The ability of non-hydrocarbon fuels such as CO and H2 to reduce nitric oxide under conditions
relevant for the reburning process is investigated experimentally and theoretically. Flow reactor
experiments on reduction of NO by CO and H2 are conducted under fuel-rich conditions, covering
temperatures of 1200−1800 K and a range of stoichiometries and reactant levels. Bench and
pilot scale results from literature on reburning with CO, H2, and low calorific value gases are
also considered. The experimental data are interpreted in terms of a detailed reaction mechanism,
and the reactions responsible for removal of NO are identified. The experimental results indicate
that under typical reburn process conditions these non-hydrocarbon fuels may remove 20−30%
of the nitric oxide entering the reburn zone. However, results indicate that the process potential
increases with temperature and reburn fuel fraction, and at high temperatures and reburn fuel
fractions of about 30%, the reduction efficiency approaches that of hydrocarbon gases. If dilution
effects and the lowering of the primary zone NO (maintaining the overall load) are accounted
for, the reduction potential is further increased. Modeling results indicate that the mixing process
may affect the NO reduction in the reducing zone. The modeling predictions are in qualitative
agreement with the experimental results but tend to underestimate the reduction of NO.
Conversion of NO to N2 in the reburn zone proceeds primarily through the following sequence:
H + NO + M ⇌ HNO + M, HNO + H ⇌ NH + OH, NH + NO → N2 + ... The implications of the
results for reburning with fuels with a low hydrocarbon content are discussed, with special
emphasis on gasified fuels.
The branching fraction for the NH2 + NO reaction has
been determined in the temperature range 1210−1370
K from flow reactor experiments on the
NH3/NO/O2 and
CO/NH3/NO/O2 systems. The branching
fraction
is defined as α =
k
1/(k
1 +
k
2), where NH2 + NO → NNH + OH
(1) and NH2 + NO → N2 + H2O
(2). The
experiments were performed at very low oxygen concentrations to
minimize the impact of secondary reactions.
The results show that α increases gradually from a value of 0.35
± 0.04 at 1211 K to 0.45 ± 0.02 at 1369
K. The data blend smoothly with the most recent direct
measurements and confirm the significant rise in
branching fraction suggested by previous high-temperature
determinations in static reactors and flames.
A laboratory study of the hybrid reburning/SNCR technique has been
performed under flow
reactor conditions. This technique involves the use of a selective
reducing agent in the presence
of combustibles (mainly CO) arising from the reburning zone. The
impact of CO and O2
concentrations, NH3/NO ratio, as well as the presence of
HCN has been investigated as a function
of the temperature in the range 700−1300 K. The results show
that CO in concentrations typical
of the rich/lean transition in reburning shift the regime for NO
reduction in the SNCR process
to temperatures below 1000 K and cause a narrowing of the temperature
window. The NO
reduction potential is largely unaffected compared to conditions with
low CO, and the effect
varying the O2 concentration in the range 0.5−4.0% as
well as of adding of HCN is found to be
insignificant. Synergistic effects between reburning and SNCR are
only observed in a narrow
range of operating conditions with very low concentrations of CO and
O2. Model predictions
using a detailed reaction mechanism generally compare favorably with
the experimental results.
The present results indicate that a reduction of the CO level from
the reburn zone is required
before the SNCR chemistry is initiated. This can be obtained
either by staging the burnout air
or by injecting the N-agent in an aqueous solution to delay
reaction.
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