rearrangement isolates the time of reaction:
t 'X [l-(^)J] (4-9)
3 tkjA]t R
Therefore, under gas-film-diffiision control, rc = 0, and we will define rf as the time for
complete reaction of the particle:
We can rewrite this equation in terms of fractional solid conversion (X) by allowing:
1 X (vo^ume unreacted core
total particle volume
4/3 it/-3 r
7 = (i)3
4/3 TiR 3 R
Whence we can define the dependence of X upon t:
i-(-)3 = X
Plotting solid conversion versus bed exposure or reaction time, as previously described,
should reveal a linear relationship having a slope of 1/ rp if gas-film-diffiision is rate-limiting.
From Figure 4-29, it can be seen that the concentration gradient, and the related
progress of reaction, are unaffected by the presence of any inert layer(s) in this situation. The
Packed Bed Region
2.5 cm 2.5 cm
316 SS Fixed-bed Reactor Schematic (Not to Scale)
Total Length Approximately 47 cm.
Figure 3-4. Schematic representation of 316 stainless steel packed-bed reactor (end connections not shown).
Figure 4-38. Plot of inverse first-order rate coefficient (1/k) versus bed exposure time ([N02]in=47.5 ppm, T=423 K, [O2]=0%).
reuseable sulfuric acid or in some cases, elemental sulfur. A magnesium oxide process similar
to lime or limestone scrubbing is sometimes used where MgO is hydrated to Mg(OH)2 which
reacts with S02 forming MgS03/MgS04 solids. These can be heated, generating S02 and
MgO. The S02 can normally be recovered as a sulfuric acid product (Cooper and Alley,
Borgwardt (1970) investigated the reaction of S02 with calcined limestones and found
a first-order chemical reaction to be the predominant process with resistance limiting S02
sorption by small particles. He found that the reaction rate decreased rapidly as CaO
conversion increased. Some of the solids contained significant quantities of MgO, which did
not readily react with S02 at the elevated temperatures evaluated. Wen and Ishida (1973)
found, through an application of the grain model, that the overall reaction rate between S02
and CaO was highly temperature dependent, particularly at lower temperatures where it was
controlled by chemical kinetics. They reported that various kinetic studies have indicated that
reaction rates may vary considerably (more than an order of magnitude) depending upon the
type of limestones used. This variability is a common problem inherent in the study of
The previously mentioned study by Hartman and Coughlin (1976), which improved
the applicability of the grain model, also described the S02-CaO reaction. The strong
relationship between surface area and the reactivity of CaO toward S02 was analyzed via the
shrinking unreacted-core model by Borgwardt and Bruce (1986). The surface area is
4-39, effective N02 removal has stabilized at a value of approximately 22% at this exposure
time. Allowing the reaction to progress for four more hours, N02 removal had only changed
to 20%. The shrinking unreacted-core model can be used to reasonably predict "effective"
complete conversion of the solid, and the time at which this will occur. This can be combined
with the empirical model to predict what the N02 removal rate will be when this occurs. The
sorbent appears to continue to remove N02 at a rate that is probably a function of the
effective diffusivity through the product layer for subsequent removal by the abundant
quantity of MgO available inside the particle.
20 ppm N02 at a Reaction Temperature of 373 K
The controlling mechanism for this low-concentration, low-temperature extreme was
difficult to discern. From Figure 4-40, there appears to be little difference between the
chemical-reaction-control equation and the product layer diffusion equation. Progress of the
reaction is visually more non-linear for both equations during the first 20 minutes than for the
remainder of the curve. Fitting the equations to the longer-exposure-time data between 20
and 60 minutes produced a better fit. The results are shown in Figures 4-41 and 4-42. From
these curves, zr is calculated to be 1023 minutes, and zd is equal to 1093 minutes. Using the
combination-of-resistances equation for the data between 20 and 60 minutes, a zr value of
952 minutes was calculated. Using the differential molar volume equation, a zd value of 515
minutes was calculated. At the mid-point of the bed, again, relative z values at this point
would be approximately half of these values.
N0X concentrations seem to point toward increased regulatory pressure to reduce NOx
emissions from jet engine test cell activities in the near future.
If NOx standards for test cell emissions are to be considered, clearly those systems
available for controlling these emissions must be thoroughly evaluated. To reduce NOx
emissions, two primary actions can be taken. These are the direct control of the reaction(s)
producing the pollutant (combustion process), or control of the process effluent. To
understand the means of controlling NOx emissions, it is critical to examine the basic
chemistry, thermodynamics, and kinetics of the formation reactions. Oxides of nitrogen
formed by combustion processes are generally caused either by the conversion of chemically
bound nitrogen in the fuel ("fuel NQX"), or by thermal fixation of atmospheric nitrogen in the
combustion air ("thermal NOx").
The principal factors affecting the formation of nitrogen oxides in combustion
processes are the amount of fiiel-bound nitrogen, peak combustion temperature, oxygen level
at peak temperature, and residence time in the combustion zone (Organization for Economic
Cooperation and Development, 1983).
When a fuel containing organically bound nitrogen is burned, the contribution of
the fuel-bound nitrogen to total NOx can be significant. The N-C bond is much weaker than
the N-N bond in molecular nitrogen, so fuel nitrogen can be more easily oxidized to NO by
layer surrounding the sorbent particle. Practical constraints on pressure drop will likely limit
gas velocity in the application of this control technology to jet engine test cells. Comparative
experiments and mathematical evaluations were performed to ensure that this source of error
was effectively minimized. Results will be presented in a subsequent section.
Gas reaction/sorption was measured by the change in concentration of the test
gas(es) with bed residence and exposure times. Gases were sampled at the inlet and outlet
of the sorbent bed, and also from three points within the bed (of nominal 0.1-m length). Both
short-term (to dynamic equilibrium) and long-term results (taking the bed to "saturation," a
function of bed exposure time) were collected. Concentration-versus-time data from within
the bed were used to evaluate intrinsic chemical kinetics. Overall kinetic data were derived
from progressive removal efficiencies and were used to model overall sorbent performance
with increasing bed exposure times.
Fixed-Bed Reactor System
General Experimental Considerations
Many gas-solid reactions are studied using individual sorbent particles or pellets.
These individual particles are placed in a controlled environment and exposed to the adsorbate
of interest. Sorption behavior is determined gravimetrically using a microbalance and mass
balance calculations. An increase in sorbent mass is directly related to solid sorbent
conversion via stoichiometry. Some fundamental gas-solid studies employ either thin films
This arrangement was chosen to ensure that a representative sample of gas was collected
from any given location within the bed, avoiding the potential bias caused by any flow
disturbances through the packed bed, or by reactor wall effects. The number of holes and
perpendicular placement were intended to prevent inconsistencies due to hole blockage during
the course of a run, although this did not appear to be a problem. A thermocouple attachment
screw mounting was placed on the outside of the reactor(s) to allow for the independent
measurement of reaction temperature for comparison with the indicated furnace temperature.
The mixing and sampling manifolds were simply sections of 316 stainless steel pipe,
approximately 70 cm long (28 inches), with six permanently emplaced 316 stainless steel
compression fittings for the connection of gas transfer lines and/or valves, as appropriate.
Before use, machined parts were cleaned and degreased with methanol, followed by
acetone and a deionized water rinse. Cleaning all parts with deionized water between runs
was sufficient during the normal conduct of experiments. For a nominal bed length of 10 cm,
the bulk volume of a packed bed was approximately 51 cm3. Individual sorbent samples were
measured out using a graduated cylinder filled to a loosely packed volume of approximately
51 cm3. These samples were transferred to preweighed sealable polyethylene sample
containers and weighed (approximate mass 7-7.5 g/sample). Since MgO comprised
approximately 45% of the total sorbent by mass, each bed contained approximately 3 g MgO.
After sampling lines were inserted into the reactor, the bed was packed between circular 316
stainless steel screens (12x12 mesh) at the center of the clean tube using a marked steel ram
rod to ensure that the bed was properly located. End connections were replaced and a Type
K (Nickel-Chromium versus Nickel-Aluminum) thermocouple (Model XCIB-4-4-3, Omega
Consideration of equation (1-8) allows insight into the effect of temperature on NO
formation, particularly in the hot flame zone. Once exhaust gases move away from this zone,
they cool rapidly, reducing the reaction rates by orders of magnitude. If excess oxygen is
present as the gas cools, the conversion of NO to N02 (reaction (1-5)) is favored.
Thermodynamics predicts that the cooled gas will consist primarily of N02. In reality,
although the favored ambient form of NOx is N02, flue gases from combustion contain
predominantly NO. Approximately 90 to 95 percent of NOx emitted from combustion
processes appears as NO, that is thermodynamically unstable in the environment as its
temperature drops. However, the decomposition of NO into N2 and 02 and the reaction of
NO with 02 to form N02 are kinetically limited. Thus, the high concentrations of NO formed
at high temperature in the combustion zone are "frozen in" and are carried out with exhaust
gases into the atmosphere. From equation (1-8), therefore, it is seen that, with respect to the
reduction of thermal NOx, combustion control strategies could be developed that are aimed
at a reduction in peak temperature, a reduction in gas residence time at peak temperature, and
a reduction of oxygen concentration in the high-temperature zone (Cooper and Alley, 1994;
Wark and Warner, 1981; Organization for Economic Cooperation and Development, 1983).
Regulation of NO.. Emissions
The federal primary air quality standard for N02 is presently 0.05 ppm, based upon
an annual arithmetic mean. Emission and performance standards for various stationary
sources of NOxhave also been established. Although the exhaust from jet engine test cells
Sorbent "Lifetime" and Regeneration
Whereas initial sorbent N02 removal rates were often greater than 90 percent
fractional N02 removal decreased while N02 concentrations leaving the bed increased with
bed exposure time (Figure 4-27). In this example, dynamic equilibrium was approached after
approximately 20 minutes of bed exposure. At approximately the same time, NO outlet
concentrations increased to values greater than NO inlet concentration. The NO produced
was much greater than that which would result from nitrate decomposition, as previously
described. Also, NO production through thermal N02 decomposition at temperatures below
500 K is minimal. These observations indicate that there must be another mechanism for NO
A consecutive multi-step chemical reaction of two or more molecules of N02 with
MgO leading to the bed surface becoming saturated with Mg(N03)2 may be proposed. One
step (which it is convenient to propose as the last) must be an oxidation process in which the
equivalent of an oxygen atom is delivered to some intermediate product having the empirical
formula MgN205 (MgO + 2N02). On a mass-ratio basis, this process appears to occur, on
average, when approximately 3 mg N02 per gram of MgO are sorbed. While this
corresponds to minimal utilization of the bed, significant capacity for N02 removal persists
long after initiation of this final oxidation process, as N02 removal efficiencies of 50-60% can
continue for hours. It may be that MgO or Mg(OH)2 at the external particle surface is
covered by a nitrated monolayer, so only internal oxide or hydroxide is available for reaction.
improved NOx reduction and increased the sensitivity of the process to temperature change.
Vermiculite coated with MgO removed approximately 70 percent of NOx and the process was
relatively insensitive to changes in waste gas composition, velocity and temperature.
It is believed that the NOx species were chemically adsorbed by the MgO/vermiculite
product and attached at the surface as complex magnesium nitrites and/or nitrates. Tanabe
and Fukuda (1974) found that MgO has a higher number of active (basic) sites compared to
other alkaline earth metal oxides (i.e., CaO, SrO and BaO). Zhang et al. (1994) further
attributed the activity of MgO surfaces to oxygen vacancies in the lattice structure. Some
selected physical properties of MgO, Mg(OH)2, and magnesium nitrite and nitrates are shown
in Table 2-1.
Table 2-1, Physical properties of selected Mg-containing inorganic compounds.
MofNf 1 -3T-T f)
Note: Loses water of hydration at 350 C.
Source: CRC Handbook of Chemistry and Physics, 73rd Edition, 1992.
Reactor Cross Section
(2.54 cm ID)
Figure 3-5. Schematic representation of internal sampling tube location and appearance.
from the figure, the bed did not remove a large amount of NO from the flowing gas stream,
even in this case, with both water vapor and oxygen present. The observed NO removal may
be the result of its oxidation to form N02, which is removed by the bed. Since the gases were
humidified, it is reasonable to assume that the MgO on the sorbent surface was hydrated to
the hydroxide form. In general, when N02 was present, NO was no longer removed after a
specific exposure time and was actually produced after sorption of sufficient N02. The latter
observed effect will be discussed later.
NO-, Removal by Sorbent Material
Overall N02 removal efficiencies were found to greatly exceed those for NO. Initial
N02 removal efficiencies were always greater than 90 percent. As bed exposure time to N02
progressed, N02 removal efficiency decreased, suggesting a "saturation" phenomenon. After
approximately one hour of exposure time, N02 removal efficiency approached a stable value
that was much greater than zero. Typical plots of N02 concentration versus residence time
data are shown in Figure 4-5. In all of the cases evaluated, an intrinsic first-order kinetic
dependence was observed:
-dC/dt = kC (4-1)
where C= N02 concentration in ppm, t=residence time in seconds, and k=first-order rate
constant in sec'1. Integrating equation (4-1) produces:
To put these numbers into perspective, the cumulative mass of N02 removed by the
sorbent bed was calculated using an iterative approach by multiplying the one-minute average
N02 removal rates by the N02 mass flow rate for each minute of the run. These were added
together to produce a cumulative mass of N02 reacted at any given exposure time. It was
assumed that all NQ2 removed from the gas stream was taken up by the MgO-vermiculite
sorbent bed. An example of these data collected from the middle of the bed is plotted in
Figure 4-36. The middle of the bed was selected as the sampling point because it was
assumed that the front half of the bed would become "saturated" more rapidly than the back
half of the bed in a long-term run. It can be seen from this figure that the rate of cumulative
mass removal is initially greater than later in the run. This trend is more evident in Figure 4-
37, which shows data collected over a 7-hour period. This long-term run was conducted to
evaluate the x values predicted by the model equations. Since samples were collected at the
center of the bed, only half of the total bed mass was used for sorption up to this point, so x
values should be divided by two for application to this reduced-sorbent-mass and associated
surface area. Plots of the amount of N02 mass adsorbed versus time were concave toward
the time axis, as in most diffusion-controlled processes in which the buildup of concentration
inside the particle progressively reduces the driving force or the accumulation of product
increases resistance (Pigford and Sliger, 1973).
From these figures, the mass removal rate does not appear to approach zero, even
after an extended exposure period. The total mass of N02 removed after 7 hours was only
21.6 mg or 4.7x 10'4 moles. This is significantly less than the predicted stoichiometric
capacity of the mass of MgO in the bed, corresponding to a utilization ratio of approximately
To account for sorbent porosity, Szekely and Evans (1970) first improved upon the
basic shrinking unreacted-core model by further defining the structure of the idealized
sorbent pellet or particle. The particle is assumed to be made up of compacting individual
grains of uniform size and shape. A schematic representation of the grain model is shown in
Figure 2-3. While in reality, this assumption may not be entirely accurate, the model presents
a means of accounting for the effects of particle and grain shapes on reaction rates. Each
grain still reacts following the shrinking unreacted-core model. A shape factor for one of
three idealized predominant shapes (either a sphere, cylinder, or flat plate) enters the relevant
shrinking unreacted-core model equations. This shape factor can be used to qualitatively
discern information about the sorbent surface physical structure as it affects sorption
This model has been further modified by Hartman and Coughlin (1976), among others,
to account for increased diffusional resistance to chemical reaction in the product layer. This
effect is greatly compounded when the molar volume of the product is significantly larger than
that of the solid reactant, causing coverage or blockage of potentially available intergrain pore
surface area. This may cause a discrepancy between the theoretical solid-surface conversion-
versus-time behavior, as predicted by the model, and actual experimental results.
Ramachandran and Smith (1977) took the model a step further in modeling the single-pore
behavior in a porous pellet to predict the conversion versus time relationship for gas-solid
non-catalytic reactions. Their model accounts for the influence of pore diffusion, diffusion
through the product layer, and surface reaction. A key parameter useful in
additive to those of other environmental contaminants (Wark and Warner, 1981; Neal et al.,
Environmental Impacts of NO.c
In addition to the direct effects on health, nitrogen oxides may create other detrimental
effects on air quality and the environment. These effects include interactions with
hydrocarbons to produce photochemical oxidants and smog; contribution to acid precipitation
through nitric acid formation; and degradation of visibility and aesthetics by formation of
high N02 levels in elevated plumes and fine particulate aerosols resulting from by-products
ofNOx reactions (Organization for Economic Cooperation and Development, 1983).
Over 95 percent of all the man-made nitrogen oxides that enter the atmosphere in
the United States are produced by the combustion of fossil fuels. As of 1990, over 55 percent
of these emissions are attributed to stationary sources, such as utility and industrial boilers,
gas turbines, and stationary engines. Approximately 40 percent are from mobile sources
(transportation). The remaining fraction is from miscellaneous sources including industrial
processes and waste disposal. On a global scale, the anthropogenic NOx emission rate is
minor compared to natural emissions and formation in the environment. As a result, air
pollution associated with NOx is mainly a local or regional problem (Cooper and Alley, 1994;
Wark and Warner, 1981).
The level of effect of nitrogen oxides on the local environment is highly dependent
upon the emission rates of sources and prevailing meteorological conditions and topological
Particle Size Distributions
A sample of MgO-vermiculite sorbent was sieved, as previously described, and
results were plotted on a log-probability graph, shown in Figure 4-2. Since many particle size
data are log-normally distributed, this type of plot should produce a linear representation from
which relevant statistical parameters most importantly, the mass median diameter and
geometric standard deviation can be determined. From Figure 4-2, it can be seen that the
distribution is fairly linear between the 10th and 90th percentiles, so these data were used for
this purpose. From the distribution, the mass median diameter (MMD) is approximately 1.7
mm, and the geometric standard deviation (Og) is approximately 1.5. Since the sorbent
particles were mechanically abraded during the sieving process, the true MMD is probably
somewhat larger, perhaps in the range of 2 to 3 mm. The median diameter determined here,
however, can be used for calculating flow characteristics for a packed bed filled with this type
A log-probability graph for the manufacturer-supplied size-distribution data on the
MgO powder used to prepare the combination sorbent is shown at Figure 4-3. From this
graph, the MMD for the MgO powder used is approximately 1.3 pm, and og is equal to
approximately 2.5. Since the chemical reaction occurs at the surface of the MgO particles,
this distribution can provide useful data for use in determining physical parameters via the
shrinking unreacted-core model. The MMD is probably not the most appropriate dimension
to use for these purposes, however, since the reactions occurring
equation, zr (the inverse of the slope of the regression line) is equal to 397 minutes. While
the coefficient of determination's value is relatively high, there is obviously some curvature.
A considerably better fit was obtained for the product-layer-diffiision-control equation, where
both the r2 and F-statistic values are higher, as shown in Figure 4-33. Only the initial point
falls outside the 95% confidence interval. From this fit, rd is determined to be equal to 820
minutes, approximately twice as large as r which would necessarily be smaller since
chemical-reaction control assumes a more-rapid rate of reaction and, relatedly, a more-rapid
solid conversion rate.
It is quite likely that both processes are simultaneously playing a role in the limitation
of the reaction rate. It would be expected that chemical reaction control would be more
important early in the reaction process. To test this, the first 15 minutes of data are replotted
as shown in Figures 4-34 and 4-35. From these figures, the two mechanisms appear to be
equally important in describing initial sorption behavior under these conditions. To test the
combined resistance equation, the value of o2 was calculated to be 2.5, which when used in
Equation 4-31, produced a value of rr equal to 357 minutes. As was previously discussed,
when the molar volume ratio of product to reactant is large, this may play a role in the
ultimate determination of the overall rate as well as solid sorbent conversion efficiency. From
the data in Table 2-1, the molar volume ratio of Mg(N03)2 (anhydrous) to MgO, Z, is
estimated to be approximately 3.7. Using Equation 4-29, a value of rd equal to 330 minutes
was calculated, a 60% smaller number than that calculated using Equation 4-28. It appears
that the model predicts a significant effect from the molar volume ratio difference.
step. A simplified expression for the rate-determining step can then be used to describe the
Three major processes are generally considered to be rate-controlling in non-catalytic
1) Mass transfer of the gaseous reactant from the bulk gas phase through the stagnant
film layer surrounding the particle to the surface of the solid sorbent. The rate of this
step is most dependent upon the fluid dynamics of the gas flow around the solid
2) Chemical kinetics of the reaction between the gaseous and solid reactants.
3) Mass transfer of the gaseous reactant or product by diffusion through any
product layer at the surface of the solid or in the internal pore structure of the solid.
The rate of this step is highly dependent on the extent of reaction and the physical
properties of the product layer or solid sorbent.
The classical Langmuir theory, which is based solely on available surface area, is often
insufficient to account for the formation of a solid product layer on the surface of the solid
reactant and associated surface changes. This theory assumes a uniform reactant surface,
with reaction ceasing after all surface area is covered (Laidler, 1987). Related non-linear
sorption models are not applicable to systems with porous sorbents where isotherms are
favorable and chemical reaction and pore diffusion resistances can be significant (Biyani and
where: JP=pressure drop, L=bed depth,
factor, absorbent surface area mean particle diameter (mass median diameter), py=gas
density, and Â£/0=superficial gas velocity, all in appropriate absolute units.
It can be seen from equation (4-3), that at low fluid velocities the first (viscous) term
predominates, and at high gas velocities that the second (inertial) term is dominant and the
pressure drop is proportional to the square of gas velocity. The shape factor term,
defined as the ratio of the surface area of a sphere of equal volume to the particle to the
surface area of the particle. The value of this term is obviously 1 for spherical particles and
normally lies in the range from 0.5 to 0.9 for naturally occurring materials. The median
sorbent particle diameter was approximately 2 mm. The value for Â£v was determined by the
mechanical compression of the sorbent to a point where gas would not flow through the bed,
reducing the volume by approximately 30 percent (
an average bed load produced an
hydrophilic, and bulk gas flow does not occur through the internal porosity of the particles,
a value of 0.4 was used for
75 Pa; and when U= 0.2 m/s, AP is equal to 163 Pa. These estimated values correspond well
with average experimental AP values of 75 and 125 Pa, respectively. Figure 4-24 depicts
a comparison between experimentally measured pressure drop and the pressure drop
predicted by the Ergun equation.
To quantify emissions from jet engines, the USAF has sponsored numerous studies
and has published jet engine emission values for many engines in the USAF inventory. These
documents describe NOx and other combustion by-product emissions correlated with power
setting or operational procedures (Spicer et al., 1990). These studies are very useful for
determining appropriate exhaust gas concentrations to simulate jet engine exhaust gas
composition in the laboratory. Many lab-scale studies have used these data in their
experimental design. Gas composition was kept constant for each run. Major components
of JETC exhaust were evaluated individually (mixed in N2 or air): NO (5-200 ppm), N02
(20-200 ppm), and 02 (0-10%). Gas concentration ranges relate to representative values at
four common engine settings (nominally, idle, 30%, 75% and 100% power) for the USAF
FI 10 turbine engine. Actual engine emissions data are shown in Table 3-1. Water vapor (3-
5% by volume at temperature) was evaluated in cohort with other gaseous components.
Water vapor may hydrate the MgO, forming a reactive hydroxide.
It is seen from this table that jet engine exhaust contains significant quantities of
unbumed hydrocarbons, carbon monoxide (CO) and carbon dioxide (CO^. Particulate matter
in the form of soot or condensation aerosols will also most likely be present in real exhaust.
All of these exhaust components have the potential to affect the NOx sorption performance
of the sorbent. For the purposes of this study, these variables were not included to allow for
the evaluation of the basic NOx-sorbent reaction(s).
jet engine to service. The engines are operated over their full range of thrust, representative
of typical operational modes. Total test times can range from less than an hour to two to
eight hours. The most common jet engine test cell design is shown in Figure 2-1. The engine
to be tested is mounted horizontally in the U- or L-shaped enclosure and combustion air is
drawn in through sound-deadening baffles. Unequal flow distributions are corrected by
turning vanes to provide an undistorted airflow at the engine outlet at a specified velocity
(often < 50 feet per second). Exhaust gases are blown into a large, long tube (augmenter
tube) with a convergent entrance section. The purposes of the augmenter are to draw air into
the test cell and engine with equal air pressure at the inlet and outlet of the engine (Note
venturi shape), to draw a portion of the air around the engine housing to provide cooling
similar to that experienced during flight, and to dilute and cool engine exhaust to prevent
damage to construction materials. Augmented gas temperatures can vary from about 200
to 2000 F (100-1100 C) depending upon engine firing rate and augmentation ratio.
Generally, the temperature of these gases is less than 500 F (260 C). The augmentation ratio
is varied by the placement of the engine relative to the augmenter throat. Some augmenter
tubes contain cooling water sprays to further quench the exhaust gases. Exhaust gases exit
the augmenter tube through a perforated basket, which helps to dissipate some jet engine
exhaust momentum as well as acoustical energy. In some cases, this basket can be adjusted
to reduce back pressure on the engine. Gases leaving the augmenter tube fill a blast room
before exiting the test cell through a stack. Cooled exhaust is vented to the atmosphere
through multiple channels within the stack to minimize noise (Johnson and Katz, 1990).
Depending upon the engine being tested, the volume flow rate of gas leaving the cell can be
n i i i 1 1
0 20 40 60
Bed Exposure Time (min)
Figure 4-32. Shrinking unreacted-core chemical-reaction-control-equation evaluation, t=397 minutes ([N02] =50 ppm
T=423 K, [O2]=0%). [ y = 0.003x + 0.023, r^O.95, Fit Std Error = 0.012, F=208.1],
Pressure Drop (Pa)
Superficial Velocity (m/s)
Predicted + Experimental
Figure 4-24. Predicted (Ergun equation) versus experimental pressure drop as a function of superficial velocity for a 0.1 m long
bed of MgOvermiculite sorbent (T=473 K).
reactions are. Chemisorption is also temperature dependent, occurring faster as temperature
increases; however, the amount chemisorbed at equilibrium decreases with temperature
(Hayward and Trapnell, 1964; Szekely et al., 1976 ).
Gassolid reactions are inherently complex due to the number of simultaneous
processes that occur throughout the course of reaction. Any equilibrium conditions reached
are often dynamic rather than static in nature, since the system continues to change with time.
In addition to mass transfer and difiusion processes, these reactions often include heat transfer
and structural changes in the solid phase. Ideally, to properly describe a particular gassolid
reaction, all of these simultaneous and consecutive processes should be taken into
consideration. In practicality, however, this would make for extremely complex mathematical
models. A good engineering model should be one that closely approximates the real situation
without too many mathematical complexities that will make it too cumbersome to use. The
use of simplifying assumptions and the careful design of experiments, to reduce or limit the
effects of variables on a given process so that it may be neglected, are often necessary to
produce useable data and models.
Generalized Non-Catalytic Gas-Solid Reactions
A generalized non-catalytic gassolid reaction may be represented by the following
aA (gas) + bB (solid) cC (solid) + dD (gas)
calcium oxide, that was highly dependent upon temperature and humidity conditions.
Kitagawa [U.S. Patent 3,382,033 (1968)] developed a dry method that utilizes inorganic salts
such as PbS04, KMn04, KC103, NaCIO, Na^O,,, K2S203, and Na2HP04 and inorganic
oxides like As03 and Pb02 as suitable adsorbents. Collins [U.S. Patent 3,674,429 (1972)]
derived a two-stage process involving silica gel and an activated crystalline zeolitic molecular
sieve. The use of activated carbon to adsorb nitrogen oxides has been studied extensively
(Badjai et al., 1958 (Wark and Warner, 1981)). Its high surface area, adsorption rate and
capacity, and regenerability are well known. James and Hughes (1977) used calcined
limestones and dolomites (MgO-containing) to remove NO at high concentrations with good
results. Kikkinides and Yang (1991) reported some success in the simultaneous sorption of
N02 and S02 using a weak-base macroreticular resin material.
Jet Engine Test Cells
With all of the previous research that has been conducted for application to industrial
processes and power generation equipment, relatively little has been done to specifically
address the control of NOx from jet engine test cells. In order to better understand the
problems associated with NOx control in jet engine test cells, it is useful to examine their
general structure, purpose and characteristics. The Department of Defense operates
approximately 180 cells, which are considered to be stationary sources by the U.S. EPA. The
purpose of a jet engine test cell is to provide a structure to evaluate engine performance
during controlled testing after maintenance to assure proper operation before returning the
discrepancies in the intrinsic first-order rate coefficients seen in the preceding tables. Best
estimates of the Arrhenius activation energy associated with this sorption process are between
20 and 36 kJ/g-mol during the first few minutes of sorption without oxygen, and between 15
and 25 kJ/g-mol with oxygen present, for the range of N02 concentrations and temperatures
evaluated. These values are within the range of activation energies generally associated with
chemisorption processes, as previously discussed.
When comparing activation energies for similar acid gas-alkaline solid reactions
reported by different investigators, it must be noted that the values depend on the
experimental arrangements used, the methods used in the analysis of experimental data, and
the accuracy by which initial reaction rates can be measured. The chemical reaction rate
coefficient usually influences only the initial stages of reaction because once a product layer
is formed, the local rate of reaction becomes diffusion controlled (Sotirchos and Zarkanitis,
1992). Hajaligol et al. (1988) determined the activation energy associated with the sulfation
of CaO by S02to be approximately 146 kJ/g-mol. The activation energy calculated from
initial rate data for the sulfation of CaO by Marsh and Ulrichson (1985) was 80 kJ/g-mole.
Zarkanitis (1991) determined activation energies of the reaction of CaO with S02 to be
approximately 17 kJ/g-mole. The latter investigator determined this reaction to be less
sensitive to reaction temperature than the reaction of S02 with calcium carbonate. He also
found that the sulfation of reagent-grade MgO proceeds at rates comparable to those for
CaO. Sotirchos and Zarkanitis (1992) confirmed that the activation energy associated with
the sulfation of CaO was 17 kJ/g-mol using an S02 concentration of 2,000 ppm at reaction
temperatures between 700 and 850 C. Borgwardt (1970) had previously reported that the
Figure 4-33. Shrinking unreacted-core product-layer-diffusion-control-equation evaluation, Td=820 minutes ([NO2]in=50 ppm,
T=423 K, [O2]=0%). [ y = O.OOlx + 0.003,rMi.999, Fit Std Error = 0.001, F=7125.9],
In presenting these reactions, it is assumed that the fuel combustion reactions
(between C, H, and O) have reached equilibrium and that the concentrations of O, H, and OH
can be described by equilibrium equations. Considering only the thermodynamics of NOx
formation, the two overall reactions of concern are those which produce NO and N02. The
relevant equilibrium reactions are
N2 + 02 ** 2NO
and NO + 1/2 02 ** N02
The equilibrium constants for reactions (1-4) and (1-5) (Kpl and Kp2, respectively) are
where: Kp = equilibrium constant,
P, = partial pressure of component i (atm),
Yj = mole fraction of component i,
and PT = total pressure (atm).
An analysis of values for Kpl and K 2 at various temperatures indicates that
thermodynamically, the forward reaction in (1-5) is favored over the forward reaction in (1-4)
at low temperatures, with very little NO formed at temperatures below 1000 K. Hence, the
Exhaust Gas Treatment
Exhaust gas treatment appears to be the most applicable method of controlling NOx
emissions due to the difficulty in using combustion/operations modifications with JETCs and
the priority placed on unperturbed engine performance during testing. The high volume of
exhaust from a military jet engine, combined with the need for higher levels of NOx reduction,
makes the selection of the optimal exhaust gas treatment a difficult task. There are two main
types of exhaust gas treatment processes, wet and dry processes. Wet processes typically
employ the absorption of NOx. The main disadvantage of wet absorption is the low solubility
of NO. Additionally, these processes often create liquid waste that may require proper
disposal at significant cost. For these reasons, dry processes are generally preferred. These
include selective or non-selective catalytic reduction, selective non-catalytic reduction,
irradiation, and dry sorption (Cooper and Alley, 1994).
In selective catalytic reduction, only the NOx species are reduced (to N2 gas), leaving
free oxygen unreacted. With a suitable catalyst (typically a precious metal, although a variety
of other catalysts have been studied) ammonia (NH3), hydrogen (H2), carbon monoxide (CO),
or hydrogen sulfide (H2S) can be used as the reducing gas. NH3 is the most commonly used
gas. A number of stoichiometries have been proposed for this reaction. For example, Davini
4NO + 4NH3 + 02 -* 4N2 + 6H20 (1-9)
Although the selective catalytic reduction process is very effective and is capable of
achieving NO reduction rates exceeding 90 percent in controlling steady-state processes, its
Mixing or Sampling Line Attachment Points
316 SS Mixing or Sampling Manifold
Total Length Approximately 47 cm.
Figure 3-6. Schematic representation of 316 stainless steel mixing or sampling manifold.
N02 Penetration (Fraction)
Bed Exposure Time (min)
Figure 4-23. N02 penetration versus bed exposure time (20 ml H20 added to 7 g MgO-vermiculite sorbent, [NO2]in=100 ppm,
[O2]=0%, T=473 K).
0.2%. It is interesting to note that the N02 removal to NO production ration was
approximately 4:1 after 3 hours, and was approximately 3:1 after 7 hours, supporting the
previously proposed mechanism of removal. The low utilization ratio is believed to be a
complex function of a number of important variables, including the low N02 concentration
in the bulk gas phase, the high product-to-reactant molar volume ratio, and reduced sorbent
Without a significant concentration-gradient driving force, formation of a layer of
Mg(N03)2 on the exterior surface area of the sorbent will render the remaining available MgO
relatively inaccessible for reaction with N02. The high product-to-reactant molar volume
ratio means that a significant amount of surface area can become blocked from reaction as
product is formed. For reactions accompanied by an increase in the volume of the solid
phase, incomplete conversion may be expected with ultimate conversion decreasing with an
increase in intrapellet diffusional resistance. In many gas-solid reactions, maximum solid
conversion approaches a constant value less than 100%. The main reasons for this
phenomenon are structural changes of the pores. Maximum conversion is reached when pore
closure occurs (Ramachandran and Smith, 1977). The reaction of S02 with CaO or MgO
forms a solid product, CaS04 or MgS04, which occupies more space than the solid reactant.
If there is no increase in the overall volume of the porous particles during reaction, the pore
space may become completely filled with or covered by solid product. Once pores become
plugged, the interior of the porous particles are practically inaccessible to gaseous reactants
since diffusion through the solid product is an extremely slow process (Sotirchos and
Zarkanitis, 1992). Bhatia and Perlmutter (1983) attributed the continued slow solid-surface
of solid sorbent reactant, or fine particles dispersed within an inert material bed such as quartz
silica sand or glass beads. While these types of studies are valuable for collecting data on
fundamental reactions occurring between the phases, in this study, by necessity, the use of the
prepared sorbent was a fundamental limitation. Experimental results may or may not be
transferable to the basic reactions between NOx gases and MgO or Mg(OH)2 solids. It is
possible that the process of making the sorbent promotes sorption through the enhancement
of available surface area. It is also possible, however, that the inefficient transfer of Mg(OH)2
slurry to the vermiculite substrate before calcination may create dense agglomerates or
otherwise make MgO unavailable for reaction with NOx. The effects on ultimate sorbent
conversion and bed utilization will be discussed later.
Often, particularly in chemical or materials engineering studies of gassolid reactions,
the emphasis is on the solid sorbent surface and its conversion as reaction progresses.
Experiments are designed for the purpose of optimizing the solid sorbent itself. Solid
conversion is generally measured directly through chemical analyses, including spectroscopic
and chromatographic methods. Physical properties of the sorbent can be evaluated using X-
ray diffraction or electron microscopy, for example. While these previously discussed studies
are invaluable, in environmental engineering and particularly, in air pollution control, the
focus is often on the gas-phase concentration and the effective removal of the pollutant of
interest. This applied engineering approach is the result of the unavoidable fact that
environmental regulations mandate the reduction of emissions to specified limits and
compliance with regulations is determined through air sampling. It is still crucial, however,
that gas-phase concentrations be correlated with solid conversion through an appropriate
Figure 2-1. Schematic Representation of a Jet Engine Test Cell.
4-38. Plot of inverse first-order rate coefficient (1/k) versus bed exposure time
([N02]in=47.5ppm, T=423 K, [O2]=0%) . 163
4-39. Experimental versus predicted N02 concentration ([NOJj^T.S ppm,
T=423 K, [O2]=0%, Gas samples collected from middle of bed) 164
4-40. Shrinking unreacted-core model evaluation ([NO2]in=20 ppm, T=373 K,
4-41. Shrinking unreacted-core chemical-reaction-control-equation evaluation, xr=1023
minutes, ([NO2]in=20 ppm, T=373 K, [OJ=0%) 167
4-42. Shrinking unreacted-core product-layer-diffiision-equation evaluation, -rd=1093
minutes, ([NOJ^O ppm, T=373 K, [OJ=0%) 168
4-43. Experimental versus predicted N02 concentration ([NOJ^^. 1 ppm, T=373 K,
[OJ=0%, Gas samples collected from middle of bed) 170
4-44. Shrinking unreacted-core model evaluation ([N02]in=200 ppm, T=473 K,
4-45. Shrinking unreacted-core chemical-reaction-control-equation evaluation, xr=495
minutes, ([N02]in=200 ppm, T=473 K, [O2]=0%) 172
4-46. Shrinking unreacted-core product-layer-diffiision-equation evaluation, xd=1015
minutes, ([N02]in=200 ppm, T=473 K, [O2]=0%) 173
4-47. Experimental versus predicted N02 concentration ([N02]in:=170.0 ppm, T=473 K,
[OJ =0%, Gas samples collected from middle of bed) 175
4-48. Cumulative mass N02 removed versus bed exposure time for a long-term run
([NO2L=170 ppm, T=473 K, [O2]=0%, Gas samples collected from center
of bed) 176
4-49. Comparative bed N02 and NO concentrations versus bed exposure time during
long-term run showing NO production ([NOJ^HO ppm, T=473 K, [O2]=0%,
Gas samples collected from center of bed) 177
implemented under the strict protocols of jet engine testing. Water or steam injection into the
fuel, combustion air, or combustion zone is very effective at reducing NOx formation by
reducing combustion temperatures (Cooper and Alley, 1994). Introducing additives into jet
engine combustion zones or fuels, however, is a potential problem due to losses in output
(which is closely monitored during testing) or physical damage to the engine or turbine blades.
Some research has been conducted on other fuel or combustion zone additives as applied to
jet engine test cells, which will be discussed in the following sections.
Combustion modifications can reduce NOx formation by lowering one or more of the
parameters peak temperature, gas residence time, or oxygen concentration in the flame zone.
Peak temperatures can be reduced by 1) using a fuel-rich primary flame zone; 2) increasing
the rate of flame cooling; or 3) decreasing the adiabatic flame temperature by dilution
(exhaust gas recirculation). Gas residence time in the primary flame zone can be reduced by
1) changing the shape of the flame zone; or 2) using the steps listed in the previous strategy.
Oxygen concentration in the flame zone can be reduced by 1) decreasing the overall excess
air rates; 2) controlling the mixing of fuel and air; and 3) using a fuel-rich primary flame zone
(Cooper and Alley, 1994). In general, it is difficult to employ these controls in a jet engine
test cell application due to the changing power settings associated with test and acceptance
runs and associated performance fluctuations. Additionally, the strict performance standards
required during military jet engine testing limit the applicability of combustion modifications.
N02 Penetration (Fraction)
T-373K T=423K T=473K
Figure 4-14. N02 penetration versus bed exposure time ([N02]in=200 ppm, [O2]=0%).
Indicated [NO] (ppm)
Standard [NO] (ppm)
Figure 3-7. Typical chemiluminescent NOx analyzer calibration curve (for NO channel).
Magnesium oxide powder was prepared for addition to the mixture by sieving with
a 28-mesh Tyler Standard sieve (600 pm opening). Forty-five grams MgO per 55 grams dry
vermiculite was added to the wet vermiculite while the mixture was manually stirred using a
stirring tool. This ratio was the same as that reported by Sorbtech and is less than the 60:40
maximum mass ratio described in the patent. The same ratio was used so that the two
sorbents could be compared. Sorbtech is able to prepare large batches of material using
mechanical stirring, perhaps allowing them to use less water, while more evenly coating the
sorbent with the Mg(OH)2 slurry.
After thorough mixing, the sorbent was allowed to air dry overnight until the
individual particles were again "free-flowing." The pans of sorbent were then placed in a
preheated muffle furnace set at 550 C and "conditioned" for 30 minutes. It is believed that
this process increases sorbent surface area by expanding the particles as a result of driving out
interior water vapor via heating. This process also dehydrates the Mg(OH)2 formed by
previously hydrating the MgO powder.
Since only small batches of MgO-coated vermiculite could be made in the laboratory,
this process had to be repeated a number of times to produce a sufficient quantity of sorbent
for experimental purposes. All of these individual batches were combined in an air-tight
polyethylene container and mixed together. While the preparation procedures were carefully
followed in making each batch, some variation could be expected in the sorbent from batch
to batch. The sorbent itself is inherently heterogeneous, however, so it was hoped that these
variations could be minimized by mixing the various batches. Samples of the combined batch
mixture were randomly selected for comparative surface area analyses as a measure of this
No other research has been reported that would delineate the intrinsic chemical kinetic
parameters associated with the reactions of NOx with MgO-vermiculite sorbents. Likewise,
the probable reaction mechanism has not yet been determined, including the identification of
rate-controlling step(s). A chemico-physical model like the shrinking unreacted-core model
may be used to explain sorbent performance characteristics and provide useful information
related to the optimization of a process employing this novel sorbent for removing NOxfrom
jet engine test cell exhaust, or even other combustion sources. Reviewing the effects of other
operating parameters such as gas concentration, temperature, flow rate, moisture, and oxygen
can provide a more complete picture of the sorptive phenomena occurring. All of these will
be useful to the engineer or scientist who may attempt to employ this medium in an air
pollution control situation in the future.
Based upon the justification for this basic research, the objectives of this study are to
1. Qualify and quantify NOx sorption, singly and in combination, by
MgO-vermiculite using appropriate isotherms. Determine appropriate kinetic parameters
associated with the sorption reactions. Determine the controlling mechanism(s) and whether
these are chemical reaction, diffusion, or mass transfer limited.
This dissertation was submitted to the Graduate Faculty of the College of
Engineering and to the Graduate School and was accepted as partial fulfillment of the
requirements for the degree of Doctor of Philosophy.
Winfred M. Phillips
Dean, College of
Karen A. Holbrook
Dean, Graduate School
NO Removal bv Sorbent Material
NO removal by MgO-coated vermiculite sorbent appeared to depend on inlet NO
concentration and bed temperature. At low inlet NO concentrations (< 10 ppm), NO removal
efficiencies varied from initial values of approximately 60 percent to over 90 percent. In
general, initial NO removal efficiency was greater at 373 K than at 423 or 473 K, indicating
removal by physisorption rather than by chemisorption. The presence of water or water
vapor did improve the removal efficiency of NO, but overall rates of removal were still low.
As previously described, apparent NO removal was enhanced by the presence of oxygen,
through the formation of N02. In their evaluation of NO removal by Ca(OH)2 solids, Chu and
Rochelle (1989) found that the gas- or solid-phase oxidation of NO to N02 played an
important role in the removal of the former. At higher NO concentrations (> 100 ppm), the
overall removal efficiencies were lower (less than 30 percent). Jozewicz et al. (1990) found
no NO (from a 400 ppm NO gas stream concentration) removal by Ca(OH)2 solids without
the presence of oxygen at temperatures between 70 and 180 C. Carbon monoxide (CO) has
been widely used as a probe molecule in surface science studies because it is one of the
simplest adsorbate-adsorbent systems. Mejias et al. (1995) found the interaction of CO on
MgO to be weak and of electrostatic origin, without noticeable chemical contributions. Since
CO and NO are similarly non-reactive, this observation suggests that there may be a fixed NO
sorption capacity, possibly the result of limited surface area available for physisorption.
Figure 4-4 is a representative concentration profile for NO removal by a
MgO-vermiculite sorbent bed, without a significant quantity of N02 present. As can be seen
NO.. Controls for Stationary Sources
Application of NO.c Control Strategies
Based upon well characterized chemical and thermodynamic principles that control
the formation of fuel and thermal NOx, several combustion modifications or changes to
operating conditions can be used for these purposes. In power generation and some waste
disposal applications, "low NOx" burners have been developed whose designs inhibit NOx
formation by controlling the mixing of fuel and air. While some research is being conducted
on jet engine designs to reduce NOx production (Beard, 1990), this approach needs to be
evaluated for its applicability in light of strict and specialized military engine performance
requirements and standards. Combustion modifications can reduce NOx formation by
lowering one or more of the parameters: peak temperature, gas residence time, or oxygen
concentration in the flame zone. It is difficult to employ these controls in a JETC application
due to the changing power settings associated with test and acceptance runs and associated
combustion exhaust fluctuations. Additionally, strict performance standards required during
engine testing limit the applicability of combustion modifications which may make test results
Figure 4-6. First-order kinetic plot ([NO2]in=100 ppm, T=473 K, [O2]=10%). Dashed lines represent 95% confidence limits.
Figure 3-1. Experimental arrangement for packed-bed studies.
TABLE OF CONTENTS
LIST OF TABLES vii
LIST OF FIGURES viii
1. INTRODUCTION 1
Properties and Health Effects of Nitrogen Oxides 1
Environmental Impacts of NOx 4
NOx Formation 7
Fuel NOx 7
Thermal NOx 8
Regulation of NOx Emissions 11
NOx Controls for Stationary Sources 13
Application of NOx Control Strategies 13
Modifications to Operating Conditions 14
Combustion Modifications 15
Exhaust Gas Treatment 16
2. CONTROL OF NOx THROUGH GAS-SOLID INTERACTION 18
Exhaust Gas Treatment Methods 18
Catalytic Methods 19
Non-Catalytic Methods 21
Jet Engine Test Cells 22
U.S. Air Force (USAF) Sponsored Research 25
Vermiculite-based Catalyst 26
Field Studies 30
Related Research 31
GasSolid Interaction 32
constant in the reaction. This light energy is detected by a photomultiplier tube, which
generates an electronic signal that is then converted to a NO concentration reading.
Nitrogen dioxide is measured by difference through its thermal conversion into NO.
A solenoid valve is used to switch to the NOx mode, where all N02 in the gas sample is
converted to NO, based upon the thermodynamic principles previously explained, and is
combined with NO originally in the sample. In the NO mode, gas does not pass through the
thermal converter and therefore contains both NO and N02, with only the NO capable of
reacting with ozone to produce light energy. Thus, the N02 concentration of the sample is
determined by subtracting the signal from the NO mode from the larger signal obtained in the
NOx mode since:
[NOJ [NO] = [N02 ] (3-2)
The instrument specifications, as reported in the manufacturer's manual, indicate
several scales providing an overall measurement range from zero to 5,000 ppm, with a limit
of detection of 50 ppb (0.050 ppm). Background noise level is 25 ppb (0.025 ppm), well
below the detection limit. The instrument exhibits linearity in response of 1% of full scale,
with a zero drift (24-hour maximum) of 50 ppb (0.05 ppm), and a span drift (24-hour
maximum) of 1% of foil scale. The separate scales are linear over their entire ranges, which
was verified by multiple-point calibrations with certified gases. While the interference of
HN03 and HONO with N02 measurements in chemiluminescent analyzers is well documented
(Spicer et al., 1994; Joseph and Spicer, 1978), the concentrations of these interferents were
expected to be low in the system employed. When sufficient moisture was present to form
The process of coal gasification often produces significant quantities of hydrogen
sulfide (H2S). Limestones (either calcined or uncalcined) have been investigated as sorbents
for the removal of these gases through the direct sulfidation of the solids via
thermogravimetric analyses (Krishnan and Sotirchos, 1994). The shrinking unreacted-core
model was employed both quantitatively and qualitatively to derive kinetic parameters and a
to provide a description of the rate-limiting mass transfer processes. In this case, since the
product, calcium sulfide (CaS) is more porous and less voluminous than the CaC03 reactant,
diflusional resistances were limited.
General Applicability of the Shrinking Unreacted-Core Model
From the previous discussion, it is readily seen that the shrinking unreacted-core
model and its derivations are useful tools for describing the complex chemical and physical
processes associated with gas-solid reactions. If the required physical parameters are known,
much detail about the physical rate-controlling mechanisms can be gleaned from a reaction
under study using these models. Combined with the traditional chemical kinetics principles
for determining intrinsic kinetic parameters, data can be collected which can ultimately be
used to improve the use of a gassolid reaction to control gaseous pollutants.
activation energy associated with the sulfation of CaO by a 3,000-ppm S02 gas stream at
temperatures between 540 and 1100 C ranged from approximately 34 to 75 kJ/g-mol. Ruiz-
Alsop and Rochelle (1988) estimated the activation energy of the reaction between S02and
Ca(OH)2 to be approximately 12 kJ/g-mol. Obviously, there can be significant variations in
the measurement of activation energies dependent upon experimental conditions.
Other studies of acid gas-solid reactions have produced results varying by a similar
magnitude. Yang and Chen (1979) used a grain model to describe the reaction between
1.87% COS and CaO in the temperature range between 600 and 900 C. They determined an
activation energy of approximately 18 kJ/g-mol associated with this reaction. The apparent
activation energy for the reaction between 5,000 ppm HC1 and CaO at temperatures between
150 and 350 C determined by Gullett et al. (1992) was approximately 28 kJ/g-mol.
Activation energies determined by Krishnan and Sotirchos (1994) for the reaction between
H2S and CaC03 ranged from 14 to 22 kJ/g-mol. The activation energy associated with the
removal of H2S by zinc ferrite was 54 kJ/g-mol, which corresponded to a strong temperature
dependence of the diffusion-controlled reaction (Karlegard and Bjerle, 1994).
These activation energies associated with initial sorption kinetics that are reported
here varied inversely with N02 concentration. Runs conducted with higher inlet N02
concentration had increasingly lower associated activation energies; in fact, it appeared that
in some cases ([NOJ > 100 ppm) these energies were reduced to zero and sometimes became
negative after 30 to 40 minutes. This finding would support a mechanistic transition from
chemical kinetic control to diffusion control through a product layer, or intraparticle diffusion
control. It is not known whether this is a function of increasing product layer thickness and
Abstract of Dissertation Presented to the Graduate School
of the University of Florida in Partial Fulfillment of the
Requirements for the Degree of Doctor of Philosophy
HETEROGENEOUS-PHASE REACTIONS OF NITROGEN DIOXIDE WITH
VERMICULITE-SUPPORTED MAGNESIUM OXIDE
Larry Thomas Kimm
Chairperson: Eric R. Allen
Major Department: Environmental Engineering Sciences
Controlling nitrogen oxides (NO*) from a non-steady-state stationary source like a jet
engine test cell (JETC) requires a method that is effective over a wide range of conditions.
A heterogeneous, porous, high surface area sorbent material comprised of magnesium oxide
powder attached to a vermiculite substrate has been commercially developed for this purpose.
Data from extensive laboratory testing of this material in a packed-bed flow system are
presented. N02 removal efficiencies, kinetics, and proposed N02 removal mechanisms over
a range of representative JETC exhaust gas characteristics are described. Exhaust gas
variables evaluated included: N02 concentration, temperature, flow rate (retention time),
oxygen content and moisture content. Availability of water and oxygen were found to be
important variables. It is probable that water is necessary for the conversion of MgO to
Mg(OH)2, which is a more reactive compound having thermal stability over the range of
T=373K T=423K ~a~ T=473K
Figure 4-17. N02 penetration versus bed exposure time ([NO2]fa=20 ppm, [O2]=0%).
Bed Exposure Time (min)
Figure 4-46. Shrinking unreacted-core product-layer-diffusion-control equation evaluation, Td=1015 minutes ([NO^j^OO ppm,
T=473 K, [O2]=0%). [ y = O.OOlx + 0.0003, rM).99, Fit Std Error = 0.002, F=822.3],
4-24. Predicted (Ergun equation) versus experimental pressure drop as a function
of superficial velocity for a 0.1 m long bed of MgOvermiculite sorbent
(T=473 K) 126
4-25. Thermal decomposition of Mg(N03)2- 6H20 on vermiculite (temperature
increasing with time) 128
4-26. Thermal decomposition of used MgOvermiculite sorbent (T=523 K) 129
4-27. Comparative bed outlet N02 and NO concentrations versus bed exposure
time showing NO production 131
4-28. Graphical representation of the shrinking unreacted-core model under diffusion-
through-gas-film control 135
4-29. Graphical representation of the shrinking unreacted-core model under chemical-
reaction control 138
4-30. Graphical representation of the shrinking unreacted-core model under diffusion-
through-inert-product-layer control 141
4-31. Shrinking unreacted-core model evaluation ([NOJ^O ppm, T=423 K,
4-32. Shrinking unreacted-core chemical-reaction-control-equation evaluation, xr=397
minutes, ([NO2]in=50 ppm, T=423 K, [O2]=0%) 152
4-33. Shrinking unreacted-core product-layer-diffusion-equation evaluation, td=820
minutes, ([NOJ^O ppm, T=423 K, [O2]=0%) 153
4-34. Shrinking unreacted-core chemical-reaction-control-equation evaluation, t =205
minutes, ([NOJ^SO ppm, T=423 K, [O2]=0%) 154
4-35. Shrinking unreacted-core product-layer-diffusion-equation evaluation, td=957
minutes, ([NOJ^SO ppm, T=423 K, [O2]=0%) 155
4-36. Cumulative mass N02 removed versus bed exposure time ([NOJ^SO ppm,
T=423 K, [O2]=0%) 157
4-37. Cumulative mass N02 removed versus bed exposure time for a long-term run
([NO2]in=50 ppm, T=423 K, [O2]=0%, Gas samples collected from
center of bed) 158
T=373K T=423K -b- T=473K
Figure 4-15. N02 penetration versus bed exposure time ([NO2]in=r00 ppm, [O2]=0%).
Stagnant Gas Film
Progress of Reaction
Unreacted Sorbent Particle
Figure 2-2. Schematic representation of the shrinking unreacted-core model.
Table 1-2. Emission Factors for Nitrogen Oxides (NOx as N02)
Average Emission Factor (as N02)
Household and commercial
8 lb/ton of coal burned
Industry and utilities
20 lb/ton of coal burned
Household and commercial
12-72 lb/1000 gal of oil burned
72 lb/1000 gal of oil burned
104 lb/1000 gal of oil burned
Household and commercial
116 lb/million ft3 of gas burned
214 lb/million ft3 of gas burned
390 lb/million ft3 of gas burned
200 lb/million ft3 of gas burned
0.65 lb/ton of waste burned
2 lb/ton of waste burned
Mobile Source Combustion
113 lb/1000 gal of gasoline burned
222 lb/1000 gal of oil burned
23 lb/flight per engine
9.2 lb/flight per engine
Nitric Acid Manufacture
57 lb/ton of acid product
Source: Wark and Warner, 1981 (Based upon U.S. EPA AP-67, 1970).
Stagnant Gas Film
Figure 4-28. Graphical representation of the shrinking unreacted-core model under diusion-through-gas-film control.
Other Acid-aas-Calcium-based-solid Reactions
Other sorption studies employing the shrinking unreacted-core model and its
derivations have been conducted to study the control of other acid gases. The reaction of
hydrogen chloride (HC1) with CaO is of interest for the control of acid vapors emitted from
municipal and hazardous waste incineration operations. Gullett et al. (1992) used a
specialized fixed-bed reactor to study this reaction and determine the controlling mechanism
and kinetics. They examined the relative importance of chemical reaction and product layer
diffusion control using the combined resistance shrinking unreacted-core model. Their
research also provided data on how operating parameters like reaction temperature and gas-
phase concentration affect sorption. The strong resistance to chemical reaction provided by
solid-state diffusion was proved to follow a grain model by Weinell et al. (1992). Pakrasi
(1992) performed kinetic studies of HC1 removal by hydrated lime powder in a bench-scale
fixed-bed reactor. His studies included a thorough examination of the chemical kinetics and
possible mechanism associated with the HC1CaO reaction. Relative humidity played a key
role in determining HC1 removal rate and the extent of solid sorbent conversion. Other
relevant variables such as gas concentration and temperature were also examined. Incomplete
conversion (compared to that theoretically predicted stoichiometrically or by the shrinking
unreacted-core model), was the result of increased diffusional resistance in the product layer.
Both the shrinking unreacted-core model and an empirical model were used to interpret
observed conversion versus time data.
condition occurred after approximately 5-10 minutes of bed exposure time, providing the
most reliable results for subsequent experiments and data analyses. While these data were
most useful for the prediction of sorbent behavior with time, it made the accurate
determination of intrinsic (or apparent) activation energies more difficult. Data on the
activation energies associated with NOx removal by surface reaction with the
MgO-vermiculite sorbent will be presented in the following section, in which the effects of
reaction temperature are described.
Effects of Operational Variables
Numerous experiments were conducted to thoroughly evaluate the effects of
operational variables of primary importance, such as reactive gas concentrations, humidity,
reaction temperature, and gas flow rate. The combination of these results provided a clear
picture, from which conclusions regarding probable reaction mechanisms and the dominant
factors governing the NOx removal capabilities of the sorbent material were drawn.
Effects of NO-. Concentration
The effects of N02 concentration on overall removal rates were dependent upon the
bed temperature at which data were collected. Figures 4-8 through 4-10 show representative
N02 penetration versus bed exposure time data as a function of inlet N02 concentration for
the three reaction temperatures evaluated. N02 penetration is defined as the percentage
(fraction) of inlet N02 exiting the bed at any given bed exposure or reaction time, or Cout/Cin.
Obviously, this value is (in percent) 100% minus the N02 removal efficiency percentage. In
1 (1-X)1/3 1 3(1-X) 2/3+ 2(1X)
* 423K-R 423K-D
Figure 4-31. Shrinking unreacted-core model evaluation ([NO2]in=50 ppm, T=423 K, [O2]=0%).
LIST OF REFERENCES
40 CFR 50, Appendix F., "Measurement Principle and Calibration Procedure for the
Measurement of Nitrogen Dioxide in the Atmosphere (Gas Phase Chemiluminesence)."
Baiker, A.; Dollenmeier, P.; Glinksi, M.; and Reller, A., "Selective Catalytic Reduction of
Nitric Oxide with Ammonia: Part I, Monolayer and Multilayers of Vanadia Supported on
Titania," Applied Catalysis. 35:351-364, 1987a.
Baiker, A; Dollenmeier, P.; Glinski, M.; and Reller, A., "Selective Catalytic Reduction of
Nitric Oxide with Ammonia: Part II, Monolayers of Vanadia Immobilized on Titania Silica
Mixed Gels," Applied Catalysis. 35:365-380, 1987b.
Bamford, C.H.; Tipper, C.F.H.; and Compton, R.G., Comprehensive Chemical Kinetics.
Volume 21, Reactions of Solids with Gases, Elsevier Publishers; Amsterdam, pp 131-134,
Beard, J., "Computer Modelling Makes Jet Engines Less Noxious," New Scientist. 30, 1990.
Berman, E.; Dong, J.; and Lichtin, N.N., Photopromoted and Thermal Decomposition of
Nitric Oxide by Metal Oxides. ESL-TR-91-32, HQ AFESC, Tyndall AFB, Florida, 1991.
Bhatia, S. K. and Perlmutter, D. D., "A Random Pore Model for Fluid-Solid Reactions: II.
Diffusion and Transport Effects," AIChE Journal. 27(2):247-254, 1981a.
Bhatia, S. K. and Perlmutter, D. D., "The Effect of Pore Structure on Fluid-Solid Reactions:
Application to the S02-Lime Reaction," AIChE Journal. 27(2):226-234, 1981b.
Bhatia, S. K. and Perlmutter, D. D., "Effect of the Product Layer on the Kinetics of the
C02-Lime Reaction," AIChE Journal. 29(l):79-86, 1983.
Biyani, P. and Goochee, C. F. "Nonlinear Fixed-Bed Sorption When Mass Transfer and
Sorption Are Controlling," AIChE Journal. 34(10): 1747-1751, 1988.
temperatures evaluated. Gaseous oxygen serves to oxidize NO to N02, the latter being more
readily removed from the gas stream. The presence of oxygen also serves to offset thermal
decomposition of N02 or surface nitrite/nitrate. Effective "lifetime" and regenerability of the
exposed sorbent material were also evaluated. N02 removal efficiencies were found to
greatly exceed those for NO, with a maximum value greater than 90 percent. The effective
conversion of NO to N02 is a crucial requirement for removal of the former. The reaction
between N02 and MgOvermiculite is first-order with respect to N02. The temperature
dependence of the first-order rate coefficients provided evidence that data were collected in
the region of chemical-reaction control. Activation energies associated with this reaction
ranged from approximately 20 and 36 kJ/g-mol when oxygen was not present and 15 to 25
kJ/g-mol when oxygen was present in the system. The shrinking unreacted-core model was
used to describe the physical and chemical mechanisms occurring in the removal of N02 from
a flowing gas stream. It appeared that the reaction begins with control by chemical reaction
and progressed to control by diffusion processes as reaction progressed. An empirical
relationship was also developed which allowed for the prediction of N02 removal with
increasing bed exposure time. The range of temperatures and concentrations evaluated, while
valid for the representation of simulated jet engine test cell conditions, appeared to be a
transition region making the absolute determination of rate-limiting mechanism(s) difficult.
With impending regulations aimed at controlling JETCs as stationary sources of NOx, results
from these studies will be useful to environmental engineers developing air pollution controls
for similar sources. Knowledge of parameters affecting the efficiency and capacity of NOx
control systems employing this medium is necessary to ensure compliance with regulations.
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LIST OF TABLES
1-1. Physical properties of nitrogen oxides (NxOy) 2
1-2. Emission factors for nitrogen oxides (NOx as N02) 6
2-1. Physical properties of selected Mg-containing inorganic compounds 28
3-1. USAF FI 10 turbine engine emissions data (as reported) 54
4-1. BET surface areas of selected samples of laboratory-prepared
MgO-vermiculite sorbent 82
4-2. Intrinsic first-order rate coefficients (s'1) for N02 removal by
MgO-vermiculite sorbent ([O2]=0%) 100
4-3. Intrinsic first-order rate coefficients (s'1) for NOz removal by
MgO-vermiculite sorbent ([O2]=10%) 106
Table 4-3. Intrinsic first-order rate coefficients (s'1) for N02 removal by MgOvermiculite sorbent ([O2]:=10%)
N02 Concentration :
Reaction Temp ( K):
C=C0 exp(-kt) (4-2)
where C0= Inlet N02 concentration in ppm and t=bed residence time in seconds.
From Equation (4-2) it can be seen that a plot of ln(C/C0) versus t should be linear,
with a slope of -k, if the reaction is first-order. Data from Figure 4-5 are plotted in this way
in Figure 4-6. A first-order kinetic expression appeared to describe N02 removal and was
used as a basis to model N02 decay. Plots similar to that shown in Figure 4-6 were used to
determine rate coefficients for different experimental conditions. Having established in all
earlier runs evaluated that data from five sampling points produced sufficiently linear first-
order plots, only three points were used to determine rate constants in subsequent runs,
concentrations at the inlet and outlet and at a point within the bed.
Since the bed surface nature is changing with time during runs, values for k also
change with time. Figure 4-7 is a representative figure showing the decrease in k-values as
reaction (exposure) progresses. Also, as reaction progresses, the rate of change in rate
coefficient values between readings decreases. This decrease in first-order rate coefficients
with increasing bed exposure time may be associated with a change in activation energy,
possibly indicative of a transition from one rate-limiting mechanism to another. Noticing this
trend allowed for the derivation of a predictive empirical relationship between the first-order
rate constant value and bed exposure time, which will be presented later. In the context of
the shrinking unreacted core model, this may represent the transition from chemical reaction
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process, which would be a slow process. It was found that an (dynamic) equilibrium
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Figure 4-27. Comparative bed outlet N02 and NO concentrations versus bed exposure time showing NO production.
means and standard deviations were shown on the control charts. Based upon control chart
results, instruments were recalibrated when necessary. Quality assurance was maintained by
showing that all quality control systems were in good order.
As the NO/NOx chemiluminescent analyzer has a flow bypass system installed to
ensure that samples are always collected at ambient pressure, all experimental measurements
were made at the same bypass flow rate used during the initial calibration. Failure to do so
can result in gas concentration measurement errors as great as 10 percent from one end of
the bypass flow scale to the other. Additionally, a NOx generator (Model 100, Thermo
Environmental Instruments, Franklin, Massachusetts) was used to determine the actual
analyzer NOx converter efficiency and ensure that the efficiency exceeded 95%.
Sorbent Surface Area Determination
In preparation for packed-bed studies, BET surface areas of selected samples of
laboratory-prepared MgO-vermiculite sorbent, Sorbtech-supplied sorbent, and raw coarse
vermiculite were determined using a Micromeretics ASAP 2000 automated surface-area and
pore size analyzer. Duplicate samples were run to verify the validity of the data. Small
samples of sorbent (approximately one gram) were first degassed at an absolute pressure of
10 to 15 mm Hg at 623 K for approximately eight hours. Nitrogen gas (in helium) was
sequentially added to the sample tube at a temperature of 77 K. The volumes of nitrogen
adsorbed at various partial pressures between approximately 0.1 and 0.3 atmosphere were
In k (In s"1)
Bed Exposure Time
B- 5 minutes 10 minutes ~b- 15 minutes -20 minutes
Figure 4-21. Arrhenius plot of In k versus 1000/T (T between 473 and 423 K, [NO2]m=100 ppm, [O2]=0%).
0 0.2 0.4 0.6 0.8 1 1.2
Residence Time (sec)
Bed Exposure Time
5 minutes 10 minutes 15 minutes 20 minutes
Figure 4-7. First-order kinetic plot ([NO2]in=100 ppm, T=473 K, [O2]=10.5%).
Performance during sorption/desorption cycles was evaluated on the basis of weight gain and
loss. It appeared that there was a loss of surface area when the material was regenerated at
excessively high temperatures (> 800 C). Regeneration consisted of three steps: 1) drying;
2) heating to a temperature above 550 C (in the presence of N2, or CO or CH4 to reduce off
gassing NOx); and 3) cooling. Of these, CO is the gas of choice. Heating during regeneration
was accomplished using a rotary-kiln calciner, a vertical tube apparatus, and a horizontal
conveyor kiln. Wickham and Koel (1988) have published an excellent review on the
reduction of NOx by CO.
A review of current literature indicates that no research other than that already
described has been conducted on this MgO-vermiculite sorbent. As a result, no data on
intrinsic kinetics or reaction mechanism(s) exist. Significant amounts of related research,
however, have been conducted on similar acid/acid anhydride gas-base/gas-solid systems.
The results of these studies have been used to design and construct appropriate experimental
systems to collect data for interpretation using proven and accepted sorption study
techniques. A short review of some of the fundamentals of gassolid interactions and
chemisorption is necessary to better understand the complex phenomena involved in these
concentrations. For this reason, the apparent first-order kinetics was not affected by the
presence of 02 in exhaust gases.
Representative plots of N02 penetration versus bed exposure time, similar to those
shown for experimental runs where oxygen was present, are shown at Figures 4-11 through
4-13. In Figure 4-11, at a reaction temperature of473 K, initial N02 penetration values were
less than 1% for all three N02 concentrations evaluated. In this case, an inlet N02
concentration of200 ppm was not evaluated, since the N02 cylinder contained only 200 ppm
gas, and therefore, dilution with air would have decreased this concentration. The shapes of
the penetration curves are similar to those seen in Figure 4-8, with N02 penetration remaining
low (and removal efficiency remaining high) for an inlet N02 concentration of 20 ppm.
Overall N02 penetrations for runs with oxygen present remained lower at a reaction
temperature of473 K when compared to runs conducted without oxygen. The presence of
oxygen may facilitate the continued N02 removal by the sorbent.
This distinction between N02 penetration in the presence and absence of 02 did not
apply for all N02 concentrations at a reaction temperature of 423 K (Figure 4-12). N02
penetration after a bed exposure time of one hour was actually higher for an inlet N02
concentration of 100 ppm when oxygen was present compared to when oxygen was absent.
At 50 ppm NO^ the penetrations were approximately the same and were less at 20 ppm. At
this temperature (423 K), oxygen may aid in the removal of low concentrations of N02. At
a reaction temperature of 373 K (Figure 4-13) the 02 effect trend was reversed. Similar to
the effect seen in Figure 4-10, at the lowest temperature evaluated, it appears that a sufficient
gassolid concentration gradient must exist to provide the driving force for reaction to occur.
1 [NO ]
Figure 4-25. Thermal decomposition of Mg(N03)2. 6H20 on vermiculite (temperature increasing with time).
1 [NO ]
Figure 4-26. Thermal decomposition of used MgOvermiculite sorbent (T=523 K).
I certify that I have read this study and that in my opinion it conforms to
acceptable standards of scholarly presentation and is fully adequate, in scope and quality,
as a dissertation for the degree of Doctor of Philosophy.
Eric R. Allen, Chair
Professor of Environmental
I certify that I have read this study and that in my opinion it conforms to
acceptable standards of scholarly presentation and is fully adequate, in scope and quality,
as a dissertation for the degree of Doctor of Philosophy.
Dale A. Lundgren
Professor Emeritus of Environmental
I certify that I have read this study and that in my opinion it conforms to
acceptable standards of scholarly presentation and is fully adequate, in scope and quality,
as a dissertation for the degree of Doctor of Philosophy.
W. Emmett Bolch, Jr.
Professor of Environmental
I certify that I have read this study and that in my opinion it conforms to
acceptable standards of scholarly presentation and is fully adequate, in scope and quality,
as a dissertation for the degree of Doctor of Philosophy. /} y /
Robert J. Har
Professor of <
I certify that I have read this study and that in my opinion it conforms to
acceptable standards of scholarly presentation and is fully adequate, in scope and quality,
as a dissertation for the degree of Doctor of Philosophy.
Joseph D. Wander
Adjunct Associate Professor of
Environmental Engineering Sciences