United States
Environmental Protection
Agency
Hazardous Waste Engineering
Research Laboratory
Cincinnati OH 45268
Research and Development
EPA/600/S2-87/098 Jan. 1988
Project Summary
Technical Resource Document:
Treatment Technologies for
Halogenated Organic
Containing Wastes, Volume I
Norman Surprenant, Thomas Nunno, Mike Kravett, and Marc Breton
This halogenated organics technical
resource document (TRD) is one of a
series of five TRDs that are being
prepared by the Hazardous Waste
Engineering Research Laboratory. It
provides information that can be used
by environmental regulatory agencies
and others as a source of technical
information describing alternatives to
the land disposal of nonsolvent halo-
genated wastes. These alternatives
include waste minimization/recovery,
treatment, and disposal of waste
streams. Although emphasis is placed
on the presentation of performance
data for proven technologies, informa-
tion dealing with the applicability of
other emerging technologies is pres-
ented as well.
The treatment technologies dis-
cussed in this TRD include biological
treatment as well as the following
physical, chemical, and thermal treat-
ment technologies:
Physical Treatment
Distillation
Evaporation
Steam-Stripping
Solvent Extraction
Carbon Adsorption
Chemical Treatment
Wet Air Oxidation
Supercritical Water
UV/Ozone Oxidation
Chemical Dechlorination
In Situ Vitrification
Thermal Treatment
Incineration
Molten Glass
Molten Salt
Pyrolysis
This Project Summary was devel-
oped by EPA's Hazardous Waste Engi-
neering Research Laboratory, Cincin-
nati, OH . to announce key findings of
the research project that is fully doc-
umented in a separate report of the
same title (see Project Report ordering
information at back).
Introduction
EPA, as directed by the 1984 amend-
ments to the Resource Conservation and
Recovery Act (RCRA), is in the process
of evaluating the availability and tech-
nical feasibility of land disposal alterna-
tives for waste containing nonsolvent,
halogenated organics. Prohibition of the
land disposal of these wastes is sche-
duled for July 8, 1987. The wastes of
concern, shown in Table 1, include
halogenated organic pesticides listed as
D type RCRA wastes on the basis of EP
toxicity; halogens identified as present in
many specific K type process waste
streams; and nonsolvent halogens, listed
in Part 261.33, identified as P and U type
RCRA wastes.1
Scope
This halogenated organics technical
resource document (TRD) is one of a
series of TRDs that are being prepared
by the Hazardous Waste Engineering
Research Laboratory. It provides infer-
-------
Table 1.
Waste
Category
DOXX
KXXX
PXXX
UXXX
Totals
RCRA -Listed Wastes Containing Halogenated Organic Compaounds (HOCs)
Total Total
Number Number
Listed in Containing Listing of Specific Hazardous Waste Codes
Part 261 HOCs (%) Containing One or More HOCs
17 6(35) DO/2
76 27(36; K001
K020"
K041
K098
107 23(21) P004
P033
P058
233 64 (26) U006
U029
U041"
U049
U073
U132
U185
U233
433 120(28)
DO/3
K009°
K021"
K042'
K099
P017
P035
P059
U017
U030
U042
U060
U081
U138
U192
U235
0014
K010*
K028"
K043
K105"
P023
P036
P060
U020
U033
U043
U061
U082
U142
U207
U237
DOTS
K015*
K029"
K073'
P024
P037
P090
U023
U034
U044*
U062
U097
U150
U212
U240
DO/6
KOI 6'
K030*
K085"
P025
P043
P095
U024
U035
U045*
U066
U127
U156*
U224
U242
DO/7
KOI 7"
K032*
K095*
P026
P050
P118
U025
U036
U046*
U067
U128
U158
U230
U243
KOI 8'
K032
K096a
P027
P051
P123
U026
U038
U047
U068
U129
U183
U231
U246
KO/3"
K033
K097
P028
P057
U027
U039
U048
U072
U130
U184
U232
U247
"Contains or represents a specific halogenated organic compound addressed in the solvent TRD.'
Source Reference 1.
mation that can be used by environmen-
tal regulatory agencies and others as a
source of technical information describ-
ing alternatives to the land disposal of
nonsolvent halogenated wastes. These
alternatives include waste minimiza-
tion/recovery, treatment, and disposal of
waste streams. Although emphasis is
placed on the presentation of perform-
ance data for proven technologies,
information dealing with the applicability
of other emerging technologies is pre-
sented as well. Many of the technologies
discussed here as applicable to halogen-
ated organcis are also applicable to
dioxms and halogenated solvent. Thus,
frequent reference is made to the pre-
viously prepared solvent TRD2 and dioxin
TRD3 since these represent extensive
sources of information and data that can
be directly related to the treatment of
halogenated organic wastes.
Hazardous Waste
Characteristics, Generation
and Management
Halogenated organic constituents of
concern include all listed halogenated
organics not classified as solvents,
dioxms, or polychlorinated biphenyls. As
shown in Table 2, they include com-
pounds present at 25°C in all physical
states (i.e., gas, liquid, and solid) and with
highly variable halogen content. The 78
halogenated organic compounds listed in
Table 2 are constituents of 120 listed
RCRA wastes identified in Table 1. An
estimated 24.2 million gallons of these
nonsolvent halogenated wastes were
generated in 1981,4 appreciably less
than the range of 765-2,600 million
gallons reported for halogenated sol-
vents in Reference 2. The quantities of
waste generated are shown below for
major halogenated organic waste
subgroups.
Estimated maximum
Halogenated quantity generated
organic subgroup (106 gal/yr)
Pesticides (D wastes)
Specific processes
(K wastes)
Single constituents
(U and P wastes)
7.6
12.5
4.1
Total.
242
About 3.2 million gallons were land
disposed in 1981. Treatment alternatives
must be found for those wastes which
exceed 1,000 ppm halogenated organics
if a land disposal ban is instituted, as
planned, in July 1987.
Treatment Technologies
A proposed scheme for the treatment
of the 3.2 million gallons land disposed
in 1981 was provided in Reference 4 and
is shown in Table 3. Treatment technol-
ogies were selected on the basis of waste
physical form and rely heavily on incin-
eration as a major means of halogen
destruction, despite the low Btu value of
most halogenated wastes. The physical
state of the waste (both that of the
constituents and the matrix) and halogen
content are key factors in assessing the
applicability of treatment technologies.
However, the impact of other pertinent
physical and chemical properties of the
halogenated organic constituents affect-
ing treatability (e.g., Henry's Law con-
stant, partition coefficient, solubility,
heat of combustion, etc.) must be con-
sidered, along with cost, in selecting the
most effective treatment technology.5'7
Most of the halogenated organic waste
streams will require some sort of pre-
treatment prior to final treatment.
General processes include phase sepa-
ration (e.g., sedimentation, filtration,
centrifugation, decantation), component
separation (e.g., distillation, separation ol
aqueous wastes from organics), and
chemical transformation (e.g., neutrali-
zation and precipitation of heavy metals)
Wastes to be incinerated may require
additional pretreatment in the form ol
particle size reduction or modification o'
viscosity by blending or heating. Some
blending of halogens will likely be needec
to reduce halogen content to specifie(
limits and to increase the heating valu(
-------
Table 2. Waste Categorization Based on Physical State
RCRA
Waste
Code
Compound Name
Molecular
Formula
Molecular
Weight
Halogen
Content
1% by Weight!
Gaseous Compounds (@25°C>
U043
U033
P033
U045
P095
U029
Vinyl chloride
Carbonyl fluoride
Cyanogen chloride
Methyl chloride
Carbonyl chloride
Methyl bromide
C2H3CI
CF2O
CCIN
CH3CI
CCI20
CH3Br
62.5
66
61.5
50.5
98.9
9.5
57 Cl
58 F
58 Cl
70 Cl
72 Cl
84 Br
Liquid Compounds (@25°Cj
P043
U062
U020
U038
U048
P028
U030
P036
U097
U042
U041
U156
P027
U024
U027
U046
U017
P023
U006
U025
U023
P017
U235
U034
U130
U128
U066
U067
U184
U138
U068
Diisopropyl fluorophosphate
Diallate
Benzene sulfonyl chloride
Ethyl-4,4'-dichlorobenzilate
2- Chlorophenol
Benzyl chloride
1 -Bromo-4-phenoxy benzene
Dichlorophenyl arsive
Dimethyl carbamoyl chloride
2-Chloroethylvinyl ether
Epichlorohydrin
Methyl chlorocarbonate
3- Chloropropionitrile
Bis(2-chloroethoxy) methane
Bis(2-chloroisopropyl) ether
Chloromethoxymethane
Benzal chloride
Chloroacetaldehyde
Acetyl chloride
Bis(2-chloroethylJ ether
Benzotrichloride
Bromoacetone
Tris(2, 3 - dibromopropyl)
phosphate
Trichloroacetaldehyde
Hexachlorocyclopendadiene
Hexachlorobutadiene
1 ,2 -Dibromo-3-Chloropropane
Ethylene dibromide
Pentachloroethane
Methyl iodide
Methylene bromide
C6H,,F03P
C,0«17C/S/VOS
C6//5C/02S
C16«,4C/203
CeHsCIO
C7H7CI
C,2H3B20
CaH5AsCli
C3HeCINO
C4H7CIO
C3H3CIO
C2H3CK>2
C3HtCIN
C5HWCI202
CeH,2CI20
C2HSCIO
C7HeCI2
C2H3CIO
C2H3CI
CtH»CI20
C7HSCI3
C3H5Be
CaH,sBr,P0i
C2HCI30
C5C/6
C4C/6
C3H5Br2CI
C2H
-------
Table 2
RCRA
Waste
Code
P058
P026
U047
U150
U035
U039
P057
U026
U158
P024
U192
U237
U073
D0 14,
U247
D0 16,
P035
DO? 7,
U233
U232
U060
U082
U081
U061
U132
P050
U231
U230
P037
DO? 2,
P051
P060
P004
U185
U212
U207
P059
P090.
U242
U036
DO? 5,
P123,
U224
Continued
Compound Name
Fluoracetic acid (Na salt)
o-(l-Chlorophenyl) thiourea
2-Chloronaphthalene
Me/phalan
Chlorambucil
p-Chloro-m-cresol
Fluoroacetamide
Chlornaphazme
4,4'-Methylene-bis-2 -
chloroanilme
p-Chloroanilme
Pronamide
Uracil mustard
3,3'-Dichlorobenzidme
Methoxychlor
2,4 -D
2,4,5-TP
2,4,5-T
ODD
2, 6-Dichlorophenol
2,4-Dichlorophenol
DDT
Hexachlorophene
Endosulfan
2.4,6- Tnchlorophenol
2,4,5-Trich/orophenol
Dieldnn
Endrm
Isodrin
Aldnn
Pentachloronitrobenzene
2,3,4,5-Tetrachlorophenol
1 ,2,4.5-Tetrachlorobenzene
Heptachlor
Pentachlorophenol
Chlordane
Toxaphene
Molecular
Formula
C2H2FNa02
C7H7CIN2
C,0H7CI
C,3W,aC/2/V202
c,4/y,9c/2/vo2
C7H7CIO
C2HtFNO
c,«w,5c/2/v
c,3/y,2c/2/v
C6W6C//V
C,2«,,C/2/VO
CeWnC/2/V302
Ci2#10C/2/V2
C16«15C/302
CttH6CI203
CaH7CI303
CaHeCI303
Cl4/VloC/4
C6«4C/2O
C6H
-------
Table 2
RCRA
Waste
Code
U183
U142
D013,
U129
U127
Continued
Compound Name
Pentachlorobenzene
Kepone
Linda ne
Hexachlorobenzene
Molecular
Formula
CsHCIs
CioC/,00
Ce^eC/e
CeC/6
Molecular
Weight
250.3
490.7
290.9
284.8
Halogen
Content
(% by Weight)
71 Cl
72 Cl
73 Cl
75 Cl
5. Turner, R. J. USEPA, HWERL.
Treatment Technologies for
Hazardous Wastes: Part V—Non-
solvent Halogenated Organics.
JAPCA. June 1986.
6. Freeman, H. USEPA, HWERL.
Innovative Thermal Hazardous
Waste Treatment Processes. EPA
Report. 1986.
7. Blaney, B. L. USEPA, HWERL.
Treatment Technologies for
Hazardous Wastes: Part II. JAPCA.
March 1986.
Table 3. Summary of Existing Waste Treatment Technologies
Waste Category
High chlorine content
KXXX wastes
Land Disposed
Waste Volume
Igal/yr)
1.673.977 (liquid)
612.291 (solid)
Existing Treatment Technology
Liquid injection incineration/ waste blending/caustic
scrubbing
Rotary kiln incineration
Comment
-4.000 Btu/lb
-4.000 Btu/lb
Halogenated aqueous 0
KXXX wastes
Halogenated aqueous sludge 23,970
KXXX wastes
Halogenated high inorganic 128
KXXX liquid wastes
Halogenated potential gases 0
Halogenated potential solids 68.216
Other halogenated organic s 759,2 74
with inorganic solids
Total 3.137.860
Filtration/steam stripping/carbon adsorption
Waste blending/liquid injection incineration
Rotary kiln incineration
Rotary kiln incineration with high efficiency scrubber
Solidification/land disposal
Liquid injection incineration/'causic scrubbing
Rotary kiln incineration with caustic scrubbing
Rotary kiln incineration with caustic scrubbing
-4,000 Btu/lb
-4,000 Btu/lb
-1.000 Btu/lb
Unknown Btu content
Assumed -4,000 Btu/lb
Assumed —1.000 Btu/lb
Source: Reference 1.
Table 4. Summary of Halogenated Organic Treatment Processes
Process Applicable Waste Streams Stage of Development
Performance
Residuals Generated
Incineration
Liquid injection
incineration
Allpumpable liquids
provided wastes can be
blended to Btu level of
8500 Btu/lb. Some solids
removal may be necessary
to avoid plugging nozzles.
Estimated that over 219
units are in use. Most
widely used incineration
technology.
Excellent destruction
efficienty f>99.99%).
Blending can avoid
problems associated with
residuals, e.g.. HCI.
TSP. possibly some PICs.
and HCI. Little ash if solids
removed in pretreatment
processes.
-------
Table 4.
Process
Continued
Applicable Waste Streams
Stage of Development
Performance
Residuals Generated
Rotary kiln
incineration
Fluid/zed bed
incineration
Fixed/ multiple
hearths
All wastes provided Btu
level is maintained.
Liquids or nonbulky solids.
Can handle a wide variety
of wastes.
Over 40 units in service;
most versatile for waste
destruction
Nine units reportedly in
operation-circulating bed
units under development.
Approximately 70 units in
use. Old technology for
Excellent destruction
efficiency (>99.99%).
Excellent destruction
efficiency (>99.99%).
Performance may be
marginal for halogenated
Requires APCDs. Process
residuals should be
acceptable if charged
properly and treated for
acid gas removal.
As above.
As above.
municipal waste
combustion.
wastes.
Industrial kilns
Generally all wastes, but
Btu level, chlorine content,
and other impurity content
may require blending to
control charge
characteristics and product
quality.
Only a few units now
burning hazardous waste.
Usually excellent
destruction efficiency
099.99%) because of long
residence times and high
temperatures.
As above.
Other Thermal Technologies
Circulating bed Liquids or nonbulky solids.
combustor
Molten glass
incineration
Molten salt
destruction
Almost all wastes,
provided moisture and
metal impurity levels are
within limitations.
Not suitable for high
(>20%) ash content
wastes.
Only one U.S.
manufacturer. No units
treating hazardous waste.
Technology developed for
glass manufacturing not
available yet as a
hazardous waste unit.
Technology under
developments/nee 1969,
but further development on
hold.
Manufacturer reports high
efficiencies 099.99%).
No performance data
available, but DREs should
be high O99.99%).
Very high destruction
efficiencies for organics
(six nines for PCBs).
Bed material additives can
reduce HCI emissions.
Residuals should be
acceptable.
Will needAPC device for
HCI and possibly PICs;
solids retained
(encapsulated) in molten
glass.
Needs some ARC devices
to collect material not
retained in salt.
Furnace pyrolysis
units
Most designs suitable for
all wastes.
Plasma arc pyrolysis
Fluid wall advanced
electric reactor
Present design suitable
only for liquids.
Suitable for all wastes if
solids pretreated to ensure
free flow
One pyrolysis unit RCRA
permitted. Certain designs
available commercially.
Commercial design
appears imminent, with
future modifications
planned for treatment of
sludges and solids
Ready for commercial
development. Test unit
permitted under RCRA.
Very high destruction
efficiencies possible
O99.99%). Possibility of
PIC formation.
Efficiencies exceeded six
nines in tests with
solvents.
Efficiencies have exceeded
six nines.
TSP emissions lower than
those from conventional
combustion; will needAPC
devices for HCI. Certain
wastes may produce an
unacceptable tarry
residual.
Requires APC devices for
HCP and TSP. needs flare
for HI and CO destruction.
Requires APC devices for
TSP and HCI.
In situ vitrification
Technique for treating
contaminated soils, could
possibly be extended to
slurries Also use as
solidification process
Not commercial, further
work planned.
No data available, but
DREs of over six nines
reported.
Off gas system needed to
control emissions to air.
Ash contained in vitrified
soil.
-------
Table 4. Continued
Process
Applicable Waste Streams
Stage of Development
Performance
Residuals Generated
Physical Treatment Methods
Distillation
Evaporation
Steam Stripping
Liquid-Liquid
Extraction
Carbon Adsorption
Resin Adsorption
This is a process used to
recover and separate
volatile organics. Fractional
distillation will require
solids removal to avoid
plugging columns.
Agitated thin film units can
tolerate higher levels of
solids and higher
viscosities than other types
of stills.
A simple distillation
process to remove volatile
organics from aqueous
solutions. Preferred for low
concentrations and
organics with low
solubilities.
Generally suitable only for
liquids of low solid content.
Suitable for low solid, low
concentration aqueous
waste streams.
Suitable for low solid
waste streams. Consider
for recovery of valuable
compounds.
Chemical Treatment Processes
Wet air oxidation
Supercritical water
oxidation
UV/Ozonation
Dechlorination
Suitable for aqueous
liquids, also possible for
slurries. Organic
concentrations up to 15%.
For liquids and slurries
containing optimal
concentrations of about
10% organics.
Oxidation with ozone
(assisted by UV) suitable
for low solid, dilute
aqueous solutions.
Dry soils and solids.
Technology well developed
and equipment available
from many suppliers;
widely practiced
technology.
Technology is well
developed and equipment
is available from several
suppliers; widely practiced
technology.
Technology well developed
and available.
Technology well developed
for industrial processing.
Technology well developed;
used as polishing
treatment.
Technology well developed
in industry for special
resin/organic compound
combinations. Applicability
to waste streams not
demonstrated.
High temperature/
pressure technology,
widely used as
pretreatment for municipal
sludges, only one
manufacturer.
Supercritical conditions
may impose demands on
system reliability.
Commercially available in
1986.
Now used as a polishing
step for wastewaters.
Not fully developed.
Separation depends upon
reflux (99+ percent
achievable}. This is a
recovery process.
This is a volatile organic
recovery process. Typical
recovery of 60 to 70
percent.
Not generally considered a
final treatment, but can
achieve low residual
organic levels.
Can achieve high efficiency
separations for certain
organic/waste
combinations.
Can achieve low levels of
organics in effluent.
Can achieve low levels of
organics in effluent.
Pretreatment for biological
treatment. Some
compounds resist
oxidation.
Supercritical conditions
achieve high destruction
efficiencies f>99.99%) for
all constituents.
Not likely to achieve
residual levels in the low
ppm range for most
wastes.
Destruction efficiency of
over 99% reported for
dioxin
Bottoms will usually
contain levels of volati/es
in excess of 1,000 ppm;
condensate may require
further treatment.
Bottoms will contain
volatiles. Generally
suitable for incineration.
Aqueous treated stream
will probably require
polishing. Further
concentration of overhead
steam generally required.
Organic compound
solubility in aqueous phase
should be monitored.
Adsorbate must be
processed during
regeneration. Spent carbon
and wastewater may a/so
need treatment.
Adsorbate must be
processed during
regeneration.
Some residues likely which
need further treatment.
Residuals not likely to be a
problem. Halogens can be
neutralized in process.
Residual contamination
likely; will require
additional processing of off
gases.
Residual contamination
seems likely.
Biological Treatment Methods
Aerobic technology
suitable for dilute wastes
a/though some
constituents will be
resistant.
Conventional treatments
have been used for years.
May be used as final
treatment for specific
wastes, may be
pretreatment for resistant
species.
Residual contamination
likely; will usually require
additional processing.
-------
Norman Surprenant, Thomas Nunno, Mike Kravett, and Marc Breton are with
Alliance Technologies Corporation, Bedford, MA 01730.
Harry M. Freeman is the EPA Project Officer (see below).
The complete report, entitled "Technical Resource Document: Treatment
Technologies for Halogenated Organic Containing Wastes, Volume I," (Order
No. PB 88-131 271/AS; Cost: $38.95) 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:
Hazardous Waste Engineering Research Laboratory
U.S. Environmental Protection Agency
Cincinnati, OH 45268
United States
Environmental Protection
Agency
Center for Environmental Research
Information
Cincinnati OH 45268
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