United States
Environmental Protection
Agency
Industrial Environmental Research
Laboratory
Research Triangle Park NC 27711
 Research and Development
EPA-600/S7-81-151  Oct. 1981
Project  Summary
Fuel  NOx  Control  by
Catalytic  Combustion

E. K. Chu, K. D. Seifert, R. M. Kendall, and J. P. Kesselring
  This report describes the results of
an experimental  study to define
operating conditions for catalytic
combustors that give low levels of
NOx emissions for fuel-bound nitrogen
compounds, and to quantitatively
determine the fate of fuel nitrogen
during catalytic combustion. Tests
were conducted with platinum  and
nickel oxide catalysts over a range of
test conditions, using ammonia  and
methylamine as model fuel nitrogen
compounds. Fuel NO > emissions were
found to be strongly dependent on
catalyst type, but varying mass through-
put, bed temperature, fuel, and  fuel
nitrogen type had virtually no effect on
fuel NO,. The dominant nitrogenous
products resulting from the catalytic
combustion of a nitrogen-containing
fuel were NO, N2, NH3, and HCN.
  This Project Summary was devel-
oped  by EPA's Industrial Environ-
mental Research Laboratory, Research
Triangle Park, NC, to announce key
findings of the research project that is
fully documented in a separate report
of the same title (see Project Report
ordering information at back}.

  As a result of this experimental study,
an improved understanding of fuel NO,
formation during catalytic combustion
has been gained. Knowledge gained in
this report may lead to further develop-
ment of catalytic burners which control
both thermal and fuel NO,. One feasible
concept which was demonstrated in
previous work and  further verified by
the  present  study is  the two-stage
catalytic combustion system. Also, data
obtained  under the present study
indicate that the design of a lean low
NO, combustor may be possible. This
summarizes the conclusions reached
and the concepts formulated under this
study, and makes recommendations for
further study.
  Based on results of screening tests,
the bed operating temperature was
shown to  have only a slight effect on
fuel NO,  emissions. Under fuel-lean
conditions, the bed operating tempera-
ture affected fuel NO,  emissions in-
directly, depending on the CO emissions
and the stoichiometry.  High CO emis-
sions tended  to  suppress fuel  NO,
emissions, and this effect became less
significant as the test condition became
leaner. Under  fuel-rich conditions, an
increase in the.bed operating tempera-
ture  tended to shift the fuel NO.
minimum slightly toward stoichiometric
conditions.
  The mass throughput was found to
have no significant effect on fuel NO,
emissions under fuel-lean conditions.
Under fuel-rich conditions, however, an
increase in the mass throughput ap-
peared to broaden the fuel NO, minimum.
In addition, a second fuel NO, minimum
was observed for cases where both the
mass throughput and the bed operating
temperature were low.
  No significant effects on fuel  NO,
emissions due  to the difference in fuel
type were observed. Under fuel-lean
conditions  with natural  gas, fuel NO,
emissions  maximized at 130 percent
theoretical air  and declined slightly a;
theoretical air  was further increased
With propane,  fuel NO, emissions alsc
maximized at the same stoichiometn
but remained  relatively constant a:

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    theoretical  air was further increased.
    Under fuel-rich conditions, the fuel NO,
    minimum for propane appeared to be
    somewhat broader and slightly deeper
    than that for natural gas.
      Fuel  NO, emissions were found to be
    strongly dependent on  the catalyst
    type—a more active catalyst results in
    higher  fuel NOX emissions  with other
    operating parameters  held constant.
    Under  fuel-rich conditions, the less
    active  NiO/Pt catalyst achieved a
    conversion  of NH3 of only 25 percent,
    while the more active Pt catalyst had a
    conversion  of 80 percent.
      Fuel  NOx formation was found  to be
    insensitive to the molecular structure of
    the  chemically  bound  nitrogen  com-
    pounds tested. This indicates that the
    pyrolysis process was not the controlling
    step for fuel NOX formation, if the
    chemically  bound  nitrogen  content  is
    highly volatile.
      The percentage of NH3 conversion to
    fuel N0« was  found  to be inversely
    proportional to  the chemically bound
    nitrogen content. This phenomenon
    was probably due to the destruction
    reaction prompted by the excess NHs.
      Based on results of detailed  tests, it
    was verified that NO, N2, NH3, and HCN
    are the dominant products  of the
    chemically  bound  nitrogen  conversion
    process. fs^O was not detected for any
    condition tested.  With the addition of
    HzS to the reactive mixture, NO emis-
    sions were slightly increased under
    fuel-rich conditions and inhibited  at
    stoichiometric conditions.  A nitrogen
    balance within  reasonable accuracy
    was not obtained with H2S addition. The
    error may be due to the interference of
    sulfide with the specific ion electrode
    measurements for HCN and NH3.
                                        To  obtain further  understanding  of
                                      fuel NOx formation during  catalytic
                                      combusiton, as well as to develop low
                                      NOx combustors, the following studies
                                      are recommended:

                                        • A study of CO-NO-catalyst reactions
                                           under fuel-lean conditions.
                                        • Test of fuels which contain chemi-
                                       Fuel/Air
  cally bound nitrogen—especially
  those which  contain refractory
  chemically bound nitrogen.
• A study of NOx-SOx interactions
  during  catalytic combustion for
  both fuel-rich and fuel-lean condi-
  tions.
• Development of  a  fuel-lean low
  NO« combustor; e.g..
                                                                               Secondary
                                                                               Fuel
CO Generating
Catalyst


Reduction
Catalyst
CO + NO - Nz


Cleanup
Catalyst
                                         £ K. Chu, K. D. Seifert, R. M. Kendall, and J. P. Kesselring are with Acurex
                                           Corporation, 485 Clyde Avenue. Mountain View, CA 94042.
                                         G. Blair Martin is the EPA Project Officer (see below).
                                         The complete report, entitled "Fuel NO* Control by Catalytic  Combustion,"
                                           (Order No. PB 82-102 351; Cost: $11.00, subject to change) will be available
                                           only from:
                                                 National Technical Information Service
                                                 5285 Port Royal Road
                                                 Springfield. VA 22161
                                                 Telephone: 703-487-4650
                                         The EPA Project Officer can be contacted at:
                                                 Industrial Environmental Research Laboratory
                                                 U.S. Environmental Protect/on Agency
                                                 Research Triangle Park.  NC 27711
United States
Environmental Protection
Agency
                              Center for Environmental Research
                              Information
                              Cincinnati OH 45268
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