United States
                   Environmental Protection
                   Agency
Hazardous Waste Engineering
Research Laboratory
Cincinnati OH 45268
                   Research and Development
EPA/600/S2-87/095  Feb. 1988
SERA         Project Summary
                   Hazardous  Waste Combustion  in
                   Industrial  Processes:  Cement
                   and  Lime  Kilns

                   Robert E. Mournighan and Marvin Branscome
                     The full  report summarizes the
                  results of several studies relating  to
                  hazardous  waste combustion  in
                  cement and lime kilns.  The tests
                  included in  this study are four kilns
                  tested by the U.S.  Environmental
                  Protection Agency (EPA), four kilns
                  tested by State agencies  or the kiln
                  operator, two Canadian tests, and
                  one Swedish test The predominant
                  types of wastes  tested included
                  chlorinated organic compounds,
                  aromatic compounds, and  metal-
                  contaminated waste oil. The kiln
                  types include lime kilns and cement
                  kilns, which included the dry, wet,
                  and preheated  processes.  Fabric
                  filters and electrostatic precipitators
                  (ESPs) were the  pollution control
                  devices used in these  processes,
                  and the primary fuels included coal,
                  coke, coal/coke, fuel  oil, and  natural
                  gas/coke.
                     The parameters examined  in this
                  study were  Destruction and Removal
                  Efficiency (ORE)  of  the Principal
                  Organic  Hazardous  Constituents,
                  particulate and  HCI emissions,
                  metals,  and the effect  of burning
                  hazardous waste on  SO?, NOX> and
                  CO  emissions.  The  primary
                  conclusion of this study is that DREs
                  of 99.99% or greater can be obtained
                  in properly operating calcining kilns.
                  Particulate matter can increase when
                  chlorinated  wastes are burned in a
                  kiln equipped with an electrostatic
                  precipitator. Those kilns equipped
                  with fabric filters showed  no change
                  in emissions.
                     This  Project  Summary was
                  developed by EPA's Hazardous Waste
 Engineering Research  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).

 Background

   With the  passage of the  Hazardous
 and  Solid Waste Amendments of 1984,
 more categories  of liquid hazardous
 wastes will be banned from land disposal
 facilities. At the  same  time, energy
 intensive industries are  increasingly
 seeking  to find new  sources of  less
 expensive fuel. Because many industrial
 waste products can be readily used as
 fuels and some hazardous wastes can be
 economically processed and  made into
 fuels, a market based on hazardous
 waste has been developing in the United
 States. If reprocessed  waste liquids do
 contain significant  quantities of toxic
 metals, halogenated materials, or PCBs,
 and have a high heating value, they can
 be  economically  substituted  for coal,
 coke, oil or natural gas in many industrial
 processes. There are many examples of
 high temperature industrial furnaces and
 processes which already burn hazardous
 waste as supplemental fuel: cement kilns
 (both wet and dry processes), lime and
 dolomite kilns, clay processing kilns,
 steel  blast furnaces,  phosphate rock
 calciners and dryers,  iron ore dryers,
 brick and tile tunnel kilns, mineral wool
 furnaces and glass melt furnaces.
   In particular, there has  been a great
 deal of interest in the use of cement kilns
 for  the disposal of industrial  wastes as
 supplemental fuel for several reasons: 1)

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the production process is highly energy
intensive; fuel savings may translate into
a  competitive  advantage;  2)  kiln
temperatures  are  higher (2700°F)  and
gas residence times are longer (6-10
seconds) than those encountered in most
hazardous waste incinerators; 3) cement
product quality is relatively insensitive to
addition of most waste trace impurities.
   A US EPA study, published in 1982,
recommended that the Agency conduct
a full assessment of the use of waste
organic materials as supplemental fuel in
cement kiln1. As  a result  of  that
recommendation, the Agency began  a
field test  program  at  facilities using
hazardous waste as fuel. In  addition to
these EPA field tests, results from  test
burns reported by other investigators are
incorporated in this study.   A summary
of the tests used in this assessment and
a description of each site  is listed m
Table 1.  The data generated by these
studies are being  used to assess health
and environmental  risks,  develop
regulations,  and define  reasonable
operating limits.
   Using the data from all test sites listed
in Table 1, the full report is intended to
evaluate  the  effectiveness  of  the
calcining  process in destroying  the
waste, to  determine any  significant
change  in  criteria pollutant  emissions,
and to measure HCI emissions from the
process  when  burning  chlorinated
wastes.

Particulate Matter

   Most of the tests conducted  at kilns
using electrostatic precipitators exhibited
little change  in particulate emissions
when burning hazardous  wastes.  A
summary  of  the data for  each test  is
listed in Table 2.  The major exceptions
are tests during which there  were either
process equipment malfunctions or  high
amounts of chlorine being fed to the kiln.
The  latter  tests  have  led  to  the
conclusion that substantial chlorine  input
(>6 kg CI/Mg clinker) to a kiln can  lead
to greater particulate emissions in kilns
equipped with electrostatic precipitators.

Destruction and Removal
Efficiencies for Principal
Organic Hazardous
Constitutents
   Cement  kilns,  burning  hazardous
wastes as a fuel, will have to meet, in the
near  future, Federal regulations  for
incinerators. Specifically, with regard  to
the  Principal  Organic  Hazardous
Constituents  (POHCs), the facility  must
achieve  a  destruction  and  removal
efficiency  (ORE)  of  99.99%  for each
designated POHC.
The ORE is determined as follows:
             W.  -W
DRE=
                      °ut
                         xlOO%
where:
   Win  = mass feed rate  of a specific
   POHC in waste feed stream

   Wout  = mass flow rate of the same
   POHC  in exhaust emissions to the
   atmosphere
Table 3 summarizes  the  results of the
tests for which ORE was determined. In
general, the results show  that cement
kilns,  when well  operated, can achieve
destruction and  removal  efficiencies
equal to those achieved by well designed
and  well  operated  hazardous waste
incinerators.

Conventional  Pollutants   and
Hydrogen Chloride Emissions
   The process materials in the cement
and lime  manufacturing process are, by
their nature, very alkaline. This property
enables the  process to adsorb  acid
gases, such as  HCI, generated in the
combustion of chlorinated organics. For
the most part, the data shows that for
typical amounts of chlorinated waste fed
to these  processes,  HCI emissions are
lower than the 1.8 kg/hr limit specified by
the incinerator regulations. HCI removal
efficiencies,  based on   stack   gas
measurements, were greater than 99%.
   The criteria pollutants,  CO, SO2 and
NOX were measured  in six of the nine
tests  evaluated.  Significant changes in
pollutant emissions were noted from test
to test, but were not related to the use of
hazardous waste  as a  fuel. Normal
fluctuations m  fuel, combustion air flow
and  air  preheater  temperature are
responsible for changes in the observed
pollutant emissions.

Lead Emissions
   Lead emissions  and  the  lead content
of process waste  dust  increase  when
hazardous waste,  contaminated   with
significant quantities of lead, are burned.
However,  baseline  emissions  (no  waste
being  burned) of lead  are very low to
begin  with and,  although  emissions do
increase  with waste  burning, more than
99 percent of the  lead  entering the
process  is  captured by  the process
materials and the resulting emission rati
are not significant.

Conclusions

   Field tests conducted at nine ceme
and  lime  producing facilities burnii
hazardous wastes  indicate  that  POH
DREs generally  exceed 99.99 perce
under good operating conditions. Crite
pollutant emissions (S02, NOX,CO) we
not  significantly  affected  by  was
burning.  HCI  and  lead  emissio
increased  with waste  burning,  b
emission  rates  were  not  significa
Particulate  emissions  increase wi
increasing chlorine content of the was
in  facilities equipped  with ESPs. Cont
of  particulate from kilns  equipped  w
baghouses is not a significant problem.

Reference
(1)  Hazelwood,  D.,  et  al,  19
Assessment of Waste  Fuel Use
Cement  Kilns, U S.  Environmen
Protection Agency,  1982.

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Table 1. Summary of Cement and Lime Kiln Tests




             Plant          Date      Process      APCD
Fuel
Wastes
1
2
3
4
5
6
7
8
9
St. Lawrence
Cement
Mississauga, ON
Stora Vika
Sweden
Marquette
Cement
Oglesby, IL
San Juan
Cement
Puerto Rico
Alpha Cement
Cementon, NY
General
Portland
Lebec, CA
General
Portland
Paulding, OH
Lone Star
Industries
Oglesby, IL
Rockwell Lime
Manitowoc. Wl
1974
1975-76
1978
1981
1981-82
1982
1982
1983
1983
1983
Dry
Wet
Wet
Dry
Dry
Wet
Dry
Wet
Dry
Lime
ESP
ESP
ESP
ESP
Baghouse
ESP
Baghouse
ESP
ESP
Baghouse
Fuel Oil Waste oil
Fuel Oil Chlorinated
organics
Coal Chlorinated
organics,
PCBs,
Freon 113
Coal Hydrocarbon
solvents
C<5%
chlorine)
Fuel Oil Chlorinated
organics
Coal Solvents
Coal Hydrocarbon
solvents
Coal Hydrocarbon
solvents,
Freon 113
Coal/Coke Hydrocarbon
solvents,
Freon 113
Coke Hydrocarbon
solvents

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Table 2. Summary of Particulate Emission
Plant Test Condition
St. Lawrence




Rockwell Lime

Stora Vika





Marquette
Alpha Cement
San Juan

General
Portland
Paulding
Lone Star

Chlorinated
aliphatics '
Chlorinated
aromatics
PCBs
Baseline
Lubricating oil
Baseline
Waste
Baseline
Aliphatics
Baseline
PCBs
Baseline
Chlorophenols &
Phenoxyac/ds
Baseline
Freon 113
Baseline
Waste solvents
Baseline
Solvents
Baseline
Wastes
Baseline
Wastes
Baseline

Waste2
Baseline
Data
Particulate Emission
grlscf Ib/hr /to/ton3
021
0286

0.078
0038
0.064
0.707
0076
0.073
0039
0.009
0.024
0077
0058
0.074
0062
0022
0.074
0093
0047
0050
0043
0047
0030
0030

0.77

723
45

44
27
83
739
2.2
2.0
27
4 7
12.7
5.9
309
7.7
333
11 7
58
80
44
53
22.4
27 7
189
196

116

3
1 1

1 1
05
07
1.1
026
024
088
0.27
0.53
0.25
7.36
0.34
7 39
049
27
208
09
7 1
066
0.64
0.65
0.64

20

Chloride Input to
Kiln (kg/Mg)
4.0
55

25
-
-
2 7
-
44
0
36
0
095
0
7 7
0
1 1

5.5
-
22
0.2

1 2
0.2
1 Process upset during test.
2ESP malfunctioned during test.
3lb of particulate emitted per ton of product material (cement).

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Table 3. Summary of ORE Data
Plant Waste Component
St. Lawrence Cement
Chlorinated ahphatics
Chlorinated aromatics
PCBs
Destruction Efficiency
> 99.990
> 99.989
> 99.986
Stora Vika
San Juan Cement
Los Robles
(General Portland)
Methy/ene chloride
Trichloroethylene
All chlorinated hydrocarbons
PCB
Chlorinated phenols
Phenoxy acids
Freon 113

Methy/ene chloride
Trichloromethane
Carbon  tetrachlonde

Methylene chloride
1,1,1-Tnchloroethane
1,3.5- Tnmethylbenzene
Xylene
    > 99.995
    > 99.9998
    > 99.988
   > 99 99998
   > 99 99999
   > 99.99998
   > 99 99986

 93.292-99.997
  92.171 -99 96
 91.043-99.996

     >9999
      99.99
     > 99.95
     >9999
Pauldmg
(General Portland)
Oglesby
(Lone Stao
Rockwell Lime
Methylene chloride
Freon 113
Methyl ethyl ketone
1.1,1-Trichloroethane
Toluene

Methy/ene chloride
Freon 113
Methyl ethyl ketone
1,1,1-Tnchloroethane
Toluene

Methylene chloride
Methyl ethyl ketone
1,1,1-Tnchloroethane
Trichloroethylene
Tetrachloroethylene
Toluene
 99 956-99.998
    > 99.999
 99.978-99.997
 99.997-99.999
 99 940-99.988

  99.94-99.99
     99999
 99 997-99.999
    > 99 999
 99 986-99.998

99.9947-99 9995
99.9992-99.9997
99.9955-99.9982
99.997 -99 9999
99 997 -99.9999
 99.995 -99.998

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  The  EPA author Robert E.  Mournighan (also the EPA  Project Officer, see
  below)  is with the Hazardous  Waste Engineering Research Laboratory,
  Cincinnati, OH 45268 and Marvin Branscome is with Research Triangle Institute,
  Research Triangle Park, NC  27709.
  The  complete report,  entitled  "Hazardous  Waste Combustion in Industrial
  Processes: Cement and Lime  Kilns" (Order No. PB 88-126 4121 AS;  Cost:
  $14.95, subject to change) will be available only from:
           National Technical Information Service
           5285 Port Royal Road
           Springfield, VA22161
           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
                                                                                                           .3  i
United States
Environmental Protection
Agency
                      Center for Environmental Research
                      Information
                      Cincinnati OH 45268
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