United States
Environmental Protection
Agency
Hazardous Waste Engineering
Research Laboratory
Cincinnati OH 45268
Research and Development
EPA/600/S2-87/064 Nov. 1987
SEPA Project Summary
Total Mass Emissions from a
Hazardous Waste Incinerator
Andrew Trenholm, Thomas Lapp, George Scheil, John Cootes, Scott Klamm,
and Carolyn Cassady
Past studies of hazardous waste in-
cinerators by the Hazardous Waste
Engineering Research Laboratory have
primarily examined the performance of
combustion systems relative to the
destruction and removal efficiency
(DRE) for Resource Conservation and
Recovery Act (RCRA) Appendix VIII
compounds in the waste feed. These
earlier studies demonstrated that in
general most facilities performed quite
well relative to the DRE. However,
subsequent review by the Environmental
Protection Agency's (EPA) Science
Advisory Board raised questions about
additional Appendix VIII or non-Ap-
pendix VIII constituents that were not
identified in the earlier tests and might
be emitted from hazardous waste com-
bustion. The full report presents results
of a characterization of incinerator ef-
fluents to the extent that the emitted
compounds can be identified and
quantified. Measurements were made
of both Appendix VIII and non-Appendix
VIII compounds in all effluents (stack,
ash, water, etc.) from a full-scale in-
cinerator. A broad array of sampling
and analysis techniques were used.
Sampling methods included Modified
Method 5, volatile organic sampling
train (VOST), and specific techniques
for compounds such as formaldehyde.
Analysis techniques included gas
chromatography (GC) and gas chromato-
graphy/mass spectrometry (GC/MS).
Continuous measurements were also
made for a variety of compounds in-
cluding total hydrocarbons by flame
ionization detection (FID).
This Project Summary was developed
by EPA'8 Hazardous Waste Engineering
Research Laboratory, Cincinnati, OH, to
announce key findings of the research
pro]ect that Is fully documented In a
separate report of the same title (see
Project Report ordering Information at
back).
Background
The Resource Conservation and Re-
covery Act (RCRA) was enacted in 1976
and amended in 1984 by Hazardous and
Solid Waste Amendments (HSWA) to
handle the present day problems of toxic
and hazardous waste disposal. Com-
mensurate with these statutes, the U.S.
Environmental Protection Agency (EPA)
regards incineration as one of the principal
technology candidates for the ultimate
safe disposal of wastes and promulgated
the following standards in the Federal
Register, Volume 46, No. 15, on January
23,1981.
1. An incinerator must achieve a
destruction and removal efficiency
(DRE) of 99.99% for each principal
organic hazardous constitutent
(POHC) designated for each waste
feed.
2. An incinerator burning hazardous
waste must not emit more than 1.8
kg/hr of hydrogen chloride (HCI) or
must remove 99% of the hydrogen
chloride from the exhaust gas.
3. An incinerator burning hazardous
waste must not emit particulate
matter exceeding 180 milligrams per
dry standard cubic meter (mg/dscm).
Commensurate with the regulation of
hazardous waste incinerators, the EPA's
Hazardous Waste Engineering Research
Laboratory (HWERL) has the responsibility
to provide information on the ability of
these combustion systems to dispose of
hazardous wastes in a manner that pro-
vides adequate protection of the public
health and welfare. Past HWERL studies
-------
in this area have primarily examined the
performance of combustion systems re-
lative to the destruction removal efficiency
(DRE) for RCRA Appendix VIII compounds
in the waste feed. These eariler studies
demonstrated that in general most facili-
ties performed quite well when deter-
mining DRE of a specific compound.
However a detailed review of these
studies raised the question of overall
performance of hazardous waste incin-
erators, and the quantitation of the emis-
sion products of incomplete combustion
(PICs). A contributing factor to question-
able incinerator performance was the
issue of operating conditions and the
effect of an occasional upset on the pro-
duction of PICs.
To address these issues, EPA initiated
a project to qualitatively and quantitatively
study the total mass emissions (TME)
generated by testing a hazardous waste
incinerator functioning under both steady
state and transient combustion conditions.
Approach
The first step in the project was to find
a hazardous waste incinerator that was
both operational and willing to participate
in the test. Table 1 summarizes the selec-
tion criteria applied to the incinerators
identified for evaluation. The unit that
was selected for testing was Dow
Chemical's, located in Plaquemine,
Louisiana. Figure 1 shows a schematic
diagram of the incinerator which includes
a rotary kiln combustion chamber,
secondary combustion chamber, vertical
quench section, three-stage ionizing wet
scrubber and emission to the atmosphere
Three types of solid waste feeds were
used during all of the runs; a substituted
cellulose, polyethylene wax, and chlori-
nated pyridine tars. Each of the solid
wastes was individually contained in
plastic drums and sealed with a metal
rim ring. One drum of solid waste was
fed every 4 minutes with the drums of
each type of waste being alternately fed
through a ram feeder into the kiln.
Liquid waste feeds were of either
organic or aqueous composition. Prior to
testing, a uniform supply of the liquid
organic waste, sufficient for about 100
hours of incinerator operation, was ac-
cumulated in a 15,000-gal. capacity tank.
The liquid organic waste feed was spiked
so as to achieve a mixture of about 10%
carbon tetrachloride, with the remainder
being primarily Isopar (C5-C8 saturated
through the stack.
The operating conditions in the incin-
erator are summarized in Table 2 and
Tabto 1. Summary of Site Selection Criteria
Required
Desirable
Incinerator type
Air pollution control system
Feed characteristics
Operating and control
flexibility
Sampling location
Rotary kiln (semicontinuous
feed)
Secondary combustion cham-
ber or afterburner
Organic liquid feed
Wet scrubber for HCI
Paniculate control device
Amenable to spiking
Volatile organic solids
(e.g., paint wastes)
Large storage capacity
Wide range of operating
conditions
Willingness to vary conditions
Access to all effluent streams
Adequate stack sampling
ports and platform
Space for mobile van and
trailer
Aqueous liquid feed
Sludge feed
Dry ash collection system
Venturi scrubber
Once through water
Variety of chlorinated
organics
indicate fairly consistent combustion
conditions throughout the test.
hydrocarbons).
A summary of the sampling and
analysis parameters and methods em-
ployed during the test is shown in Table
3. The sampling methods, field measure-
ment methods and analytical methods
are presented in greater detail in Ap-
pendix A of the final report.
Discussion of Results
The combustion of organic materials in
an incinerator and the resultant formation
of products of incomplete combustion
(PICs) are always in a dynamic state.
Regardless of the degree of control over
the incinerator operating parameters, the
products resulting from the combustion
may not be identical from one time period
to another; concentrations of specific
compounds will vary with time. Table 4
shows the identification and concentration
of the volatile organic compounds identi-
fied in the tests that were conducted
under steady state conditions. In general,
the volatile organic constituents found
in the incinerator stack gas during the
steady state conditions were aromatic
and aliphatic hydrocarbons and halo-
genated hydrocarbons, primarily chlori-
nated aliphatic hydrocarbons. Acetonitrile
and dichloroacetonitrile were the only
volatile nitrogen-containing compounds
identified. The presence of the hydrocar-
bons and the chlorinated hydrocarbons
as the principal organic emissions was
not surprising considering the composition
of the liquid organic waste. In terms of
specific volatile organic constituents, the
principal constituent found by MRI was
methane at an average level of approxi
mately 1,400 ppb. Two other compound:
present in major quantities were chloro
methane at an average concentration o
213 ppb (based on field GC data) anc
chloroform with an average level of 6^
ppb (based on VOST data). The data ob
tained by Dow showed chloroform to be <
major volatile organic constituent of the
stack gas at an average level of 24 ppb.
Data similar to that presented in Tabli
4 is also shown in the final report for thi
semivolatile organic compounds derivei
under steady state and transient operatini
conditions, plus the volatile organii
compounds produced under transien
operating conditions. The difference;
between the two sets of operating condi
tions produced few if any changes in th<
resulting combustion products produce)
or their concentrations. This was true fo
both volatile and semivolatile compounds
The total mass (organic) emissions fron
the stack are summarized in the repor
and the various measurements of or
ganics have been converted into a com
mon basis of dry methane equivalen
using FID. Table 5 sums up all the contri
buting factors and compares it with thi
values collected on the total Hydrocarboi
Analyzer. The data show that for thi
steady state tests the closure on thi
hydrocarbon material balance was 56.:
± 5% while on the transient conditions i
was 69.3 ±21%.
Table 6 presents the particulate an
HCI emissions and the HCI removal e1
-------
ficiency for each run. The range of
paniculate emissions was 9.0 to 35
mg/m3. The range of HCI emissions was
0.016 to 0.038 kg/hr. HCI removal ef-
ficiencies averaged 99.98%. These rates
are all very low compared to the regula-
tory limits and to typical results from
other hazardous waste incinerator tests.
No levels of cyanide ion were found in
the analysis of any of the runs.
Conclusions
1. The transient upsets during Runs 4
to 6 did not cause significant in-
creases in concentrations of semi-
volatile compounds or most volatile
compounds. The three volatile
compounds that did increase were
methane, methylene chloride, and
benzene. Methane increased the
most dramatically.
2. The percent of the total hydrocarbon
(THC) emissions that were detected
as specific compounds ranged from
50 to 67% for five of the six test
runs; 91 % was detected in one run.
3. Methane accounted for the largest
fraction of the THC.
4. Oxygenated aliphatic compounds
were the largest class of compounds
among the semivolatiles, both in
total mass and number of com-
pounds.
5. Particulate and HCI emissions were
low and did not change between
the steady state and transient test
runs.
Secondary Combustion Chamber
• Liquid
Waste
Aqueous
Waste
~ • Water in
Ionizing I Wet
Scrubber System
I
• MM5
Plant VOST
MRI VOST
• Aldehydes
Orsat
\V
Waste in
Plastic Barrels
Wastewater
I
• Scrubber
Water Out
Blower j
• Plant CO Analyzer /
i
Plant *
z Analyzer /
•—Sampling Points
Figure 1. Process schematic.
MRI Trailer
GC/PID S Ha/I
Continuous THC
n
EPA/Acurex Van
Continuous Monitors
GC/FID
-------
Tabfo 2. Summary of Key Process Parameters
Average Value, Run No.
Parameter
Total methane mass flow. Ib/hr
Kiln temperature. °F(°C)
SCC* temperature, °F(°C)
Stack gas temperature. °F (°C)
Stack gas flow rate, acfm x TO'3
Oxygen (% 02) in stack
Kiln vacuum, in. H2O
SCC vacuum, in. H2O
Atomization steam pressure (kiln), psig
Atomization steam pressure (SCC), psig
1
372
1550
(843)
1857
(1014)
163
(73)
21.8
10.1
-0.34
-0.05
25.0
50.0
2
414
1386
(752)
1738
(948)
160
(71)
20.1
11.1
-0.33
-0.05
25.0
50.0
3
423
1438
(781)
1708
(931)
154
(68)
21.2
11.5
-0.30
-0.05
25.5
50.0
4
552
1440
(782)
1776
(969)
160
(71)
23.4
11.2
-0.35
-0.04
25.0
50.0
5
615
1364
(740)
1782
(972)
165
(74)
24.9
10.6
-0.35
-0.04
25.0
50.0
6
532'
1467
(797)
1852
(1011)
167
(7sr
23.4
9.9
-0.35'
-0.04
25.0
50.0
' Dow Incinerator Control Center data logger was inoperable for the first 110 min of the run. Average values based on last 65 min of the run.
* SCC = Secondary Combustion Chamber.
Table 3. Summary of Sampling and A nalysis Parameters and Methods
Sample
Sampling
frequency
for each run
Sampling
method
Sample size
Analytical
parameters
Preparation
method'
Analytical method3
Liquid organic waste One grab sample
every 15 min
composited into one
sample for each run
Once at end of run
Tap (SO04)
1 L
Aqueous waste
One grab sample
every 15 min
composited into one
sample for each run
VOA viaf1 filled 40 mL
from
composite
Tap (S004) 4 L
SVPOHCs"
Chlorides
Heating value
Ash
Viscosity
VPOHC"
One VOA vial every Tap (S004)
15 min
40 mL per vial VPOHC
Solid waste
One grab sample per Scoop (S007) « 250 g per
solid charge, grab
composited at end of
test
Scrubber water inlet One grab sample
every 30 min
composited into one
sample each run
Dipper (S002) 4 L
One VOA vial every VOA vial filled 40 mL/VOA
30 min from grab
sample
VPOHC
SVPOHC
Chlorides
Heating value
Ash
SVPOHC
VPOHC
Sample dilution
NA
NA
NA
NA
Purge and trap
SVPOHC"
Chlorides
Heating value
Ash
Solvent extraction
NA
NA
NA
Purge and trap
NA
NA
GC/MSC
Organic halide (D432'/
84orD808-81)
Calorimeter (D240- 73
Ignition (D482-80)
Viscometer (D-88-81J
GC/MS
GC/MS
Organic halide (D432'i
84 or D808-81)
Calorimeter (D240-73
Ignition (D482-80)
GC/MS
Tetraglyme disper- GC/MS
sion/purge and trap
Solvent extraction GC/MS
NA
Organic halide
(D4327-84)
Calorimeter (D2015-
77)
Ignition (D482-80)
Solvent extraction GC/MS
Purge and trap
GC/MS
-------
Table 3. (Continued)
Sampling
frequency
Sample for each run
Scrubber water outlet
Ash
Stack gas
One grab sample
every 30 min
composited into one
sample each run
One VOA vial every
3O min
One grab sample per
run
2-hr composite per
run
2-hr composite per
run
Three trap pairs at 40
min per pair per run
One composite
sample per run
One composite
sample per run
1 min averages
1 min averages
1 min averages
1 min averages
~ once/5 min
~ once/30 min'
~ once/30 min'
~ once/30 min'
Samp/ing
method
Dipper (S002)
VOA vial filled
from grab
sample
Scoop (S007)
MM5'
MM5
VOST(S012)h
EPA Reference
Method 3
Midget
impinger
Continuous
Continuous
Continuous
Continuous
Gas sampling
valve
Gas sampling
valve
Gas sampling
valve
Gas sampling
valve or
syringe
Sample size
4L
40 mL/VOA
500 g
-60-1 00 ft3"
60-1 00 ft39
20 L per trap
pair
~20L
-100L
NA
NA
NA
NA
NA
NA
NA
NA
Analytical
parameters
SVPOHC
VPOHC
SVPOHC
Paniculate
HCI
Moisture
Temperature
Velocity
SVPOHC
Moisture
Temperature
Velocity
Method 624
compounds
Oxygen, carbon
dioxide
Aldehydes
CO, C02
o,
NO,
THC
THC
C, to C3 hydrocarbons
Aromatics
Halogenated organics
Preparation
method3
Solvent extraction
Purge and trap
Solvent extraction
Desiccation
NA
NA
NA
NA
Solvent extraction
NA
NA
NA
Purge and trap
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
Analytical method"
GC/MS
GC/MS
GC/MS
Gravimetric (EPA RMS)
Color imetric (EPA
325.2)
Gravimetric
Thermocouple
Pilot tube
GC/MS
Gravimetric
Thermocouple
Pitot tube
GC/MS
Orsat
HPLC
NDIR
Paramagnetic
Chemiluminescent
FID
GC/FID
GC/FID
GC/PID
GC/Hall or P1D
Note: Sampling method numbers (e.g.. S004) refer to methods published in "Sampling and Analysis Methods for Hazardous Waste Combustion,"
December 1983; analytical methods beginning with prefix D and E refer to ASTM methods.
" Sample preparation and analytical methods are described in detail in Appendix A referencing the A. D. Little, EPA 600, and SW-846 methods.
* Semivolatile principal organic hazardous constituents.
c Gas chromatography/mass spectroscopy.
d Volatile organic analysis vial.
8 Volatile principal organic hazardous constituents.
'MMB = Modified Method 5.
a Exact volume of gas sampled will be dependent on isokinetic sampling rate.
h VOST = Volatile organic sampling train.
' Maximum rate permitted by analysis time.
-------
Tab/* 4. Stack Concentrations of Volatile Constituents During Steady State Conditions
Concentration (ppb)
Constituent
Priority Pollutants
Methyl chloride
Methyl bromide
Vinyl chloride
Dichloromethane
Trichlorofluoromethane
1, 1 -Dichloromethylene
Chloroform
1 ,2-Dichloroethane
1.1. 1 -Trichloroethane
Carbon tetrachloride
Dichlorobromomethane
1 ,2 -Dichloropropane
Trichloroethylene
Benzene
Chlorodibromomethane
2-Chloromethyl vinyl ether
Bromoform
1. 1 ,2,2-Tetrachloroethylene
Toluene
Chlorobenzene
Ethylbenzene
Total
Nonpriority Pollutants
CM
Dimethyl ether
Dichlorodifluoromethane
Acetonitrile
C«rT(0
C4H/Acetone
Chloropropene
Bromochloromethane
Tetrahydrofuran/CsH,2
CsHg/CfHfo
CsH,2/CeH,2
CsHi2/CeH,4
CSH,20,
CeH,2
Table 4. (Continued)
MRI
(VOST)
4.4
0.0
0.9
2.4
4.1
1.0
62.2
2.6
0.2
3.8
14.0
1.2
0.1
4.6
2.3
1.8
0.1
1.2
7.9
0.1
1.0
116.0
0.0
18.8
0.2
0.0
0.0
4.1
0.0
0.0
0.4
0.0
0.8
1.8
0.0
0.2
Run 1
MRI
(GC)
226.0
O.O
1.9
4.7
0.0
15.4
0.0
0.3
4.4
0.0
0.0
3.0
0.0
0.0
0.0
255.7
0.0
Dow
(VOST)
29.6
O.O
2.1
0.9
0.0
0.0
16.3
1.2
0.2
2.0
4.4
0.0
NA
8.0
1.3
0.0
1.2
0.4
7.3
0.1
0.7
NA
MRI
(VOST)
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
Run 2
MRt
(GC)
309.9
0.0
2.8
1.1
0.0
37.5
0.4
0.6
7.8
0.0
2.3
6.4
0.0
0.0
0.0
368.8
3.4
Dow
(VOST)
3.7
0.0
0.0
0.7
0.0
0.0
30.7
1.3
1.5
0.8
5.6
0.0
NA
11.4
0.9
0.0
0.1
0.3
2.4
0.1
0.2
NA
MRI
(VOST)
1.7
0.1
0.6
1.0
0.1
0.0
64.2
0.2
1.2
1.3
13.4
0.0
0.1
1.7
1.7
0.2
0.0
0.4
0.9
0.1
0.1
89.1
0.0
0.3
0.2
0.1
0.2
3.4
0.2
0.0
0.1
0.2
0.2
0.1
0.0
0.0
Run 3
MRI
(GC)
102.8
0.0
6.6
1.2
0.0
36.1
0.0
1.0
6.0
0.1
0.0
3.0
0.0
0.0
0.0
156.7
9.4
Avg. 1-3
Dow
(VOST)
0.0
0.0
0.0
0.8
0.0
0.0
26.2
0.2
0.8
0.6
5.7
0.0
NA
3.4
0.8
0.0
0.0
0.3
4.7
0.1
0.1
NA
MRI MRI
IVOST) (GC)
3.1 212.9
0.1 0.0
0.8 3.8
1.7 2.3
2. 1 0.0
0.5 0.0
63.2 29.6
1.4 0.0
0.7 0.1
2.5 0.6
13.7 6.1
0.6 0.0
0. 1 0.8
3.1 4.1
2.0 0.0
1.0 0.0
0.1 0.0
0.8 0.0
4.4 O.Q
0.1 0.0
0.6 0.0
102.6 260.4
0.0
9.6
0.2
O.I
0.1
3.7
0.1
0.0
0.2
0.1
0.5
0.9
0.0
0.1
Dow
(VOST)
11.1
0.0
0.7
0.8
0.0
0.0
24.4
0.9
0.8
1.1
5.2
0.0
NA
7.6
1.O
0.0
0.4
0.3
4.8
0.1
0.3
NA
Concentration (ppb)
Constituent
Nonpriority Pollutants (continued)
Dichloroacetonitrile
CjH^/Cf^l^
CjHjf/CjHte
CeH,2
CjH^/CjHff
Hydrocarbon
C,H,2
Isooctane
Hydrocarbon
Total
MRI
(VOST)
0.6
0.0
0.0
0.0
1.4
O.I
0.4
44.0
1.1
58.9
Run 4
Mm
(GC)
0.0
RunS
Dow
(VOST)
MRI
MRI
(VOST) (GC)
0.3
0.2
0.0
0.1
0.2
0.1
0.4
3.7
0.0
14.2
11.5
Dow
(VOST)
MRI
(VOST)
0.0
O.O
0.1
0.5
0.2
0.0
0.3
0.0
0.0
16.8
Run 6
MRI
(GC)
2.9
Avg. 4-6
Dow
(VOST)
MRI MRI
(VOST) (GC)
0.3
O.I
0.0
0.2
0.6
0.1
0.3
15.9
0.4
30.0 4.8
Dow
(VOST)
-------
Tables.
Total Hydrocarbon Response and Total Mass (Organic) Emissions
Organics
Run No. THC
1 7.6
2 6.8
3 6.2
4 8.8
5 145
6 106
Methane
1.7
1.2
1.3
4.3
93
51
Ethylene
ND
ND
ND
1.1
1.3
0.6
Other
volatiles
0.6
0.8
0.2
1.1
0.5
0.7
Semi-
volatiles
2.5
1.6
1.9
1.6
2.0
1.5
Total
organics
4.7
3.6
3.3
8.0
96.8
53.7
Fraction
of total 1%)
62
53
54
91
67
50
Note: All values are ppm methane (FID} equivalent, dry gas basis.
ND = not detected.
Tab/0 6. Paniculate and HCI Emissions
HCI
Paniculate emissions' HCI
Run (mg/m3) (kg/hr) efficiency"
1
2
3
4
5
6
15.9
14.2
9.0
11.1
23.6
35.5
0.022
0.016
0.016
0.028
0.030
0.038
0.99993
0.99989
0.99990
0.99978
0.99985
0.99984
'Average of two values.
Andrew Trenholm, Thomas Lapp. George Scheil, John Cootes, Scott Klamm,
and Carolyn Cassady are with Midwest Research Institute, Kansas, City, MO
64110.
Robert C. Thurnau is the EPA Project Officer (see below).
The complete report, entitled "Total Mass Emissions from a Hazardous Waste
Incinerator," (Order No. PB 87-228 508/AS; Cost: $24.95, 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 Officer can be contacted at:
Hazardous Waste Engineering Research Laboratory
U.S. Environmental Protection Agency
Cincinnati, OH 45268
-------
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Penalty for Private Use $300
EPA/600/S2-87/064
0001961 HWER
LIBRARY REGION ¥
H30ES*DEARBORN ST
CHICAGO I*- 6060*
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