United States
                   Environmental Protection
                   Agency
Industrial Environmental Research
Laboratory
Research Triangle Park NC 27711
                   Research and Development
EPA-600/S9-83-001  May 1983
&EB\         Project  Summary
                   Proceedings  of the  Fifth
                   Fundamental Combustion
                   Research  Contractors Workshop
                    M. P. Heap
                     These proceedings are for The Fifth
                   EPA Fundamental Combustion Re-
                   search Contractors Workshop, held
                   January 23, 24.  and 25, 1980, in
                   Newport Beach. CA. The purpose of
                   the workshop was to exchange infor-
                   mation between the various contrac-
                   tors engaged in fundamental combus-
                   tion research for EPA and to coordinate
                   their activities. In addition, the work-
                   shop provided for a review of EPA's
                   Fundamental Combustion Research
                   (FCR) Program by EPA's Science Ad-
                   visory Board. The five conference ses-
                   sions dealt with gas-phase chemistry
                   and heterogeneous NO reduction,
                   chemical and physical effects of ther-
                   mal decomposition, bench-scale reac-
                   tor studies, two-phase turbulent flames,
                   and model development
                     The main thrust of the FCR program
                   is elucidating the mechanism of NO
                   formation from fuel bound nitrogen.
                   Several papers addressed the gas-phase
                   conversion of fuel nitrogen species to
                   NO, N2, HCN. or NH3. Advanced diag-
                   nostic techniques were used to inves-
                   tigate the physical  changes  taking
                   place during the thermal decomposi-
                   tion of pulverized coal particles. Bench-
                   scale reactor data were presented on
                   the conversion of fuel bound nitrogen
                   to NO in liquid- and solid-fuel flames.
                   Studies on turbulent diffusion flames
                   included detailed  characterization of
                   nonswirling coal flames and methods
                   of measuring droplet size from fuel oil
                   atomizers.  Engineering analysis is a
                   strong  component of EPA's FCR pro-
                   gram, and papers were presented on
                   the analysis of turbulent diffusion
                   flames.
  This Project Summary was developed
by EPA's Industrial Environmental Re-
search Laboratory, Research triangle
Park. NC, to announce presentations
at the workshop that are fully docu-
mented in  a separate report of the
same title (see Project Report ordering
information at back).

Introduction
  This report summarizes the proceed-
ings of the Fifth EPA Fundamental Com-
bustion Research (FCR) Contractors Work-
shop, held January 23,24, and 25,1980,
in Newport Beach, CA. The workshop
brought together current EPA contractors
engaged in combustion research activities,
to ensure efficient technology transfer
between the various groups working in
related areas Members of EPA's Science
Advisory Board also attended the work-
shop to review the activities for EPA
management
  The workshop was opened by W. &
Lanier of IERL-RTP, Project Officer for the
FCR program He welcomed the partici-
pants, expressing the hope that the work-
shop would be a forum for discussion and
interchange which would benefit all of the
projects. He informed the participants of
EPA/I ERL-RTFs Combustion Research
Branch activities in the area of NOx control
and  how the research programs were
planned to  provide input  for the tech-
nology development programs. It was
stated that many of the research projects
had  relatively short-term goals because
low-NOx systems  were currently being
developed and installed  However, in
keeping with the fundamental nature of
the program, several programs had been
included which were expected to pay off in
the long term.

-------
  The FCR program focuses on the control
of NOX and primary related pollutants
generated by large, confined, one-atmos-
phere,  turbulent diffusion flames from
pulverized coal,  synfuels, or residual oils
which radiate to cold walls. The various
projects funded  by FCR were selected to
provide a deeper insight into the spectrum
of processes characterizing these flames.
  W.  S. Lanier, EPA/IERL-RTP,  chaired
Session I, Gas-Phase Chemistry and Heter-
ogeneous NO Reduction, which included
the following papers:

  "Modeling of  Fuel-Nitrogen Chemistry
  in Combustion: The Influence of Hydro-
  carbons," J.  M.  Levy,  MIT  Energy
  Laboratory.

  "Development of a Kinetic Mechanism
  to Describe the Fate of Fuel Nitrogen in
  Gaseous Systems," T. L Corley, Energy
  and Environmental Research Corpora-
  tion.

  "NOX Formation in Flat, Laminar, Op-
  posed-Jet Methane Diffusion Flames,"
  W. A. Hahn and J. 0. L Wendt, University
  of Arizona.

  "The  Formation and  Destruction of
  Nitrogenous Species During Hydrocar-
  bon/Air  Combustion,"  D.  W.  Blair,
  Exxon Research and Engineering Com-
  pany.

  "Laboratory Scale  Coal Studies," J. M.
  Beer, A. F. Sarofim, J. M.  Levy, D.
  Altrichter, and L Timothy,  Massachu-
  setts Institute of Technology.

  " Mechanisms of Nitric Oxide Reduction
  on  Solid Particles," G. G. de Soete,
  Institut Francais du Petrole.

Papers in Session II, Thermal Decompo-
sition-Chemical  and  Physical  Effects,
chaired by A. F. Sarofim, MIT, were:

  "Volatility of Fuel Nitrogen," R Gay, A.
  E.  Axworthy,  V. H.  Dayan,  and H. L.
  Recht Rockwell International.

  "High Temperature Pyrolysis of Oil
  Droplet and Coal Particle Streams," J.
  M. Beer, A. F. Sarofim, S. P. Hanson, and
  A.  K. Gupta, Massachusetts Institute of
  Technology.

  "The Characterization of Coals During
  Thermal Decomposition," P. R Solomon,
  United Technologies Research Center.

  "The Physical  and  Chemical  Effects
  Occurring During the Thermal Decompo-
  sition of Coal Particles and Oil Droplets,"
  W. R Seeker, G. S. Samuelsen, and M.
  P.  Heap, Energy and Environmental
  Research Corporation.

Session III, Bench-Scale Reactor Studies,
was chaired by J. P. Longwell, MIT. The
papers presented included:

  "Pollutant Formation During the Com-
  bustion of Residual Fuel Oils in a Well-
  Stirred Reactor," M. Murphy,  Battelle
  Columbus Laboratories.

  "Pollutant Formation from Combusting
  Pulverized Coal Clouds," P. M. Goldberg,
  H. Tong, and R. Kendall, Acurex Corpo-
  ration.

  "Reactor Studies to Assess the Impact
  of  Fuel  Characteristics on  Fuel  NOX
  Formation," M. P. Heap, D. W. Pershing,
  G. C. England, S. L. Chen,  R. Nihart, and
  D.  P. Rees,  Energy and Environmental
  Research Corporation.

  "Pollutant Formation During Fixed-Bed
  and Suspension Coal Burning," D. W.
  Pershing, University of Utah.


The  papers  in Session  IV,  Two-Phase
Turbulent Diffusion Flames, chaired by W.
S. Lanier, were:

  "An Experimental Approach to the Study
  of Heavy Oil Spray Combustion in Shear
  Layers," A. Vranos, United Technologies
  Research Center.

  "Spray Characterization,"  W. R. Seeker,
  and G. S. Samuelsen, Energy and Envi-
  ronmental Research Corporation.

  "The Application of Droplet Sizing Inter-
  ferometry and Holography to the Mea-
  surement of Spray Droplet Size and
  Velocity," C. F. Hess and W. D. Bachalo,
  Spectron Development Laboratories.

  "Characterization  of  Long Turbulent
  Pulverized Coal Diffusion Flames,"  R.
  Payne, The International Flame Research
  Foundation.
The chairman of Session V, Model Devel-
opment was T. J.  Tyson,  Energy and
Environmental Research Corporation.  He
introduced the following papers:

  "Development of a Coherent Flame
  Model for Turbulent Chemically React-
  ing Flows,"  F. E. Marble  and J.  E.
  Broadwell, California Institute of Tech-
  nology.

  "General Kinetic Analysis Codes," C. J.
  Kau and T. J. Tyson, Energy and Environ-
  mental Research Corporation.
Abstracts of Papers

Introduction to the Fifth EPA
Fundamental Combustion
Research Contractors
Workshop

W. S. Lanier
  Organizationally, the Fundamental Con
bustion Research (FCR) Program is fun(
ed through the Combustion Researc
Branch (CRB) of EPA's Industrial Enviror
mental Research Laboratory at Researc
Triangle Park(IERL-RTP). The CRB chart)
calls for  the development  of emissic
control technology for pollutants gene
ated by stationary combustion  source
through modification of the basic combu,
tion process. Consequently, the  primai
focus of the FCR program is the formatic
and destruction of NOX in flames. Boile
firing  pulverized coal and high-nitrog<
liquid fuels  produce most of the  N(
emitted by stationary sources. Thus, tl
projects funded as part of the FCR pr
gram concentrated on the mechanism
fuel nitrogen  conversion in large tw
phase turbulent diffusion flames.
  As regards the mechanics of the FC
program, when a particular research top
is selected for  investigation, a number
options are open. If the prime contract
Energy and Environmental Research (EE
Corporation, has an existing expertise, o
no expertise is  known to exist there is t
option to pursue the research topic at EE
This has been the dominant choice 1
numerical  modeling activities. Other c
tions  open  include sole-source,  limit
source, or full competitive procurement
general, the sole-source or limited co
petitive route has been selected.  Anotf
option allows the CRB to fund the activ
directly through either a contract or gra
Consequently,  a variety of contracting (
tions are available, and many have be
used.

Modeling of Fuel Nitrogen
Chemistry in Combustion: Tl
Influence of Hydrocarbons

J. M.  Levy
  Despite  uncertainties in the currer
available mechanistic and  kinetic  d
base,  it is possible to  model (althoi
imperfectly)  fuel nitrogen conversion
the presence of simple fuels. Unfortun<
ly, there is a strong coupling between 1
nitrogen and hydrocarbon chemistry.
the heat release mechanism for real fi
is complex,  it  is necessary to develo
methodology  to treat the hydrocarl

-------
Tiechanism in some global manner which
:an be linked with the fuel nitrogen mech-
jnism. Consequently, the conversion of
:uel  bound nitrogen in  a hydrocarbon
combustion environment requires a reac-
ion mechanism which can be viewed as a
synthesis of three subsets: fuel nitrogen,
hydrocarbon oxidation, and hydrocarbon/
nitrogen  interactions.  The outstanding
phenomenological question raised in con-
nection with the modeling of hydrocarbon
chemistry pertains to the fate of the free-
radical pool. Hydrocarbon fragments ef-
fectively catalyze radical recombinations,
and free radical overshoots are much less
in hydrocarbon  systems than  in hydro-
carbon-free systems.

Development of a Kinetic
Mechanism to Describe the
Fate of Fuel Nitrogen in
Gaseous Systems

T. C. Corley
  This paper concerns the development of
a kinetic mechanism which can  predict
adequately the conversion of fuel nitrogen
compounds to NO in gaseous systems. A
four-step approach was used to develop
the mechanism: ( 1 ) assemble elements of
the reaction model, (2) select data sets for
malysis to resolve critical questions under
well-defined reaction conditions, (3) iden-
tify and correct deficiencies by comparing
with data generated in shock tubes and
flames, and (4)  use the completed sub-
element of  the reaction mechanism as a
known element of more complex systems.
  Application of the procedure to elements
of the reaction model indicates:

  •  CH2O - CO - H2 - Oa system is
      complete.
      — HCO is  important for chain-
         branching in rich, wet CO flames.
      — Decomposition and oxidation of
         CHaO is slower than previous
         predictions.
            a mechanism requires addi-
      tional analysis.
      — Chain-branching path required:
         NH2 + NO = N2 + H+OH.
      — Ignition  delay  controlled by:
         NH2 + 02 =  HNO + OH.
      — N2 HI species may be important
         for rich processing of NHa.
      — Overall oxidation  of NHs too
         slow with present mechanism.
  •   HCN-02 reaction model must be
      compared with other data.

  •   Hydrocarbon mechanisms require
      further study.
      —  Ignition delays for CH4-02 pre-
         dicted


NOx Formation in Flat, Laminar,
Opposed-Jet Methane Diffusion
Flames

W. A. Hahn and J. 0. L Wendt
  The detailed structure of a flat, laminar,
opposed-jet diffusion flame can be mod-
eled. By properly coupling the momentum
and energy conservation equations and by
using detailed finite rate combustion kine-
tics,  it is possible to model the detailed
structure of a flat laminar, opposed-jet
diffusion  flame.
  Such a flame is one-dimensional, if the
proper velocity boundary conditions are
used.  Measurements with a laboratory
CH4/N2/02 opposed-jet diffusion flame
gave good agreement  with predictions
with respect to one-dimensionality, tem-
perature,  and species profiles within the
reaction zone.  However, the actual loca-
tion  of the reaction zone was displaced
slightly.   The theoretical/experimental
tool  developed was used to test kinetic
mechanisms of NO formation from fuel
nitrogen.  In this case, anhydrous ammonia
was introduced first with the fuel, and then
with the  oxidizer.  The formation of NO
was predicted reasonably well by using a
detailed kinetic mechanism developed by
others, when ammonia was  introduced
with the  fuel; but agreement was poor
when ammonia was injected in the  air
side.  This indicates that there are some
deficiencies in the ammonia pyrolysis
kinetic mechanism when it  is used in the
absence of hydrocarbon fragments. The
qualitative dependence of the NO profile
on flame stretching was correctly pre-
dicted by the model.


The Formation and Destruction
of Nitrogenous Species During
Hydrocarbon/Air Combustion

D. W. Blair
  An experimental investigation was car-
ried  out  of the  critical  aspects of the
formation and destruction of nitrogenous
chemical  species during hydrocarbon/air
combustion. The primary purpose of the
work was to provide reliable experimental
information to aid in developing detailed
kinetic models. The experiments were run
in two significantly different laboratory
combustors over a wide range of indepen-
dent thermochemical variables (equiva-
lence ratio, temperature, fuel species, fuel
nitrogen  species, and characteristic resi-
dence times). Two reactors, the jet-stirred
combustor and the multiburner, both de-
veloped with EPA funds, were used. Con-
clusions drawn from this work include:
  •  With both  equivalence  ratio  and
      flame  temperature held constant,
      specific hydrocarbon chemistry in-
      fluences both thermal nitrogen fixa-
      tion and fuel nitrogen conversion.
  •  Fuel chemistry is more important in
      the multiburner than it is in the jet-
      stirred combustor.  Contributions
      of combustion environment to this
      difference appear to exceed those
      of reaction time.
  •  While the conversion of fuel nitro-
      gen depends on fuel nitrogen spe-
      cies, the dependency in the multi-
      burner considerably exceeds that in
      the jet-stirred combustor. This ar-
      gues that differences  in combus-
      tion environment between the two
      combustors are important.
  •  Because: production of'fixed nitrogen
      products differs significantly be-
      tween the multiburner and the jet-
      stirred  combustor, choosing be-
      tween these combustors, as mod-
      els of given practical combustors,
      should be based on which one best
      approaches conditions that will exist
      in the given combustor.

Laboratory Scale Coal Studies

J. M.  Beer, A. F. Sarofim, J. M.
Levy,  D. Altrichter, and L. Timothy
  There is a possibility that, in pulverized
coal flames, NO  produced early in the
combustion process is later reduced by
char generated by  the partial combustion
of coal.  Indirect evidence for the impor-
tance of NO reduction reactions in  coal
combustors is provided by the observation
in pilot-scale combustors that the NO
concentration passes through a maximum
and  undergoes substantial reduction in
later stages  of combustion, particularly
under fuel-rich conditions. To assess the
role of char in reducing NO, a three-part
research program  has been undertaken
involving: (1) determining kinetics of the
NO/char reaction under conditions of in-
terest to pulverized coal combustion, (2)
measuring temperature/time histories and
burning times of coal particles to provide a
basis for testing models for coal com-
bustors, and (3) using the kinetic informa-
tion to develop a model to predict (first)
char loading and temperature profiles, and
(then) the reduction of NO by char under
different simulated coal combustion con-
ditions.  Preliminary data is presented on

-------
NO/char reactions and on the burning
temperatures and times of coal particles
for conditions encompassing the range of
interest in pulverized coal flames.
Mechanisms of Nitric Oxide
Reduction on Solid Particles

G. G. de Soete
  In the last few years, attention has been
focused on the role played by flame-born
solid particles (e.g. soots, coal and char
particles,  fly ash)  in the process of in situ
(i.e., within the flame or in the hot combus-
tion products) heterogeneous reduction of
NOX.   Three main problems must be
solved: (1) elucidating the kinetic mech-
anisms of heterogeneous NO reduction
under typical flame and flue gas condi-
tions,  (2) determining the reaction rates
which control the disappearance of NO,
the formation of intermediate species, and
the rate of their transformation of N2, and
(3) checking the  relevance of heterogen-
eous reduction paths compared to homo-
geneous  reduction mechanisms.  This
paper describes a study which will provide
information  on the first two problems
using packed-bed reactors which will then
lead into a general investigation  of the
heterogeneous NO reducing mechanisms.
Data are  presented which indicate that
both IMH3 and HCN can be formed during
the reduction process, depending on the
type of solid and  the gas-phase composi-
tion.
Volatility of Fuel Nitrogen

R L. Gay, A E. Axworthy, V. H.
Dayan, and H. L. Hecht
  An  experimental  program  has been
completed for the measurement  of fuel
nitrogen volatility using a quartz two-stage
pyrolysis  reactor. Solid  and liquid fossil
fuels were  heated in helium in the first
stage of the reactor at temperatures up to
1100°C The volatile nitrogen compounds
released  were measured by converting
them to HCN in the second stage of the
reactor at 1100°C. The HCN was collected
in dilute  sodium carbonate solution and
measured colorimetrically.
  Twenty fossil fuel samples were stud-
ied, consisting of petroleum-based fuel
oils, synthetic oils from coal and shale, and
coals. All of the samples tested produced
the greatest  yield   of  volatile nitrogen
compounds at a first-stage temperature of
1100°C.  The maximum yields of  volatile
nitrogen from petroleum fuel oils were 35-
48 percent of the nitrogen in the sample.
The yield curves increased continuously
from 300°C with a slight dip at 600-
750°C  The maximum volatile nitrogen
yields from shale oils were 70-79 percent,
while the coal liquids yielded 50 percent
The nitrogen species in shale oils were
very volatile at low temperatures, giving
HCN yields  of  about  65  percent at a
pyrolysis temperature of only 200°C.
  A variety of bituminous and lignite coals
were tested  In general, the coals  ex-
hibited much lower fuel nitrogen evolution
than did the  fuel oils.  Maximum coal
volatile nitrogen yields obtained at a pyrol-
ysis temperature of 1100°C were about
15-25 percent. A plot of the percentage of
fuel nitrogen converted to NO during
combustion (measured elsewhere) vs  the
percentage of fuel nitrogen volatilized at
1100°C was found to give a strong linear
correlation with a variety of coals. This
correlation may provide an excellent means
of predicting NO formation for any given
coal, simply by measuring its nitrogen
volatility at 1100°C.
High-Temperature Pyrolysis of
Oil Droplet and Coal Particle
Streams

J. M. Beer, A.  F. Sarofim, S. P.
Hanson, and A. K. Gupta
  A series of high-temperature flow reac-
tor experiments were carried out with coal
particles under pyrolysis and combustion
conditions. Techniques are described to
study the pyrolysis of heavy liquid fuel
droplets. The purpose of these investiga-
tions was to provide kinetic data on fuel
nitrogen evolution and general volatile
release  In addition, experimental evidence
was sought to determine if the ignition of
volatiles in the vicinity of coal particles
influences the  further evolution of nitro-
genous  compounds from  the pyrolyzing
particle.  Preliminary results indicate during
droplet  pyrolysis the evolution rates of
fuel-nitrogen compounds are affected
strongly by rapid heating to high-tempera-
ture conditions similar to those encount-
ered in practical flames. The development
and application of a technique to obtain
time-resolved particle  temperatures  are
reported The  nature of the data acqui-
sition, storage, and analysis permits statis-
tical studies to be made of coal particle
time/temperature histories. Information
of this  type would perhaps explain  the
observations which indicate different yields
of NOX from fuel of seemingly similar fuel
characteristics.
The Characterization of Coals
During Thermal Decompositioi

P. R. Soloman
  A relation between coal organic struc
ture and the products of thermal decorr
position has been developed by measui
ing the modeling vacuum devolatilizatio
of 12 bituminous coals and a lignite. Th
relation allows the prediction of the tim
and temperature dependent evolution c
the major products of pyrolysis  from
knowledge of the coal's functional grou
distribution using a general kinetic modi
with  rate constants independent  of co
rank.   The model assumes that larc
molecular fragments (monomers)  are n
leased from the coal "polymer" with on
minor alteration to form tar, while simi
taneous cracking of the chemical structu
forms the light molecules of the gas. At
chemical component of the coal can, ther
fore,  evolve as part of the tar or as  •<
independent species. The model may  I
used to predict the amount of volatile fi
nitrogen  evolved in pyrolysis, which
essential in estimating the conversion
fuel nitrogen to NOX.
The Physical and Chemical
Effects Occurring During the
Thermal Decomposition of Co
Particles and Oil Droplets

W. R Seeker, G. S. Samuelsen, f
P. Heap, J. 0. Trolezer, and
C. F.  Hess
  Events occurring during the  them
decomposition of liquid droplets and c
particles in the initial stages of heat relez
in turbulent  diffusion flames are of a
siderable significance to the designers
low pollutant  emission  combustors.
pulverized coal flames the partition off
nitrogen  between  the volatile and  c
fractions, for example, will  impact
production of fuel NO. Earlier studies hi
demonstrated  that holography could
used to observe the behavior of coal \.
tides during combustion. The appro;
taken in the present study was to obse
particles/droplets  under well-contro
conditions which simulated those encoi
ered in  real systems. This was accc
plished by the construction of a reai
which allowed the particle/droplets tc
injected  into  high temperature ga
whose temperature and composition 
-------
and high-speed photography. Two-color
particle pyrometry was used to measure
particle temperatures, and solid and gas-
eous samples were extracted to investi-
gate the variation of composition with
time. Initial evaluations of the results ob-
tained to date, on the physical phenomena
which occur during the thermal decom-
position of pulverized coal particles,  in-
dicate that:

  •  Volatile  coal fractions are ejected
      from coal particles in jets; for large
      bituminous coal particles, these jets
      produce a trail  of small particles.

  •  Coal composition and volatile evo-
      lution rate influence particle tem-
      perature.

  •  Large soot structures can be formed
      from the bulk gases produced when
      bituminous coal  particles decom-
      pose.

Pollutant Formation From
Combusting Pulverized Coal
Clouds

P. M. Goldberg, H. long, and
R Kendall
  The objective of this experimental study
was to provide information on the mech-
anisms  of coal combustion and subse-
quent NOX formation under conditions
similar to those found in the near-burner
region of a high-intensity pulverized coal
flame. A jet-stirred reactor system is used
in this  study  to  simulate this  type  of
combustion environment The stirred com-
bustor can roughly simulate a flame region
where a high  degree of recirculation is
present The first goal of the program was
to design  a well-mixed  coal reactor cap-
able of operating at residence times of 20-
200 ms. After completing the design and
fabrication, noncombusting mixing studies
were conducted to verify that a high level
of gas-phase mixing exists in the reactor.
Once gas-phase mixing performance was
verified, subsequent  experiments  were
directed at quantifying  particle mixing
behavior. Combustion experiments began
after completion of this task
  Combustion results show that devolatil-
ization may be essentially completed in
the 50-100 ms time range. The exhaust
concentrations and temperature depen-
dence on equivalence ratio are similar to
those expected in larger time scale sys-
tems. This might  lead to the conclusion
that enhanced volatile yields play a  major
role in combustion. It has been observed
that fuel nitrogen conversion is correlat-
able with equivalence ratio, reaction effici-
ency, and temperature. It was also found
that the nitrogen depletion of the char
corresponds roughly to the weight loss
exhibited by the char, although a limited
range of weight loss (75-95 percent) was
examined.

Reactor Studies to Assess the
Impact of Fuel Characteristics
on Fuel NO* Formation

M. P.  Heap, D.  W. Pershing, and
Q C. England
  This paper describes results obtained to
date in two ongoing investigations to
assess  the  impact of fuel properties on
pollutant formation. The approach taken in
both investigations was experimental,
wherein both solid and liquid fuels were
burned in the absence of molecular nitro-
gen. The oxidant consisted of a mixture of
Oa, Ar, and C02 (21  percent by volume
Oa). The COa was added to maintain the
same adiabatic flame temperature for both
the artificial oxidant and air. NO formed
during combustion with this artificial N2-
free oxidant is called fuel NO.
  Data are presented showing the impact
of fuel properties on NOX formation from
liquid fuels  under both  excess  air  and
staged  conditions. These  data indicate
that:
  • The  formation of fuel  NO from
     petroleum and alternative liquid
     fuels mainly depends on their total
     fuel nitrogen content.

  • NOX  control techniques for high
     nitrogen fuels, which rely on the
     generation of a high-temperature
     primary fuel-rich  zone,  appear to
     give the maximum opportunity for
     NOX reduction.

  Twenty-six coals have been tested under
fuel-lean conditions:  it appears that al-
though fuel nitrogen content is important
it is not the only  fuel characteristic dic-
tating fuel NO formation. It appears that
the volatility of the fuel nitrogen has an
important impact  on fuel NO  formation,
particularly  under well-mixed conditions.
Under fuel-rich conditons, the coal com-
position impacts the gas-phase nitrogen
species distribution. With bituminous
coals, ammonia represents a substantially
smaller fraction of the total fixed nitrogen
than with subbituminous or lignite coals.
Of the nine coals tested in detail, only one--
a Utah  bituminous-formed substantial
amounts of HCN under well-mixed condi-
tions. Contrary to liquid fuel,  increasing
the temperature of a fuel-rich primary zone
does not appear to reduce stack emissions
from a coal-fired staged combustor.


Pollutant Formation During
Fixed-Bed and Suspension Coal
Combustion

G. P. Starley, S. L  Manis, S.  P.
Pearcell, D. M. Slaughter, and
D. W. Pershing
  Recent large-scale pilot and field tests
have (at least partially) demonstrated the
potential of combustion modifications for
NOX control in stoker-fired boilers. The
overall objective of this program is to study
the formation of NOX and  SOX  under
carefully controlled experimental condi-
tions  typical  of stoker-fired boilers.  In
particular,  the following major research
areas are being considered: (1) the evolu-
tion and oxidation of  fuel nitrogen and
sulfur,  (2) the retention of SOX by ash
and/or solid-chemical sorbents  in both
suspension- and fixed-bed burning, and
(3)  the effectiveness  of distributed air
addition for NOx  control in stoker-fired
coal systems.
  Results with the suspension furnace do
not support the hypothesis that a large
fraction of the NOX is formed in the over-
throw phase; however, many additional
heating rates must be studied before any
firm  conclusions  can  be  reached. The
following tentative conclusions have been
reached regarding the formation of NOX in
a fixed-bed combustion system:

  1.   NO formation is not uniform through-
      out the burning time of the bed. The
      formation maximizes early in  the
      process, prior to the peak combus-
      tion rate, and then  gradually  de-
      creases.

  2.   Staged air addition is a potentially
      effective means  of  NO control.
      Exhaust concentrations decrease
      approximately linearly with decreas-
      ing bed stoichiometry.


An Experimental Approach to
the Study of Heavy Oil Spray
Combustion in Shear Layers

A Vranos and B. A. Knight
  This  paper describes a two-phase pro-
gram: (1)  design and fabrication of an
apparatus, and (2) preliminary combus-
tion experiments.  A unique shear layer
mixing and combustion apparatus was
developed which simulates high-shear
diffusive combustion with heavy oil drop-

-------
let  injection as found  in the near-field
combustion zone of boilers and furnaces.
The apparatus provides: (1) two-dimen-
sional mixing and combustion of uniform
streams of air and rich combustion pro-
ducts fed from opposite sides of a splitter
plate, (2)  uniform  injection of a  mono-
disperse heavy  oil spray into  the  shear
layer by a  linear array of fuel injectors
beneath the combustor wall, (3) control of
droplet path, residence time, and extent of
vaporization, (4) control of hot and cold
stream  inlet properties, and  (5)  three-
dimensional probing of the flow field.

  The design  phase of the program con-
sisted  of  two tasks:  aerodynamic and
thermodynamic design and mechanical
design. A wind tunnel, hot gas  generator,
combustion chamber, droplet injection
system, and  phase-sensitive  sampling
probe were designed in the first task. The
design of the apparatus was influenced
most strongly by the diverse requirements
of the fuel injection system. The injector
was designed so that the angle of droplet
penetration into the shear layer could be
varied over a wide range. Droplet trajec-
tories were computed for vaporizing No. 6
oil droplets injected from the floor of the
combustor into a hot rich environment
provided by a hot gas generator. Hot gas
generator dimensions and injector  loca-
tions were selected to accommodate the
required droplet trajectories, provide com-
plete vaporization  if desired, and provide
sufficient hot soak time for substantial
conversion of fuel nitrogen compounds to
molecular nitrogen.

Spray Characterization

W. R Seeker and G. S. Samuelsen
  A program has been  established  to
explain the dependence of NOX emissions
from fuel-oil fired combustors on atomiz-
ing nozzle type, and nozzle operating con-
ditions. Toward this end, a cold chamber
spray rig, patterned after the firetube sim-
ulator at EER, was built to characterize
nozzle spray behavior. As the initial step in
the program, nonintrusive optical  tech-
niques are being applied and evaluated for
(1) consistency of data, and (2) applicabil-
ity  to the study of spray behavior which
impacts NOX  emission. The optical  tech-
niques  include  diffraction, visibility, and
holography. At  this juncture in the pro-
gram,  visibility  measurements are con-
cluded. Significant differences exist be-
tween these data and data acquired in an
independent  program conducted at the
IFRF. The resolution of these differences
is not in progress.
The Application of Droplet
Sizing and Interferometry and
Holography to the Measurement
of Spray Droplet Size and
Velocity

C. F.  Hess and W. P. Bachalo
  Droplet sizing interferometry (DSI) and
laser holography are used in a fuel spray
study. The size and velocity distributions
of the fuel droplets produced by a Sonicore
nozzle in a cylindrical rig are obtained. The
two techniques  are  evaluated and com-
pared. The power and  flexibility of the
interferometer in the study of the  fuel
droplet size and velocity are demonstrated.
The data obtained by the two techniques
are compared and are shown to agree very
well. Although holography is adequate for
sizing droplets,  the analysis of the holo-
grams is time-consuming. The DSI mea-
sures size and velocity of the individual
droplets, provides an immediate data dis-
play, and  is therefore a  very powerful
diagnostic tool for liquid sprays.

Development of a Coherent
Flame Model for Turbulent
Chemically Reacting Flows

F. E. Marble  and J.  E.  Broadwell
  The coherent  flame model is applied to
the methane/air turbulent diffusion flame
with the objective of describing  the pro-
duction of NO. The example of a circular jet
of methane discharging into a stationary
air atmosphere  is used to illustrate appli-
cation of the model. In the model,  the
chemical reactions take place in laminar
flame elements  which are lengthened by
the turbulent fluid motion and shortened
when adjacent flame segments consume
intervening reactant The rates with which
methane and air are consumed  and NO
generated in the strained laminar flame are
computed numerically in an independent
calculation. The model predicts NO levels
of about 80 ppm at the end of the flame
generated by a 30.5 cm (1 ft) diameter jet
of methane issuing at 3.05 x 103 cm/sec
(100 ft/sec). The model also predicts that
this level varies directly with the fuel jet
diameter and inversely with the jet velocity.


General Kinetic Analysis Codes

C. J. Kau and T.  J. Tyson
  A computer code, capable of predicting
or analyzing premixed or diffusion flames,
is reported The generality of the code
allows the computation of various  con-
figurations;  e.g. one-dimensional time-
dependent planar/spherical, steady two-
dimensional  planar, and steady axisym-
metric nonrecirculating reacting flow sys-
tems. Physical phenomena such as laminar
unequal  species diffusivities, radiation,
flame holder recombination  effect and
heat loss are treated Several phenomeno-
logical turbulent eddy viscosity models,
based on  mixing length theory, are also
incorporated into the coda Kinetically the
code can treat up to 200 two- or three-
body basic reactions and up to 52 species.
  A  linearized implicit finite difference
network is used. Thus, all the dependent
variables, except cross-stream velocity, of
all the grid points at the same coordinate
line (or at the same integration step) are
solved simultaneously in coupled fashion.
The inversion of a block tridiagonal matrix
is required at each  integration step.
  For illustrative purposes, detailed cal-
culation of four types of laminar flames are
presented: a  flat flame, an opposed-jet
diffusion flame, a  coflowing  diffusion
flame, and a nonrecirculating confined
flame.
                                                                            •&U. S. GOVERNMENT PRINTING OFFICE: 1983/659-095/1941

-------
     M. P. Heap, compiler, is with Energy and Environmental Research Corp., Irvine,
       CA 92714.
     W. Steven Lanier is the EPA Project Officer (see below).
     The complete report, entitled "Proceedings of the Fifth Fundamental Combustion
       Research Contractors Workshop," (Order No. PB 83-164 483; Cost: $44.50,
       subject to change} will be available only from:
            National Technical Information Service
            5285 Port Royal Road
            Springfield, v'A 22161
            Telephone: 703-487-4650
     The EPA Project Officer can be contacted at:
            Industrial Environmental Research Laboratory
            U.S. Environmental Protection Agency
            Research Triangle Park, NC 27711
United States
Environmental Protection
Agency
Center for Environmental Research
Information
Cincinnati OH 45268
Postage and
Fees Paid
Environmental
Protection
Agency
EPA 335
Official Business
Penalty for Private Use $300
               PS    0000389
                                               AGtNCV
               230  S DEARBOKN  SIRtET
               CHICAGO   IL  606U4

-------