United States
                    Environmental Protection
                    Agency
 Industrial Environmental Research
 Laboratory
 Cincinnati OH 45268
                    Research and Development
EPA-600/S2-84-086 July 1984
SEB\          Project  Summary
                    Laboratory-Scale Flame-Mode
                    Hazardous  Waste  Thermal
                    Destruction  Research
                    J. C. Kramlich, M. P. Heap, J. H. Pohl, E. M. Poncelet, G. C. Samuelsen,
                    and W. R. Seeker
                     This program was performed to gen-
                   erate fundamental flame-mode data on
                   the incinerability of hazardous waste
                   compounds. Other objectives included
                   the comparison of flame and nonflame
                   data, and the development of guidelines
                   for future work on the development of
                   an acceptable incinerability ranking
                   methodology.
                     Two reactor systems were selected to
                   provide flexibility in  simulating the
                   failure conditions that can occur in liquid
                   injection incinerators. In the microspray
                   reactor the reaction characteristics of
                   single droplets of waste compounds
                   were studied. The turbulent flame re-
                   actor consisted of a  swirl-stabilized
                   turbulent spray flame in which the waste
                   compounds were doped into an auxiliary
                   fuel. In this reactor the effect of flame
                   parameters such as  stoichiometry,
                   atomization quality, and quench  phe-
                   nomenon were studied. The approach
                   was to establish conditions that yielded
                   high destruction efficiencies, and then
                   to perturb the flame by changing one or
                   more flame parameters until incomplete
                   destruction occurred. The waste com-
                   pound concentration was then meas-
                   ured at the reader exit to establish the
                   ranking. Five test compounds were
                   utilized: acrylonitrile, benzene, chloro-
                   benzene, chloroform, and 1,2-dichloro-
                   ethane.
                     The results indicated that when oper-
                   ated under conditions of optimal com-
                   bustion efficiency flames were capable
                   of high waste destruction  efficiency.
                   Under  off-optimum conditions  the
                   destruction efficiencies were typically
                   90-99.9 percent. No single ranking
                   procedure adequately  described  the
rankings observed under all conditions.
Rather, the flame rankings were
condition-dependent. These data indi-
cate that a realistic incinerability ranking
methodology must be  a synthesis of
waste properties and system-dependent
parameters.
  This Project Summary was developed
by EPA's Industrial Environmental Re-
search  Laboratory, Cincinnati, OH, 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).


Introduction
  Permitting procedures for hazardous
waste incinerators are defined by the
Resource Conservation and Recovery Act
(RCRA). A permit to operate is issued after
a trial burn has been executed or other
appropriate test data obtained which
demonstrate that  the incinerator satis-
factorily converts  hazardous waste into
non-hazardous  compounds .when oper-
ated under specified conditions. Satisfac-
tory conversion is defined in terms of
destruction and removal efficiency (ORE).
However, since most hazardous waste
streams contain many compounds, a trial
burn which involves the measurement of
all of them would be prohibitively expen-
sive. Consequently, the trial burn involves
the  measurement of a subset of com-
pounds (the principal organic hazardous
constituents—POHC's) which are present
in the input stream. If the ORE of these
POHC's is 99.99 percent or greater, and
certain  other conditions are met (e.g.,
chlorine and particulate matter removal

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  and emissions standards), then a permit
  to operate is granted. Thus, the burden of
  responsibility rests with the permit writer
  who must select the subset of compounds
  (POHC's) based upon concentration and
  incinerability. This constitutes the final
  report of a project which was carried out
  to examine methods of ranking incinera-
  bility and to compare flame with nonf lame
  waste destruction.
    Several procedures have been proposed
  to rank incinerability,  namely:
  • The heat of combustion.
  • Autoignition temperature (AIT).
  • A computational approach based upon
     AIT, compound structure, and  other
     compound-dependent parameters.
  • The temperature necessary for a  given
     destruction level within a given time
     under dilute   premixed conditions
     (Tgggg).
  • Susceptibility of the compound-bound
     structure to attack  by flame  radicals.

  These procedures have their merits, but
  fail to take into account all the conditions
  which  may exist  in actual incinerators.
  The heat of combustion, for example, of a
  particular compound maybe insignificant
  if it is present in  small quantities and is
  mixed with an auxiliary fuel. In addition,
  some of these procedures do not consider
  processes and reactions  that occur  in
  flames. The times and temperatures
  which exist under nonflame experimental
  conditions may be inappropriate for large-
  scale diffusion flames.
    The concept of incinerability is used to
  describe the relative degree of difficulty of
  incineration of  the various hazardous
  organic constituents  present in a  given
  waste stream. If, during the trial burn, it is
  demonstrated that compounds  most diffi-
  cult to destroy have a ORE greater than
  99.99 percent, then  it is assumed that
  compounds ranked  more  incinerable
  under  the  accepted  hierarchy  will be
  destroyed at the  same or greater ORE
  than the difficult compounds. Thus, there
  is a need for some ranking methodology
  that will aid the  permit writer in his
  selection of difficult  compounds.  If the
  ranking methodology is in error, or  is not
  applicable to a particular system, then a
  condition could exist wherein a POHC
  was destroyed satisfactorily,  but  other
  hazardous compounds in the waste
  stream  were not  destroyed sufficiently.
  Under these circumstances, a trial burn
  designed to measure  only the POHC may
  have incorrectly demonstrated the  satis-
  factory operation of the incinerator.
  Because of the nature of flames, waste
compounds  which experience a flame
environment are rapidly and completely
destroyed. This can be demonstrated by
considering nonflame thermal  decompo-
sition data obtained under dilute premixed
conditions. As an example, nonflame data
indicates that chlorobenzene will decom-
pose to  99.99 percent of its original
concentration  in  1 sec at 1038°K. At
typical flame temperatures (approximately
2000°K), the time required to obtain the
same destruction  level  is much smaller
(<10~13 sec. using  the same thermal
decomposition data) than the typical 0.10
sec. flame residence time.
  Thus, nonf lame thermal decomposition
data obtained under dilute  premixed
conditions  indicate  that  temperatures
much lower than  those encountered in
typical  incinerator flames will destroy all
the organic hazardous waste compounds
which  have been tested  to date.  Also,
because of high reactant concentrations
in flames, free radicals which must be
present to propagate the flame will con-
tribute to destruction of the compounds in
the flame.  These free  radicals will in-
crease the  rate of decomposition above
those predicted from dilute decomposition
kinetics. Under ideal flame conditions, in
which all of the waste is exposed to flame
temperatures, the concept of incinerabil-
ity has little significance  since all haz-
ardous compounds would be expected to
be completely destroyed.
  Incomplete destruction of a hazardous
waste compound in an actual incinerator
must be caused by conditions that allow
some of the material to escape or bypass
the flame, since organic compounds are
destroyed rapidly in a flame environment.
Most incinerators  include long residence
time hold-up zones or afterburners to
destroy material that has not completely
reacted in the flame zone. Thus, inciner-
ability would be expected to be influenced
not only by the chemical properties of the
compound, but also  by  its physical pro-
perties and their interaction with the
incinerator operating conditions because
these may  influence the failure mode.
The  term  "failure  mode" is used to
describe  those conditions that might
occur in  a  practical  incinerator, which
preclude complete  processing of the
waste  material by a high-temperature
turbulent diffusion flame. Thus, the term
in the  present context does not include
conditions that may affect other parts of
an incinerator (e.g., afterburner or scrub-
ber). It is important to evaluate inciner-
ability  under conditions  that  simulate
those failure modes which could occur in
practice.
  Various phenomena  account for the
failure of turbulent diffusion  flames,
typical of those used in liquid injection
incinerators, to completely destroy a liquid
waste. The destruction efficiency in the
flame maybe less than quantitative (100
percent) because of any of the following
reasons:

  1.  Atomization Parameters. When the
     waste material is injected as a liquid
     that must be atomized, poor destruc-
     tion efficiency can result from inap-
     propriate atomization. (a) Droplets
     that are too large to evaporate may
     be  produced,  (b) Their trajectory
     may be such that they penetrate the
     flame  zone and ignition  does not
     occur, (c) Droplets that are too small
     may promote concentrated evapora-
     tion zones which produce fuel-rich
     pockets.
  2.  Mixing Parameters. In  a turbulent
     diffusion flame the reactants are
     supplied  separately and reactant
     contacting takes place via turbulent
     mixing. Poor mixing can result in
     low destruction  efficiencies be-
     cause  the waste material may not
     be  mixed with  oxygen before it
     escapes from the flame region.
  3.  Thermal Parameters. The destruc-
     tion efficiency may be low because
     flame  temperatures are too low.
     This can occur if the calorific value
     of the waste/auxiliary-fuel mixture
     is low or heat removal rates are
     high.
  4.  Quenching Parameters. The reac-
     tants  can  be  quenched  before
     destruction is complete by hetero-
     geneous or homogenous phenom-
     ena. Quench rates are  high due to
     mixing with excessive excess air
     levels  in fuel injection systems in
     which the  flame impinges on an
     aqueous jet,  or  the flame  may
     contact a relatively cool surface.

Consequently, it is essential to investigate
the concept of incinerability in flames
under conditions that could account for a
failure to completely destroy the waste
compound and under conditions that are
typical of real systems.
  The primary goal of this study was to
compare the proposed incinerability rank-
ing procedures  with those  measured
under flame conditions typical of liquid
injection  incinerators. The approach util-
ized was to  measure the exhaust com-

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pound concentration under  different
simulated failure modes and to compare
the ordering of the compounds to those
given by several  incinerability ranking
procedures. Two reactors were required
to simulate failure conditions for all the
parametersexpected to influence inciner-
ator performance; i.e., thermal atomiza-
tion, mixing, and quenching. A microspray
reactor consisting of a laminar premixed
flat-flame into  which test  compounds
were  injected was used to investigate
thermal parameters. Asubscale turbulent
diffusion spray flame was used to investi-
gate atomization, mixing, and quenching
parameters.  Secondary goals included
the generation  of fundamental flame-
mode destruction data necessary to com-
pare flame and nonflame decomposition.
The results  are primarily  a means of
guiding future experimental work, since
further work is necessary  to select  a
reasonable ranking protocol.

Experimental Approach
  Extensive investigations are  being
carried out at the University of Dayton
Research Institute under EPA sponsorship
to define the kinetics of waste decomposi-
tion in post-flame regions. The  emphasis
of the present study  was  on the  flame
zone  itself and the  impact of failure
conditions associated with mixing, ther-
mal, quenching, and atomization param-
eters  on the relative  destruction of five
compounds. These  compounds  were
selected  because they represented  a
broad range of incinerability asdefined by
existing ranking procedures, and because
data within each of the procedures were
available for the compounds. The study
was restricted to conditions typical of
liquid injection incinerators. No attempt
was made to include phenomena associ-
ated with waste  destruction in beds such
as those that exist in fluidized beds, rotary
kilns,  or hearth  incinerators. Two  flame
reactors were used to study destruction
efficiency under different conditions:

  1.  Microspray Reactor.  In the micro-
     spray reactor, monodisperse waste
     droplets were injected into a hot,
     uniform post-flame gas. These ex-
     periments  investigated the destruc-
     tion  efficiency (DE) behavior and
     ranking that resulted from individ-
     ual  droplet evaporation and  flame
     decomposition reactions. The exper-
     iment was designed to bridge  the
     gap between the nonflame thermal
     decomposition experiments and the
     turbulent flame data.  As such,  it
     included two processes in addition
     to the thermal decomposition exper-
     iments: droplet vaporization dynam-
     ics  and flame reactions. The data
     were used for the following pur-
     poses:
     • To determine what portion of the
        turbulent flame  rankings was
        due to laminar flame and evapo-
        ration processes.
     • To compare flame (microspray)
        with nonflame (thermal decom-
        position) destruction on a funda-
        mental level without the compli-
        cating influence of turbulence.
  2.  Turbulent Flame Reactor.  A turbu-
     lent flame reactor (TFR) was used to
     investigate DE  and ranking  in a
     turbulent spray diffusion flame. The
     TFR was operated under conditions
     to simulate many of the processes
     occurring in the flame zone of a
     liquid  injection  incinerator;  these
     could be exaggerated to simulate
     different failure modes.

  Five compounds (chloroform, acryloni-
trile, benzene, chlorobenzene, and 1,2-
dichloroethane) were selected as repre-
sentative  of  liquid organic  hazardous
wastes. All the compounds are listed in
the 1980 RCRA regulations. Part  261,
Appendix VIII (Federal Register. May 19,
1980).  The compounds were chosen to
represent a broad range of incinerability
based on the most commonly proposed
ranking procedures. They cover greater
than 90 percent of the range in heats of
combustion for the listed compounds (. 13
to 10.14kcal/gm). Since a direct compar-
ison between nonflame thermal decom-
position rankings and the flame-mode de-
struction was an objective of this study,
compounds were selected for testing for
which nonflame data were available. In
addition,  the selection  also took into
account the NBS ranking system, a range
of autoignition temperatures and a variety
of molecular structures. Two compounds,
a highly chlorinated  methane and  a
chlorinated ethane, are aromatic; another
compound contains nitrogen.
  Compound  DE was measured in the
reactor exhaust by adsorption onto Tenax-
GC, followed by thermal desorption and
flame ionization gas chromatographic
analysis. The use of Tenax for concentra-
ting the sample provided the necessary
rapid turnover of samples with sufficient
separation and sensitivity.  The break-
through volumes of all the test compounds
were directly measured and were found
to be greater than the utilized sample
volumes. Benzene and 1,2-dicloroethane
were not separable by the column and
hence mixtures containing both  com-
pounds were avoided.

Microspray Results
  The microspray was used to investigate
the impact of thermal parameters for two
conditions:

• Fuel-lean—excess oxygen available to
   oxidize test compounds.
• Fuel-rich—insufficient  oxygen avail-
   able to oxidize test compounds.

In addition, the effect of using  pure
compounds was compared with that for
mixtures of compounds. The other failure
mode parameters (atomization, quench-
ing,  and mixing) cannot  be  effectively
investigated in  the microspray  reactor
and were  investigated  in the  turbulent
flame reactor.
  Figure 1 presents data for two mixtures
of four compounds shown separately in
Figures 1(a) and 1(b). In these tests, 38
//m droplets of  the two mixtures  were
injected separately into a lean (10 percent
excess oxygen) Ha/air/IVU flame  with
different flat-flame temperatures. Ex-
haust concentrations  of  the individual
test compounds were measured and the
data are shown in Figure 1  in terms of the
fraction of each compound  remaining
versus the measured flat-flame tempera-
ture. This temperature  is  determined by
extrapolating the  axial  temperature
measurements to the burner face and is
the highest temperature of the flat-flame
gas.  Under these excess  oxygen condi-
tions, flames were observed to surround
each individual droplet for both mixtures
for flat-flame temperatures in  excess of
850°K. However, the  minimum droplet
ignition temperature was observed at
slightly lower temperatures for the 1,2-
dichloroethane  mixture, probably due to
the substitution of compounds. When the
flat-flame temperature is greater than the
ignition temperature of the specific com-
pound mixture, the exhaust concentration
of the test  compounds were below the
detection limit of the analytical technique
which indicated a  destruction level in
excess of 99.995 percent.
  Calculations using nonflame kinetics
indicate that almost no  decomposition
should occur below 800°K for the resi-
dence times (~1 sec.) available in the
microspray reactor.  However, as shown
in Figure 1, significant destruction was
measured  at flat-flame  temperatures
below 800°K. This destruction at low flat-
flame temperatures is probably due to a

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(stoichiometric  ratio  =  0.83} H2/air/N2
flames of different temperatures. In these
tests, the oxygen was rapidly and com-
pletely consumed by the hydrogen in the
flat-flame so that no oxygen was available
to oxidize the test compounds. The frac-
tion of each compound  remaining in the
exhaust as a function  of the flat-flame
temperature is shown in Figure 2. Even
with mixtures, the temperature, 1050°K,
required to destroy the compounds was
found  to  be  very similar to the 199.99
temperatures of the individual compounds
(920 to 1037°K); and were much higher
than those required if droplet ignition
occurred (Figure 1).  The fractional de-
struction was strongly  dependent upon
flame temperature. In fact, the data show
that a very small change in flame temper-
ature above 1050°K produced a substan-
tial change in the compound concentra-
tions, particularly for benzene. A difference
between the  compounds was observed
only at a temperature just below the flat-
flame temperature required for complete
destruction. At  that temperature,  the
compound that was  most predominant
was chlorobenzene, followed by benzene,
chloroform, and acrylonitrile. This ranking
was identical to that measured for the low
temperature  oxidation  data  (Figure  1).
The nonflame  Tgg.gg did identify  the
temperature range required for complete
destruction and the  most predominant
compounds (chlorobenzene and benzene);
however, acrylonitrile and chloroform are
reversed from the T98.gg ranking.
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A Benzene
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Figure 2.   Fraction of test compound re-
           maining in exhaust when 38 fjm
           droplets of mixtures of com-
           pounds were injected into rich
           (stoichiometric ratio = 0.83)
           Ht/air/Nz flame as a function of
           flame temperature. Incinerabil-
           ity order at 1050°K (highest to
           lowest concentration) is  chloro-
           benzene, benzene, acrylonitrile,
           and chloroform.
 Turbulent Flame Reactor Results
  The turbulent flame reactor was oper-
 ated  and tested under a  number  of
 conditions. However, many of these condi-
 tions resulted  in high destruction effi-
 ciency of all the test compounds. Only
 those parameters resulting in significant
 deterioration of destruction efficiency are
 presented. The conditions investigated in
 the turbulent flame  reactor that had a
 strong influence on destruction efficiency
 were primarily associated  with  three
 failure parameters:

 • Atomization  parameters—poor atom-
   ization quality.
 • Combustion parameters—high excess
                          air
                        —low excess
                          air
                        —low heat
                          release
 • Mixing (or turbulence)—swirl
                       —air velocity

Those parameters found to be  of less
importance included burner velocity, fuel
type (No. 2 fuel oil), and concentration of
hazardous waste compounds (from 3 to
25 percent).
  It was generally found that exhaust
concentration measurements of carbon
monoxide (CO)  and total hydrocarbons
were  good indicators of flame perform-
ance  and compound destruction effici-
ency.  The exhaust CO level in particular
appeared to be  well correlated with the
exhaust concentration of the test com-
pounds. This result was expected since
the high heat removal rates in the TFR
emphasize flame performance over post-
flame reaction.  Since CO is an inter-
mediate in the oxidation of hydrocarbons
to carbon dioxide (CO2), it is directly linked
with combustion efficiency. Therefore, an
examination of the relative CO levels for
each failure condition indicates the overall
combustion efficiency which can be com-
pared to the destruction efficiency of the
hazardous waste compounds. The rela-
tionship between exhaust CO, total hydro-
carbons measured by the flame ionization
detector, and  destruction  efficiency
measured for a mixture of compounds is
shown in Figure 3. The  maximum ORE
O99.995 percent) was measured at 30-
40 percent  excess air, which corre-
sponded to the minimum in both exhaust
CO and hydrocarbon.
  Figure  4 presents data obtained with
the TFR at high heat-release rates (44
kW).  Very  high destruction  levels
O99.995 percent) were measured for all
compounds at 20 percent excess air at
this heat-release rate with the exception
of benzene.  It is possible that benzene
was a product of incomplete combustion
of either the auxiliary fuel or one of the
test compounds (e.g., chlorobenzene). The
actual source of the benzene, whether it
is a product of incomplete combustion or
an  indication of incomplete  benzene
destruction,  has not been  determined.
Benzene is a possible intermediate in the
formation  of soot which was observed in
the flame in the  form of luminosity,
especially at  low excess  air levels. Be-
cause of the relatively large amounts of
heptane present (97 percent), only a small
conversion of heptane to benzene is
required to account for the exhaust levels
of benzene measured at this low excess
air condition. However, the benzene could
also be the result of a chlorobenzene
reaction.
  At higher  excess air  levels (>150
percent) theoretical air, the exhaust con-
centrations of CO and the test compounds
increased. This is probably due to lower
flame temperatures and increased quench-
ing, which can occur when large amounts
of unheated air are present. The lowest
ORE level obtained for these heat-release
rates  (44  kW) was 99.9  percent.  The
compound differences  were small but
measureable at 150 percent theoretical
air. The ranking  from highest to lowest
concentration was: chloroform, acryloni-
trile, benzene, and chlorobenzene.  This
particular  order, which was found to exist
for a number of failure conditions tested
with the turbulent flame reactor, does not
agree with any of the proposed rankings,
although  the  heat of  combustion did
identify the most predominant compound
(chloroform).
  The data obtained at low heat-release
rates (24-42 kW) are shown in  Figure 5.
This data  set was achieved by  lowering
the fuel flow rate from the  nominal
operating  conditions, while maintaining
the air flow  constant. This drop in  load
and increase in theoretical air resulted in
a significant increase in the fraction of
waste compounds in the exhaust. Under
this failure conditions,  chloroform  and
benzene had similar high exhaust concen-
trations, followed by 1,2-dichloroethane
and similar low exhaust concentrations
for acrylonitrile and chlorobenzene.
  The data presented in  Figure 6 indicate
that atomization parameters had signifi-
cant impact upon compound destruction.
In these tests, a nozzle designed for 1.5
gal/min was operated  at .75  gal/min
dropping the pressure from 161 psigto40
psig. This increases the  mean droplet

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 99.995  percent)  de-
stroyed. Even in the absence of oxygen,
the microspray data were consistent with
the high destruction efficiencies achiev-
able in a turbulent diffusion spray flame
environment.
  The TFR  was operated at high heat
removal rates by operating  with water-
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Under all failure conditions investigated,
exhaust  CO  concentration  increased
when the test compound concentration
increased.  These results suggest the
feasibility of using  exhause CO  and
potentially total hydrocarbons to monitor
the performance of liquid injection incin-
erators once  the  conditions  giving the
maximum destruction  efficiency  have
been defined.
  The incinerability  or  ordering of the
compounds was found to depend on the
actual failure condition which caused the
inefficiency. When both the microspray
and the  turbulent flame reactor  were
operated under conditions that simulated
failure modes of practical incinerators,
measurable differences in the destruction
efficiency of  the  five test compounds
were obtained. For example, chloroben-
zene was the most difficult to eliminate in
the microspray  when the temperature
was too low to ignite the droplets, but was
the least difficult to eliminate for a variety
of failure conditions  in the TFR, such as
poor atomization quality.
  Figure 8 presents a series of bar graphs
which allow a comparison between incin-
erability as defined by the various failure
modes and  the  rankings indicated by
procedures based upon Tgggg, heat of
combustion, the  NBS method, and AIT.
The bar graph shows the concentrations
measured in the experiment normalized
so that the most predominant compound
shows full-scale and the lesser concen-
trations are expressed as a percentage of
that  maximum concentration. This ap-
proach gives an indication of the meas-
ured  magnitude  of  the difference in
destruction  efficiency   between  com-
pounds. A comparison of these relative
concentration measurements with pro-
posed incinerability  ranking techniques
demonstrates that none  of the proposed
techniques agree with  the data for all
failure conditions. However, some of the
ranking procedures  were found  to be
appropriate for specific failure conditions.
For example, the  nonflame thermal de-
struction (Tgg.gg) and AIT procedures both
agreed with the compound concentration
measurements  when the temperature
was below droplet ignition temperature
and under oxygen-deficient conditions.
Heat of combustion was found to correlate
the pure compound data when the micro-
spray was operated below droplet ignition
temperature. In most instances, chloro-
form was the most difficult compound to
incinerate  for  the  failure  conditions
investigated with the TFR, and this was
anticipated by only one of the four ranking
techniques: heat of combustion.
                                   8
  Although measurable differences in the
destruction efficiency of the five  test
compounds were obtained,  the  differ-
ences were not large under any of the
conditions tested. For the most part, the
variation in the concentration (between
highest and lowest) of the compounds in
the exhaust was typically of the order of
five, although variations larger than ten
were  measured under  some circum-
stances. This suggests that the selection
of POHC may not be very critical because
the differences between compounds are
small. If the permit writer selects three
compounds based upon two or more
ranking techniques, and it is demonstra-
ted that their ORE is greater than 99.99
percent, then it is very unlikely that any
other compounds will be destroyed to a
significantly lesser degree.
  This study has identified the differences
between compound destruction efficiency
caused by failure conditions associated
with the flame zone. High destruction
efficiencies have been demonstrated in
the flame alone. However, many inciner-
ators are equipped with post-flame hold-
up zones and  afterburners in order to
achieve additional thermal decomposition
of compounds  which  escape  the flame
zone. In order for an incinerator to fail to
destroy  a compound, the material must
both escape the flame and the tempera-
ture be too low in the post-flame hold-up
zone to destroy the compound (less than
Tgg.gg). The differences in the concentra-
tion of compounds in the exhaust of the
incinerators is  associated with both the
flame and nonflame zones. The thermal
decomposition which occurs in the post-
flame zone can alter the ranking in the
exhaust. As an example, consider a flame
zone in which the DE of chloroform and
chlorobenzene was 95 percent and 99
percent,  respectively  (a flame  ranking
consistent with the data of Figures 6 or 7).
Utilizing nonflame kinetics and a 1.0 sec
isothermal post-flame zone for post-flame
temperatures below about 870°K, the
flame zone ranking will  persist  in the
exhaust. Above 1008°K both compounds
are destroyed to 99.99 percent DE. Hence,
there are potential situations, dependent
on incinerator  conditions, for either a
flame zone or a post-flame ranking to
prevail within a given unit.
  It was not the purpose of this study to
ascertain why destruction efficiency
under flame conditions can be compound
and failure mode specific. More detailed
measurements, such as  fundamental
kinetic flame studies, are necessary to
provide a full explanation of the causes of
the rankings. It could be associated with
flame inhibition due to the presence of
halogens, which are known to reduce
burning rates. Under quenching condi-
tions, these effects could be enhanced.
The formation of products of incomplete
combustion (PIC's), as a consequence of
the partial destruction of  the waste
compound, was not investigated.  An
alternate method of  assessing  inciner-
ability could be based upon the potential
to form  PIC's,  which are  themselves
hazardous.
Conclusions
  1.  Under optimum conditions, flames
     are capable of destroying hazardous
     waste compounds with very high
     efficiencies (greater than  99.995
     percent) without the need for long
     residence  time, high-temperature
     post-flame zones, or afterburners.
  2.  Reduced flame destruction effici-
     encies are the result of operation
     under some failure mode, such as
     poor atomization,  poor mixing, or
     flame quenching.
  3.  Incinerability, or ordering of com-
     pounds in terms of their  relative
     destruction efficiency, is dependent
     on  the actual  failure condition
     which caused the inefficiency.
  4.  Optimum conditions for destruction
     of hazardous waste compounds in
     turbulent  diffusion spray  flames
     correspond to minimal exhaust CO
     and total hydrocarbons.
  5.  No one incinerability ranking sys-
     tem appears to predict correctly the
     relative destruction efficiency of the
     five compounds tested for all failure
     conditions investigated. However,
     several rankings did correctly pre-
     dict relative DE for specific failure
     conditions.
  6.  More data are  required on other
     compounds and on other failure
     conditions more appropriate to dif-
     ferent types  of hazardous waste
     incinerators to fully determine the
     limitations of incinerability ranking
     systems and to develop an appro-
     priate incinerability ranking meth-
     odology.
  7.  Future experimental effort should
     be directed toward extending the
     compound  data base beyond the
     current five, and in particular, the
     extension  of experimental  capabil-
     ities to consider additional failure   .
     modes (e.g., those associated with   (
     post-flame thermal processes  of
     afterburners).

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ncinerability Rankings
Chloroform

1 2 Dichloroethane

Benzene
Acrylonitrile
Chlorobenzene
Microspray
Chloroform
1,2 Dichloroethane

Benzene
Acrylonitrile

Chlorobenzene
Turbulent Flame
Chloroform
1,2 Dichloroethane
Benzene
Acrylonitrile
Chlorobenzene
Turbulent Flame
Chloroform

1,2 Dichloroethane
Benzene
Acrylonitrile
Chlorobenzene
Non-Flame
Temperature
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Figure  8.    Comparison of proposed ranking techniques and concentration measured in the experiments under flame failure conditions normalized
             so most predominant compound shows full scale.

-------
 J. C. Kramlich, M. P. Heap. J. H. Pohl, E. M. Poncelet, G. S. Samuelson, and W. R.
    Seeker are with EERC, Irvine, Ca 92714-4190.
 C. C. Lee is the EPA Project Officer (see below).
 The complete report, entitled "Laboratory-Scale Flame-Mode Hazardous Waste
    Thermal Destruction Research," (Order No. PB 84-184 902; Cost:  $16.00,
    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 Protection Agency
         Cincinnati,  OH 45268
•U9GPO:  1984-759-102-10618

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