United States
                     Environmental Protection
                     Agency
 Hazardous Waste Engineering
 Research Laboratory
 Cincinnati, OH 45268
                     Research and Development
EPA/600/S2-86/091 Feb. 1987
&EPA          Project  Summary
                     Incinerator  Operating
                     Parameters  Which  Correlate
                     with  Performance
                     Laurel J. Staley, Mart a K. Richards, George L Huffman, and Daniel P. Y.
                     Chang
                       A research project entitled "A Study of
                     Incinerator Operating Parameters Which
                     Correlate  With Performance" was con-
                     ducted  by the Thermal Processes Re-
                     search  Staff  of the Hazardous Waste
                     Engineering Research Laboratory. This
                     project  evaluated  how  closely  carbon
                     monoxide (CO) reflected incinerator per-
                     formance as measured by emission levels
                     of unburned or incompletely burned sim-
                     ulated chemical waste. The results of this
                     research are contained in a report entitled
                     "Incinerator Operating Parameters Which
                     Correlate With Performance."
                       Within this report are results of two dif-
                     ferent sets of tests; in the first set, a series
                     of six experiments were conducted in
                     which five different chemicals frequently
                     found in hazardous waste streams were
                     diluted in heptane and burned in a water-
                     jacketed pilot-scale combustor under a
                     series of excess air levels which span the
                     range from fuel-rich to fuel-lean combus-
                     tion. In  the first five experiments, com-
                     pounds  were diluted with heptane and
                     burned   individually  (either 1.1,2,2,-
                     tetrachloroethane, 1,1,2-trichloroethylene,
                     carbon  tetrachloride, chlorobenzene or
                     Freon-113). In  the  sixth  experiment,
                     Freon-113 and chlorobenzene were burned
                     together to test for mixture effects. Car-
                     bon monoxide levels in the combustor ex-
                     haust were continuously monitored as
                     was exhaust temperature. Emission levels
                     of unburned  and  incompletely  burned
                     hydrocarbons were determined by sam-
                     pling the combustor exhaust using Tenax-
                     GC®  filled sorbent  traps which were
                     subsequently analyzed by a gas chromato-
                     graph equipped with a Hall Detector. In the
                     second set of tests, CO concentration and
                     Destruction Efficiency (DE)  were meas-
                     ured as  a  function of Swirl Number and
fuel nozzle position. The second set of
tests was accomplished using a GC/MS
(gas chromatograph/mass spectrometer)
for analysis.
  In general, the results of these experi-
ments  indicated that CO levels in the
research combustor exhaust did not di-
rectly reflect the exhaust emissions of un-
burned and incompletely burned chlori-
nated hydrocarbon. Rather, these emis-
sions were more directly affected by the
specific nature of the  chemical being
burned and by the combustor operating
temperature.
  This Project Summary was developed
by EPA's Hazardous Waste Engineering
Research Laboratory, Cincinnati, OH, to
announce key findings of the research pro-
ject That is fully documented in a separate
report of the same title (see project report
ordering information at back),

Introduction
  Performance standards developed under
the Resource Conservation and Recovery
Act require that hazardous waste inciner-
ator operators achieve 99.99% Destruc-
tion and Removal Efficiency (DRE) on the
Principal Organic Hazardous Constituents
(POHCs) present  in  the waste streams
they burn. (POHCs are  generally waste
chemicals designated by the permit writer
on the basis of their concentration, toxi-
city and non-combustibility relative to the
other constituents of the waste stream.)
Compliance with this standard is usually
determined in a trial burn in which a waste
stream representative of what the inciner-
ator would usually receive is incinerated.
Extensive sampling is done at the inciner-
ator's stack to measure POHC emission
levels.  These samples are analyzed to
determine the level of POHC in the ex-

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haust. This information, along with infor-
mation on the composition of the feed, is
then used to determine ORE and ultimately
compliance with the RCRA incineration
regulations.
  Not only is this method of determining
compliance time-consuming and expen-
sive, it only provides information on the in-
cinerator's performance during the time of
the test. Since an incinerator's waste feed
may vary widely in composition, it may not
be valid to assume that if the incinerator
is operated as it was during the trial burn,
it will continue to  be in compliance with
the RCRA regulations regardless of varia-
tions in waste feed.  Therefore, there is a
need for some way to continuously mon-
itor incinerator performance, to immedi-
ately warn the operator of the onset of
performance deterioration so that correc-
tive action can be taken before an air pollu-
tion problem results.
  One method being considered involves
using CO levels in the exhaust to indicate
ORE.  Readily available  and inexpensive
methods exist to monitor CO levels in in-
cinerator exhaust. If  the level of CO in the
exhaust could in some way be tied to the
levels of unburned POHCs in the exhaust
and, ultimately, to  ORE, then CO could be
used as a continuous indicator of ORE
which  would  alleviate the  above-
mentioned uncertainties.
  The  purpose of this preliminary study
was to examine the  usefulness of CO as
an indicator of ORE under well-controlled
laboratory conditions.

Description  of  the Research
Conducted
  In the first  set of tests, a series of
five compounds, common constituents of
waste streams and often  chosen as
POHCs, were burned in a water-jacketed
pilot-scale research combustor under a
range of excess air levels. The compounds
chosen were  1,1,2,2-tetrachloroethane
(TCA), 1,1,2-trichloroethylene  (TCE),
carbon tetrachloride (CCI4), chloroben-
zene (CLBZ), and Freon-113, F113 (1,1,2-
trichloro-1,2,2-trifluoroethane).  Each com-
pound was tested separately. In each run,
the compound was diluted in normal hep-
tane to produce a two-mole percent solu-
tion. In a sixth run, chlorobenzene  was
burned with Freon-113 (CB/F), each at 2
mole percent. For each run, the combus-
tion air flow rate was varied while fuel flow
was held constant, thus producing differ-
ent excess air levels and causing the CO
levels in the combustor exhaust to span
the range of observable values. At five or
sometimes six different sets of operating
conditions, incinerator exhaust samples
were drawn through Tenax-GC®  sorbent
traps  for  purposes of  determining the
levels of unburned POHC being emitted
from the incinerator under these various
conditions. These traps were analyzed by
a gas chromotograph equipped with a Hall
Detector. In the second set of tests, CO
concentration and DE were measured as
a function of Swirl Number and fuel noz-
zle position. A GC/MS was used for the
analyses required by  the second set of
tests.
  The  Turbulent  Flame Reactor  (TFR)
shown in Figure  1 was the experimental
combustor used for this study. Fuel en-
tered the TFR through a Delavan pressure-
atomizing nozzle located at the bottom of
the reactor. Combustion air also entered
       at the bottom of the TFR through an Inte
       national Flame Research Foundation win
       box which was  designed so  that tf
       amount of angular momentum  ("swirl'
       imparted  to  the  incoming air  could t
       closely controlled.  A water jacket su
       rounded the  entire combustion  chamb
       and  removed approximately  45,OC
       BTU/hr from the system. All samples we
       taken from probes in the exhaust port
         In addition to taking Tenax-GC® trs
       samples,  the exhaust was also contini
       ously monitored for CO, carbon dioxid
       oxygen, and Total Unburned Hydrocarbo
       Non-dispersive infra-red analyzers we
       used to monitor CO and carbon dioxic
       levels. A paramagnetic analyzer was USE
       for monitoring oxygen  level and a Flarr
       lonization Detector was used to monit
                            Turbulent Flame Reactor
         To CO. C02 + O2
           Monitors  _
           To TENAX
          (Heated Line)
,i

                Air
               (From
            Compressor)
                                   EC
                   —»•  to THC monitor

                   ' T.C. for Exhaust
                      Gas Temp.
                 Swirl Vane
                 Adjustment
                                  Heptane &
                               Waste Compound
 Figure 1.    Turbulent Flame Reactor (TFRI.

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unburned hydrocarbon level. Exhaust tem-
perature was monitored through the  use
of a  type-K (chromel-alumel)  thermo-
couple.

Summary  of  Test  Results and
Recommendations

Continuous  sampling for conventional
measures of incinerator performance such
as CO, CO2, O2 and integrated sampling
of POHC DE and PIC (Products of Incom-
plete  Combustion) formation were  per-
formed under conditions of strong thermal
quenching and variable levels of excess air.
Preliminary studies of the effects of mix-
ing resulting from changes in inlet air swirl
and nozzle position were also carried  out.
A summary  of the  results  obtained is
presented below, as are recommendations
for future research.
  1.  Over the range of  excess air  ex-
amined (120% < Percent Theoretical Air
[%TA] < 230%),  CO concentration  and
exhaust gas temperature were functions
of the %TA in the TFR  (see Figure 2 for
a pictorial representation of the former).
The CO functional dependence was non-
linear and non-monotonic, exhibiting a
minimum at about 140% TA.  CO produc-
tion as a  function of theoretical air  ap-
peared to  be  relatively insensitive to  the
particular POHC mixed with the fuel at the
level tested, two mole  percent. The be-
havior of CO as a function of excess air
could plausibly be attributed to poor mix-
ing leading  to locally fuel-rich  pockets
under conditions of low excess air, and to
thermal quenching under conditions of
high excess air. Exhaust temperature was
a monotonically  decreasing function of
%TA over the range tested.
  2. The existence of two limbs to the CO
concentrations versus  %TA curve sug-
gested correlating CO with POHC DE for
one limb of the curve at a tima Adequate
data were only available for the high ex-
cess air case. For the high excess air limb,
POHC penetration appeared to increase as
CO increased,  but was dependent upon
the POHC burned (see Figure 3). Qualita-
tive agreement with the thermal stability
incinerability ranking scale was observed
for the POHCs:  TCE,  CLBZ, CCI4 and
TCA. Freon-113 exhibited anomalous be-
havior which possibly was related to an in-
ability of the analytical method employed
to distinguish Freon-113 from chloroform
(a common  PIC). The  utility of CO as a
continuous measure of POHC DE appears
to be limited by the multiple-valued nature
of the CO versus excess air curve as well
as by dependence upon the POHC burned.
Thus, it follows that the relationship be-
tween  CO and ORE could be  even more
tenuous.  Increase  of  CO emission  did.
                                  CO vs. %TA





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however, precede or occur simultaneously
with the increase  in POHC  penetration
above about 130% to 140% of theoretical
air. Therefore, CO concentration might still
serve as a useful upper bound for pur-
poses of incinerator  permitting, but will
likely be combustor  dependent. Further
research investigating the low excess air
limb of the curve needs to be pursued.
   3. The formation of PICs was observed
to increase  as a function of excess air
under conditions of high excess air. For an
example of this, see Figure 4. The relative
amounts of  a given PIC formed was de-
pendent upon the POHC burned, but nu-
merous PICs were common to all POHCs
tested.  As  shown in  Figure 4, it was
observed  that a recalcitrant PIC,  TCE,
could be formed from a relatively easily
destroyed POHC, TCA. In fact, the PlC-to-
POHC ratio  was observed to be greater
than unity in that instance, consistent with
larger pilot-scale combustor  tests under
similar  conditions  of  strong  thermal
quenching. The potential importance of
this  finding  applied  to boilers  co-firing
waste is evident.
  4. The common  occurrence  of PICs
(benzene, chloromethane,  dichlorometh-
ane, chloroform, carbon tetrachloride and
chlorobenzene) formed  from the fuel and
chlorinated POHCs may contribute to an
understanding of the  previously  found
phenomena of increasing DE with increas-
ing POHC concentration  in the waste feed.
POHCs  which could also  be formed as
PICs would appear to be more difficult to
destroy. The same phenomenon could be
one possible explanation for the difficulties
in using incinerability ranking scales to
predict destruction efficiency. As a prac-
tical application of these findings, it is sug-
gested that, for trial burns, one  select
recalcitrant POHCs which are not likely to
be formed as PICs, but which also yield
readily identifiable recalcitrant  PICs as
well. Further research to  better understand
the role of radical recombination in the for-
mation of PICs should be pursued.
  5. Hardware-related  parameters such
as degree of mixing produced by inlet air
swirl and nozzle position were found to af-
fect  flame stability and CO emissions in
preliminary testing. More comprehensive
tests of the influence of such parameters
on POHC DE should be  carried out in the
future.
Figun 2.    CO vs. % Theoretical Air (%TA): All compounds.

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                             Log (POHC Penetration} vs. CO




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1
1

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      The EPA authors LaurelJ. Staley (also the EPA Project Officer, see belo w), Marta
       K.  Richards, and George  L.  Huffman are  with the Hazardous Waste
       Engineering Research Laboratory. Cincinnati, OH 45268; and Daniel P. Y.
       Chang is with the University of California, Davis, CA 95616.
      The complete report, entitled "Incinerator Operating Parameters which Correlate
       with Performance," (Order No.  PB 87-104 626/AS; Cost: $9.95, 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:
             Hazardous Waste Engineering Research Laboratory
             U.S. Environmental Protection Agency
             Cincinnati, OH 45268
                                                                                                    6250109 I
United States
Environmental Protection
Agency
Center for Environmental Research
Information
Cincinnati OH 45268
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