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V -'! -'?'' y" _;
ENVIRONMENTAL
PROTECTION
AGENCY
DALLAS, TEXAS
UBMW
TREATMENT OF REACTIVE WASTES AT HAZARDOUS WASTE LANDFILLS
by
Douglas Shooter, Goo Hooi Ong
Alan Preston, John R. Ehrenfeld
Arthur D. Little, Inc.
Cambridge, Massachusetts 02140
Contract No. 68-01-5949
Project Officer
Robert Landreth
Solid and Hazardous Waste Research Division
Municipal Environmental Research Laboratory
Cincinnati, Ohio 45268
MUNICIPAL ENVIRONMENTAL RESEARCH LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
CINCINNATI, OHIO 45268
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TABLE OF CONTENTS
Page
I. ABSTRACT 1
II. CONCLUSIONS 3
III. RECOMMENDATIONS 7
IV. INTRODUCTION 8
A. Scope of Work 8
B. Approach 8
V. IDENTIFICATION OF PROBLEM WASTES 12
A. Classification Scheme for Reactive Wastes 12
B. Safety Precautions 23
VI. IDENTIFICATION OF TREATMENT ALTERNATIVES 24
A. Definition of Alternatives 24
B. Isolation/Containment 26
C. Hazard Destruction 27
VII. DATA GAPS AND RESEARCH NEEDS 32
APPENDICES
A. Representative Chemicals in Each Reactivity Class
B. Examples of Alternative Treatment Technology
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CONTENTS
X- _
>>>. C
Foreword iii
Abstract r iv
1. Introduction. . : 1
2. Conclusions
3. Recommendations
4. Identification of Problem Wastes
Classification Scheme for Reactive Wastes
Safety Precautions
5. Identification of Treatment Alternatives
Definition of Alternatives
Isolation/Containment
Hazard Destruction
6. Data Gaps and Research Needs
Bibliography of Primary Literature Sources
Appendices
A. Representative Chemicals in Each Reactivity Class . . .
B. Examples of Alternative Treatment Technology
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I. ABSTRACT
The segregation of reactive waste as a special class of hazardous
waste is provided for in the RCRA regulations, but the specifics of
the treatment and disposal methods which are applicable are not
documented by the present regulations. Providing adequate specific
information on reactive wastes is made more difficult by the wide
variety of chemical behavior which can be expected from materials
which fall into this category. In addition, many hazardous reactive
wastes, if improperly handled, are capable of acute physical damage to
personnel and property through fire and explosion. Thus, although
reactive hazardous wastes constitute only about 5% of the total
hazardous wastes, extreme caution must be used during transportation,
handling, storage, treatment and disposal.
This report is intended to provide an information base for personnel
accepting hazardous waste at existing disposal sites, or performing
remedial action at uncontrolled waste sites, to make the appropriate
decisions regarding the disposition of reactive wastes. It emphasizes
simple treatment and disposal schemes which are likely to be the most
cost effective. It provides information on the hazards to be
anticipated and the appropriate safety precautions necessary to
protect personnel and property and to prevent any further
environmental damage. The data in this report was obtained by
reviewing the extensive in-house background information on the
characteristics of reactive hazardous wastes; by reviewing the recent
literature, particularly information pertaining to the handling and
treatment of hazardous chemicals and finally by seeking information
and comment from operators of hazardous waste disposal sites,
including those specializing in the handling of reactive wastes.
The report is divided into three major sections: (1) Identification
of Problem Wastes; (2) Identification of Treatment Alternatives; and
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(3) Identification of Data Gaps. Additional information on classes of
chemical reactive wastes and treatment and disposal methods identified
from the literature, which were used to develop the more generalized
schemes, is provided in Appendices A and B, respectively.
Conclusions and Recommendations are summarized separately in Sections
II and III.
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II. CONCLUSIONS
1. Reactive wastes exhibit a broad spectrum of chemical behavior,
therefore, it is necessary to have a classification scheme which
allows for this diversity. Reactive wastes can be broadly
classified into two groups: those which may cause explosion and
those which do not. Many of the wastes which "do not explode are
water reactive, some are also reactive to air (e.g.,
pyrophoric) and some only react in acid solutions (e.g., cyanides
and sulfides) . Overall, the eight reactivity classes listed in
the Federal Register account for the chemical diversity of
reactive wastes quite well. However, a further subdivision of
classes I and II is proposed to allow for a better definition of
wastes which are pyrophoric, polymerizable or oxidizers.
2. Reactive wastes represent acute hazards to personnel and property
in addition to potential longer term'environmental hazards. It
may be necessary to employ blast protection, protective fire
resistant clothing and breathing apparatus as appropriate.
Materials which may cause explosion, particularly wastes which
are not well characterized should not be moved but should be
isolated from other wastes, property and personnel. For wastes
which are not subject to explosion, it is preferable to move the
waste to a safer location in order to isolate it from other
wastes, property and personnel. At that point, the further
containment, handling and treatment requirements can be
determined.
3. There is no universally applicable technique for isolation/
containment which is satisfactory for all reactive wastes.
Hazards in transportation, handling and storage of water reactive
federal Register, Vol. 45, No. 98, p. 33122, May 19, 1980.
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wastes can be reduced by dilution of material with an inert
solid or absorbent (vermiculite, sand, etc.) and protecting from
moisture. Conversely, the handling of explosive materials is
best done by keeping the materials in a wet state. Most
explosives are much more shock and friction sensitive when dry.
DOT regulations forbid transportation of certain recognized
explosive materials unless they are diluted with water or a
solvent such as alcohol. However, for many types of explosive
wastes, any handling or transportation can be extremely
hazardous, particularly since containers may be deteriorated and
the condition of the waste material the waste is not known.
Wastes of this type often have to be destroyed on site to avoid
handling and transportation.
4. Two destruction techniques appear to be more broadly applicable.
The first is open burning which may be applicable to most or all
reactive materials except cyanides and oxidizers. This method
has been applied to various types of water reactive materials,
e.g., alkaline metals and avoid, some of the complex equipment
required for other destruction techniques. It has also been
applied to the destruction of explosives and is still a permitted
use for destruction of explosive wastes vhich cannot be safely
incinerated. Local permit requirements for open burning may be
an obstacle to use of this method at some sites except as an
emergency response technique.
Destruction of reactive wastes by reaction with water (Classes
I-IV) ±s the second broadly applicable technique. Equipment
requirements may be more complex than for open burning, but
energy requirements are low.
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Destruction of water reactive wastes in aqueous media may lead to
the production of explosive or toxic gases which must be vented
or scrubbed from the atmosphere. Application of the open burning
technique to these wastes results in different reactions which
generally avoid the formation of explosive or toxic gases.
Explosive wastes are stable in water although some wastes can be
destroyed by alkaline solution.
5. Reaction with calcium hypochlorite (or other similar chlorine
containing compounds) is a well developed and widely practiced
technique for the destruction of inorganic cyanides. Although
other techniques are available there appears to be little
advantage in supplanting this technique with any other. Sulfides
can be oxidized by the same technique. Organic sulfides and
cyanides can be destroyed by combustion.
6. The field interviews covered three major companies in hazardous
waste management and three companies specializing in management
of reactive wastes. Each company has its own procedures for
management of reactive wastes and is selective about the type of
wastes it will or will not accept. The major companies tend to
be conservative and refer the more dangerous reactive wastes
(e.g., explosive wastes) to the specialist companies.
All the companies stressed the importance of obtaining expert
advice about the specific waste, and its location, before
attempting to handle it, prior to treatment and disposal. Some
wastes, e.g., ethers, which are easily handled as solvents, when
new may become extremely dangerous on ageing due to peroxide
formation.
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7. A number of data gaps have been identified by this preliminary
study. Some of the most important are:
(a) Lack of a comprehensive listing of hazardous wastes
detailing reactive properties, hazards and necessary safety
precautions (although a useful body of data does exist in
the OHM-TADS computerized hazardous materials data base).
(b) Lack of inventory data indicating the types and quantities
of reactive wastes being received by TSDF operators.
(c) Limited documentation of the effectiveness of simple,
broadly applicable techniques for isolation or destruction
of reactive wastes.
^IH/EPA Chemical Information System (CIS), Oil and Hazardous
Materials, Technical Assistance Data System (OHM-TADS).
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III. RECOMMENDATIONS
1. Further work should be carried out to expand the documentation of
reactive hazardous wastes which is contained in the appendices to
this report to make it comprehensive. Much of this information
is available in the literature or from industry sources. It
should be accessed by an expanded field interview program and
should be documented in a way which makes is more accessible to
TSDF operators. For those wastes where actual data is not
available, conservative estimates should be made based on
expected chemical properties.
2. Simple techniques and equipment for destruction of reactive
wastes by reaction in water or aqueous media need to be
developed. Information is needed on appropriate feed rates
requirements, venting or scrubbing of off-gases, and treatment
and disposal of spent reaction and scrubber solutions.
3. A program should be instituted to further develop techniques and
equipment for the open burning of reactive wastes which would
define the following parameters. Maximum quantities of waste to
be treated, potential hazards and necessary safety precautions
for personnel and equipment, requirements for auxiliary fuel and
disposal of residuals.
4. Estimates should be developed to compare the costs of destruction
of reactive wastes with the costs of alternative technologies,
particularly long term containment or landfill.
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IV. INTRODUCTION
The RCRA regulations provide a special category for reactive wastes
and prohibitions with respect to the treatment and disposal methods
employed for these wastes. Reactive wastes cover a wide spectrum of
physical and chemical properties. They generally display one or more
acute physical or chemical hazards and form an immediate potential
hazard to human health in addition to their potential danger to the
environment.
The number of chemical compounds or species which can be classified as
reactive hazardous is very large. A representative sample is listed
in Appendix A. Although many of these materials are not routinely
sent for treatment and disposal, most appear as wastes periodically
and even small quantities of less than 1 kilogram may pose a distinct
and severe acute hazard to health.
A. Scope of Work
The objective of this report is to aid Federal and state agency
personnel, remedial action coordinators and operators of TSDF's to
define the specific hazards posed by reactive wastes, the necessary
safety precautions to be taken and potential treatment methods.
Emphasis has been placed on documenting simple and practical measures
for treatment and disposal of reactive wastes which are already in
use, or alternatively on promising techniques which do not require
much further development and which should be applicable after develop-
ment with a high probability of success.
B. Approach
Three information sources were evaluated and combined to produce this
preliminary report. Each of these is described below.
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1. Our extensive background on existing hazardous wastes was
reviewed to identify examples of reactive hazardous wastes to
determine the characteristics of these wastes and document
information about treatment and disposal practices.
2. A comprehensive literature search was undertaken, particularly of
a number of standard works dealing with hazardous chemicals to
provide examples of specific classes of reactive wastes and
information on potential hazards and safety precautions. The
major sources are listed in Table 1.
The computerized literature was searched by means of the NIH/EPA
Chemical Information System (CIS), Oil and Hazardous Materials
Technical Assistance Data System (OHM-TADS). Material pertaining
to definition of the reactivity codes was obtained from the
Federal Register of Regulations. (FR 45, p33122, May 19, 1980).
Definitions for the various classes of explosives was obtained
from the Code of Federal Regulations (CFR 49.173, 1981).
3. A selected group of field interviews were undertaken to provide
additional information on actual field experience and field
practices. Personnel from the following six companies provided
information which is incorporated into this report.
CECOS International
Chemical Waste Management, Inc.
SCA Services Inc.
Battery Disposal Technology, Inc.
Advanced Environmental Technology Corporation (AETC)
Emergency Technical Services Corporation (ETSC)
CECOS, Chemical Waste Management and SCA Services are full
service companies who handle certain types of reactive hazardous
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TABLE 1 - PRIMARY LITERATURE SOURCES
1. Kirk-Othmer Encyclopedia of Chemical Technology, Volume 14, pg. 807,
2nd ed., Interscience Publishers, John Wiley & Sons, New York, 1967.
2. Strauss, H.J., Handbook for Chemical Technicians, McGraw Hill Book
Co., New York, 1976.
3. NIH/EPA Chemical Information System (CIS), OIL and Hazardous
Materials Technical Assistance Data System (OHM-TADS), Chemical
Information Systems, Inc., 7215 York Road, Baltimore, MD, 21212.
4. CHRIS Hazardous Chemical Data, Department of Transportation,
Coast Guard, CG 446-2, January 1974, available - Superintendent
of Documents, U.S. Government Printing Office, Washington, D.C.
20402.
5. Environmental Pollution Control Alternatives: Economic of Waste-
water Treatment Alternatives for the Electroplating Industry.
EPA 625/5-79-016, Technology Transfer, EPA, IERL, Cincinnati, OH,
June 1979.
6. Alternatives to the Land Disposal of Hazardous Wastes, An Assess-
ment for California, Toxic Waste Assessment Group, Governor's
Office of Appropriate Technology, State of California, 1600 Ninth
Street, Sacramento, CA, 95814, 1981.
7. Alternatives for Hazardous Waste Management in the Inorganic
Chemicals industry, prepared for EPA Office of Solid Waste,
Contract # EPA 68-01-4190, Report PB 274 656, 1977.
8. Survey of Solidification/Stabilizition Technology for Hazardous
Industrial Wastes by U.S. Army WES, Vicksburg, Mississippi, for
US EPA MERL, Cincinnati, OH, 45268, under Interagency Agreement
No. EPA-IAG-04-0569.
9. Partington, J.R., General and Inorganic Chemistry, 2nd ed. ,
McMillan and Company, limited, St. Martins Street, London,
925 pp., 1951.
10. Fire Protection Guide on Hazardous Materials, 6th Edition, National
Fire Protection Association, Boston, MA, 1975.
11. Phillip R. Powers, How to Dispose of Toxic Substances and Industrial
Wastes, Environmental Technology Handbook No. 4, Noyes Data Corpor-
ation, NJ, 1976.
12. Sax I.N. Dangerous Properties of Industrial Materials, 3rd Edition,
Van Nostrand/Reinhold, New York, 1968.
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wastes. They do not normally handle explosive materials.
Battery Disposal Technology Specializes in water-reactive wastes,
but does not treat explosive materials. AETC and its associated
company, ETSC, handle a wide variety of reactive wastes and
specialize in the treatment and disposal of explosive wastes.
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V. IDENTIFICATION OF PROBLEM WASTES
A. Classification Scheme for Reactive Wastes
The initial classification scheme adopted in this work was that
published as part of the RCRA Federal regulations. This classifica-
tion scheme which is reproduced in Table 2 separates reactive wastes
into eight different classes. In practice, reactive wastes exhibit a
wide range of chemical behavior and many chemicals do not fall
exclusively into one or other of these classes. However, two broad
subdivisions can be established between those wastes which may explode
or detonate and those wastes which do not. The hierarchy given below
is proposed for assigning chemicals to each of these classes based on
their potential for causing acute physical damage (fire and
explosion) and exposure to toxic gases.
VII > VI > VIII > I > IV > III > II > V
It is useful to provide subdivisions under some reactivity classes in
order to adequately describe the type of reactive behavior. For
example, Class 1 is subdivided into three sections: (la) pyrophoric
materials, (Ib) polymerizable materials, and (Ic) oxidizers. The
reactive effects Consequent hazards and necessary safety precautions
are somewhat different in each case. Similarly, Class 2 is provided
with two subdivisions: (2a) those materials which cause a large
evolution of heat in contact with water, but do not decompose, and
(2b) those materials which decompose in water and usually decompose
(more slowly) in moist air. A format for describing each of the
different reactivity classes is given in Tables 3-10. Each table
provides a definition of the class, the properties of reactive wastes
in that class, specific examples ("representative only), the hazards
associated with that type of reactive material, and the necessary
safety precautions.
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TABLE 3
CLASS I
Definition
It is normally unstable and readily undergoes violent change without
detonating
Properties
IA: Pyrophoric. Spontaneous ignition in contact with air
IB: Polymerizable. Spontaneous polymerization in contact with air or on
heating
1C: Oxidizers. Violent reaction in contact with organic materials or
strong reducing agents
Specific Examples
IA: Metal alkyls, finely divided metal powders (Magnesium, Aluminum and Zinc)
IB: Divinyl benzene
1C: Perchloric acid, fuming nitric acid
Hazards
Acute physical harm from fire or mechanical explosion caused by rupturing
of containers
Safety Precautions
Full protective, fire resistant clothing with gloves and face shield.
Seek expert advice before handling.
Take precuations to avoid rupture of the container. If the container is intact,
move the material and isolate from other incompatible wastes, personnel and
equipment.
Pyrophoric wastes - prevent contact with air or water
Polymerizable wastes - keep cool (below 70°C), prevent contact with water
Oxidizers - prevent contact with organic materials (paper, wood, cellulose,
solvents, oil, etc.)
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TABLE 4
CLASS II
Definition
It reacts violently with water.
Properties
HA: Causes a large evolution of heat in contact with water.
IIB: Decomposes in moist air and violently decomposes with liquid
water.
Specific Examples
HA: Sulfuric acid, chlorosulfonic acid
IIB: Phosphorus pentachloride, titanium tetrachloride
Hazards
Physical harm from fuming in moist air causing exposure to corrosive
and/or toxic gases. Splashing of material due to the violent reaction
and subsequent skin contact with corrosive materials.
Safetv Precautions
Protective, acid resistant, rubber or plastic clothing with gloves and
face shield.
Seek expert advice before handling.
Take precautions to avoid rupture of the container. If corroded,
cover to prevent access of moisture. If the container is intact or
sealed, move the material and isolate from other incompatible wastes 4
and prevent exposure to water or moist air.
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TABLE 5
CLASS III
Definition
It forms potentially explosive mixtures with water.
Properties
Decomposes violently in water with evolution of heat and flammable
gases which may ignite if exposed to a source of ignition. Evolution
of heat with water may be sufficient to cause auto-ignition and
explosion.
Specific Examples
Alkali metals, alkali metal hydrides, alkali metal nitrides
Hazards
Acute physical harm from fire or explosion caused by ignition of
flammable gases.
Safety Precautions
Full protective fire resistant clothing with gloves and face shield.
Seek expert advice before handling.
Take precautions to avoid rupture of the container. Cover to prevent
access of moisture. If the container is intact, move the material and
isolate from other incompatible wastes, exclude all possible sources
of ignition - sparks, heat flames.
Provide ventilation to disperse flammable gases. Use of water as a
fire extinguisher may aggravate the fire potential hazard. Use dry
sand to smother material.
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TABLE 6
CLASS IV J|
Definition
When mixed with water it generates toxic gases, vapors or fumes in a
quantity sufficient to present a danger to human health or the
environment.
Properties
Reacts rapidly with water with the production of gases or vapors which
are acutely toxic to human health.
Specific Examples
Alkali metal phosphides, toluene diisocyanate
Hazards _
Acute health through inhalation or possibly through skin contact with
hazardous toxic vapors.
Safety Precautions
Wear self-contained breathing apparatus. Full protective clothing
with gloves and face shield.
Seek expert advice before handling.
Take precautions to prevent rupture of the container. If the
container is intact, move the material and isolate from other
incompatible wastes and personnel. Seal to prevent contact with
moisture and provide adequate ventilation to disperse toxic gases.
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TABLE 7
CLASS V
Definition
It is cyanide or sulfide bearing waste, which when exposed to pH
conditions to between 2 and 12.5 can generate toxic gases, vapors or
fumes in a quantity sufficient to present a danger to human health or
the environment.
Properties
Cyanide and sulfides produce extremely toxic hydrogen cyanide gas or
hydrogen sulfide gas, respectively, on contact with acids or materials
which form acids in the presence of moisture or liquid water.
Specific Examples
Potassium cyanide or other metal cyanides, lead sulfide and similar
metal sulfides. Organic cyanides and sulfides.
Hazards
Acute toxic effects from inhalation of hydrogen cyanide or hydrogen
sulfide. Acute toxic effects from skin contact with hydrogen cyanide.
Safety Precautions
Wear self-contained breathing apparatus. Full protective clothinp
with gloves and face shield.
Seek expert advice before handling.
Take precautions to prevent rupture of the container. If the
container is intact, move the material and isolate from other
incompatible wastes nnd personnel. Seal to prevent contact wirh
moisture
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TABLE 8
CLASS VI
Definition
It is capable of detonation or explosive reaction if it is subjected
to a strong initiating source or if heated under confinement.
Properties
Detonation or explosion if heated above ambient temperature or if
exposed to an initating source such as shock, mechanical shock, spark
or flame or a catalyst which accelerates decomposition.
Examples
Lead amide, parathion, isoamyl nitrite, ammonium nitrate, hydrazine
Hazards
Capable of causing acute physical hazard to human health and property
through energy transfer resulting in a violent mechanical force«
accompanied by shock, heat and possibly fire.
Safety Precautions
It is imperative to seek expert advice before approaching containers
of these materials. Do not touch or move. Do not subject to heat or
shock.
Wear full protective fire-resistant clothing before approaching the
container location.
Proceed with extreme caution. If possible, isolate by moving all
other hazardous materials in the immediate vicinity. Shield the
container from sun to prevent heating. Clear the area of other
valuable equipment and property.
It is often advisable to provide destruction of Class VI material
on-site to avoid additional hazards during transportation
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TABLE 9
CLASS VII
Definition
It is readily capable of detonation or explosive decomposition or
reaction at standard temperature and pressure.
Properties
Capable of detonation or explosive decomposition under ambient
conditions of temperature and pressure without any external initiating
source.
Specific Examples
Organic peroxides such as benzoyl peroxide, acetyl peroxide, other
materials which may form peroxides on standing, e.g., ethers, dioxane
and tetrahydrofuran.
Hazards
Capable of causing acute physical hazard to human henlrh .ird property
through energy transfer resulting in a violent mechanical force
accompanied by shock, heat and possihlv fire.
Safety Precautions
It is imperative to seek expert advice before approaching container;.
of these materials. Do not touch or move. Do not subject to heat or
shock.
Wear full protective fire-resistant clothing before approaching the
container location.
Proceed with extreme caution. If possible, isolate by movine nil
other hazardous materials in the immediate vicinity. Shield the
container from sun to prevent heating. Clear the area of other
valuable equipment and property.
It is often advisable to provide destruction of Class VII material
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TABLE 10 m
CLASS VIII
Definition
It is a forbidden explosive as defined in 49 CFR 173.51. or a Class A
explosive as defined in 49 CFR 173.53, or a Class B explosive as defined
in 49 CFR 173.88.
Properties
Forbidden Explosives. Capable of detonation or explosive decomposition
under ambient conditions, considered too dangerous for transportation.
Class A Explosives. Highly explosive, capable of detonation but safe to
transport if handled in accordance with DOT regulations and segregated
from initiating compounds.
Class B Explosives. Flammable explosives capable of rapid combustion but ^
not detonation. Safe to transport in accordance with DOT regulations.
Specific Examples
Forbidden Explosives. Diethylene glycol dinitrate, acid metal salt or
ammonium salt and chlorate.
Class A Explosives. Commercial dynamite, desensitized nitroglycerine,
initiating explosives such as lead azide, mercury fulminate.
Class B Explosives. Rocker propellants, smokeless powder.
Hazards
Capable of causing acute physical hazard to human health and property
through en-ergy transfer resulting in a violent mechanical force
accompanied by shock, heat and possibly fire.
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TABLE 10
(continued)
Safety Precautions
It is imperative to seek expert advice before approaching container:
of these materials. Do not touch or move. Do not subject to hent
shock.
Wear full protective fire-resistant clothing before approaching the
container location.
Proceed with extreme caution. If possible, isolate by moving all
other hazardous materials in the immediate vicinity. Shield the
container from sun to prevent heating. Clear the area of other
valuable equipment and property.
It is often advisable to provide destruction of Class VIII material
on-site to avoid additional hazards during transport/it ion
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B. Safety Precautions
Reactive wastes have the capability of causing acute adverse effects
to human health and, therefore, must be stored, handled, treated, and
destroyed by experienced operators. Three types of acute effects can
be distinguished: explosion, fire, and exposure to toxic gases. For
many wastes, at least two of these effects may occur simultaneously.
In particular, those materials which may detonate must be treated with
extreme caution. Transportation of hazardous materials is extensively
covered by DOT regulations. Many reactive wastes can be classified
under these regulations. In some cases the requirements may be more
stringent than necessary for transportation of wastes. However, some
wastes may be dangerous and unacceptable for transportation due to
aging, lack of inhibitors, or deterioration of the container. In
those cases, it becomes necessary to seek expert assistance and treat
or dispose of the material on site as safely as possible.
Reactivity of individual chemicals in a specific chemical class, e.g.,
alkali metals, will vary considerably. This rate of activity may also
vary as a result of aging or contamination by other wastes.
Therefore, it is prudent to handle, treat, and dispose of such
materials in accordance with the harmful effects of the most hazardous
member of that particular class.
Tables 3-10 indicate the nature of safety precautions (personnel,
equipment and property protection) which should be taken for each
class of reactive wastes. This information is only intended to
provide a general guide and is not sufficiently detailed to permit
handling of reactive wastes without prior experience and more detailed
information. In addition, specific requirements may be imposed by
local codes and ordinances.
Transportation, Hazardous Material Regulations Code of Federal
Regulations (CFR) 49 parts 171-175, p. 51 et seq., 1981.
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VI. IDENTIFICATION OF TREATMENT ALTERNATIVES
A. Definition of Alternatives
Our first approach to defining alternative treatment technology was to
assess our background information and search the literature for
specific examples using commonly recognized chemicals or waste materials
from each reactivity class. An example of the format used for this
analysis is shown in Table 11. The data organized under this format
are collected together in Appendix B. At first, the treatment
technology was separated in three groups: (1) isolation or
containment, (2) hazard reduction, and (3) detoxification. However,
in many instances, it was found that the difference between groups 2
and 3 were attributable more to differences in the chemical properties
of the waste than to differences in treatment technology. Therefore,
->
these two subcategories were combined into a single subrcategory
entitled "Destruction". Each technology was assessed qualitatively in
terms of the following criteria:
Technical Feasibility; Applicability; Chemicals and Equipment
Requirements; Operator Requirements; Residual Production;
Advantages/Disadvantages; and Relative Cost.
Differences in ranking were expressed in the following way:
+ - Above Average Ranking
0 - Average Ranking
Below Average Ranking
NA - Not Applicable
For example, in terms of feasibility, a plus ranking would indicate
that this is a well-established, well-documented technology which has
bear, used commercially on similar wastes. A negative ranking would
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indicate that the technology appears feasible as demonstrated by
laboratory experiments, but actual commercial operation or
applicability to real wastes has not been well documented. Further
explanation to back-up -e the qualitative ranking for each of the
technologies described is also provided in Appendix B.
The cost ranking was the most subjective element in this list because
of the general absence of cost data for the types of technology
described and evaluated in this report. A plus value indicates that
the cost is expected to be lower than average because the technique
requires less than average operator experience and only simple
low-cost equipment. A negative value indicates an expected higher
than average cost because the technique requires more complex chemical
processing equipment, instrumentation or analysis, and a high level of
operator experience due to the difficulty of operating the process or
the hazards involved.
The purpose of isolation containment technology is to reduce the
immediate hazards associated with the reactive wastes so that it can
be handled, stored and transported in accordance with accepted
practices, e.g., DOT regulations for the chemicals involved.
B. Isolation/Containment
From an evaluation of the available data, we have selected eight
isolation/containment techniques which are broadly applicable to a
number of reactive waste classes. Applicability is indicated in Table
12 in terms of a check for applicable, X for not applicable and ?
where the technique may only be acceptable for some members of the
reactive class. Not surprisingly no technique is applicable to all 8
classes of reactive wastes. The primary dividing line is between
those classes which can cause explosion or detonation (VI, VII, VIII)
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and those which do not. The general procedure for each technique is
indicated in Table 12. Detailed specific operating procedures for
each of these methods have not been documented or evaluated for all
the examples indicated. The selection has been made on the basis of
background knowledge and experience and the available literature data.
In addition, the appropriate safety procedures must be followed.
Two procedures stand out as being generally applicable. The first
involved dilution, by mixing with excess solid and sealing in a dry
container. The solid can be an inert material such as sand or
vermiculite or an absorbent such as ground clay (kitty litter) or
limestone. Some wastes such as acids or acid-forming materials
(e.g., TiCl.) may react with limestone evolving gas which can
pressurize and cause failure of a hermetically sealed container. This
method is generally applicable for reactive waste classes I - V.
The second procedure involves mixing with water and excess inert or
absorbent solid. Wet explosive materials are less susceptible to
shock and heat. Transportation of many explosive materials in the dry
state is forbidden by DOT regulations. Use of ethanol/water
mixtures may ha"e an advantage in solubilizing some organic wastes.
Alkaline solutions may have an advantage in stabilizing or decomposing
some wastes.
C. Hazard Destruction
A listing of broadly applicable techniques for hazard destruction is
shown in Table 13. As might be anticipated, the rtin« techniques
listed are not as broadly applicable to a group of waste classes as
Many explosive materials are extremely friction and shock sensitive
in the dry state and should only be handled or transferred by
experts.
27
Arthur D. Little, Inc.
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for containment isolation because destruction requires more specific
technology. The same symbols are used in this table ( /, x and ?)
with the addition of a 0 in Class V. The latter indicates that mixing
with weak alkali may stabilize reactive cyanides and sulfides, but
will not cause destruction.
Mixing with an inert solid, such as vermucilite, followed by open
burning may be the most broadly applicable technique (it is not
applicable to Class V, Cyanides and Sulfides).
Water reactive compounds should be kept dry and may need auxiliary
fuel to ensure complete destruction. Incineration of some water
reactive wastes, e.g., alkali metal wastes, is used commercially.
One environmental problem with open burning of reactive wastes is
potential air pollution from release of toxic gases, e.g., sulfur
dioxide, nitrogen oxides, hydrogen chloride. Thus, to be
environmentally acceptable only small amounts can be destroyed in this
manner. Open burning of explosive wastes was widely practiced to
2
destroy both commercial and military explosive wastes . Open pit
burners have been developed and used extensively by DuPont, Union
Carbide and others. Visible smoke can be eliminated but this type of
incineration does not provide good control over particulate or noxious
gas emissions. This type of burning has proven effective for the
destruction of many types of explosives and is particularly effective
with solid wastes. Explosive materials are destroyed while wet which
increases the auxiliary fuel requirements.
Battery Disposal Technology, Inc., Clarence, N.Y.
R.S. Ottinger, et al., Recommended Methods of Reduction
Neutralization, Recovery or Disposal of Hazardous Waste,
PB 224 582, NTIS, Springfield, VA, August 1973.
30
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Hydrolysis by controlled reaction with excess water is an effective
technique for many reactive wastes in Classes I - IV. Process
efficiencies may be increased by use of alkaline solutions which may
also serve as scrubbing solutions for effluent toxic gases. This
process is used commercially for the destruction of acidic, water
reactive wastes. It is also applicable to reactive metals and their
reactive compounds. Venting must be provided to prevent accumulation
of flammable or toxic gases.
Alkaline chlorination is a widely used technology for destruction of
cyanides and sulfides. The level of sophistication (equipment,
control, analysis) increases with the scale of operations. However,
the technique can "be safely used in small-scale, batch operations
using sodium or calcium hypochlorite as the oxidizing agent.
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VII DATA GAPS AND RESEARCH NEEDS
1. The OHM-TADS computerized data base is very useful for charting
the properties, hazards, treatment requirements and safety
precautions for reactive hazardous wastes. However, many fairly
common examples of reactive hazardous wastes are not presently
included in the OHM-TADS system. The relevant data on chemicals
and other wastes now included in this system should be collected
and evaluated to increase its utility to hazardous waste
personnel. A listing of incompatible reactive wastes should be
developed because mixing of certain incompatible wastes may cause
an unacceptably large increase in hazard or even a change in the
type of hazard to be expected, i.e., from fire to explosion.
This is particularly important to personnel who are assembling
lab packs of chemicals for transportation and disposal at remote
sites.
2. EPA and others have developed directories of EPA registered,
r. hazardous waste transporters and TSDF operators, together with
information on the types of wastes that they process. However,
reactive wastes often present acute hazards unlike other
hazardous wastes and there is an urgent need for a separate
directory or section which clearly indicates those companies who
are qualified and willing to accept specific classes of reactive
wastes together with a list of waste they are able to accept for
treatment or disposal.
, 3. Most reactive wastes occur in small quantities of 1-2 pounds, but
55 gallon drums or even tank car loads are by no means uncommon.
The TSDF operator needs guidance on the maximum quantity of a
particular waste which can be handled by simple procedures.
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Arthur D. Little, Inc.
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4. Further research is required to develop an inventory of the
specific type and quantities of reactive wastes which are
presently entering the market for treatment and disposal. The
inventory should differentiate between small quantities of lab
chemicals and larger volumes of industrial wastes and assist in
defining future needs for waste disposal technology and services.
5. Two generalized simple techniques have been identified for the
destruction of a variety of reactive hazardous wastes classes.
The most widely applicable technique appears to be a modified
form of open burning and the second is reaction with water for
those wastes which are destroyed by this treatment. However,
simple, effective equipment for this purpose has not been
developed and tested by either the Federal government or
commercial firms (although some may be in use within specific
companies). Thus, there is an urgent need for further
development of these two methods to determine the form of
equipment which is most suitable; the maximum quantities of
material which can be safely handled; reliable, safe operating
procedures; and techniques for treating effluents. Finally,
capital and operating costs estimates for such processes need to
be developed.
6. Data on true costs for treatment and disposal of reactive wastes
by simple techniques has not been developed. The components of
the cost data also fall outside the typical engineering cost
element approach and are highly weighted by elements such as
transportation, handling, personnel protection,
recontainerization, and analysis. There is a need to develop
applicable cost data based on the existing field experience and
generalized so as to be applicable to a wide spectrum of reactive
wastes.
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Evaluation of field experience was unavoidably restricted by the
time and budget limitations of the present study. This
deficiency should be remedied by a more extensive field interview
program to more fully document experience and present practices.
34
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APPENDIX A
REPRESENTATIVE CHEMICALS IN EACH REACTIVITY CLASS
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CLASS I
Reactivity Characteristic - Normally unstable, undergoes violent change
without detonating
IA: Pyrophoric. Spontaneous ignition in contact with water
IB: Polymerizable. Spontaneous polymerization in contact with air or
on heating.
1C: Oxidizers. Violent reaction in contact with organic materials or
strong reducing agents.
Example s
IA PYROFORIC
Metal alkyls (Mg, Zn, Al, Ti, Sn)
Sodium hydrazide
Metal powders, finely divided
(Mg, Al, Zn, Ni)
Ferrous sulfide
Sodium superoxide
Phosphorus
Manganese bicyclopentadienyl
Ammonium oersulfate
Nature of Hazard
ignites in air
ignites in air
oxidizes in air becoming incandescent
oxidizes in air becoming incandescent
decomposes liberating oxygen
ignites in air
ignites in air
ignites in air
IB POLYMERIZABLE
Divinyl benzene
liberation, of heat which may
lead to ignition
1C OXIDIZER
Perchloric acid
Chromic acid
Nitric acid
Hydrogen peroxide (above 90%)
rapid intense reaction
with organic materials
which may cause ignition
and fire
Al
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CLASS II
Reactivity Characteristic - Reacts violently with water
1IA: Causes a large evolution of heat in contact with water.
IIB: Decomposes in moist air and violently decomposes with liquid
water.
Example s
IIA HEAT EVOLUTION
Sulfuric acid
Oleum
Chlorosulfonic acid
Phosphorus trioxide and pentoxide
Nature of Hazard
vigorous reaction, liberation of heat
splashing of corrosive liquid
IIB DECOMPOSITION
Acetyl halides
Phosphorus halides
Titanium tetrachloride
Gyloxal
vigorous reaction, liberation of
heat and acid fumes
polymerizes rapidly
A2
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CLASS III
Reactivity Characteristic - Forms potentially explosive mixtures with water
Examples
Alkali metals
Alkaline earth metals
Alkali metal silicides
Aluminum hydride
Lithium Borohydride
Alkali metal nitrides
Alkali metal hydrides
Alkali metal carbides
Nature of Hazard
reaction, evolves H2
reaction, evolves H£
reaction, evolves silane
violent reaction, evolves H2
violent reaction, evolves H£
reaction, evolves H2 and NH3
reaction, evolves H2
reaction, evolves acetylene
A3
/tti Arthur D. Little, Inc.
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CLASS IV
Reactivity Characteristic - Generates toxic gases which present a danger to
health or the environment
Examples Nature of Hazard
Alkali metal phosphides decomposition, evolves phosphine
Aluminum phosphide decomposition, evolves phosphine
Phosphorus sulfides decomposition, evolves l^S
Phosphorus halides decomposition, evolves HX
Toluene diisocyanate violent decomposition, evolves
toluenediamine
A4
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CLASS V
Reactivity Characteristic -
Cyanide or sulfide bearing waste which may
generate toxic gases
Examples
Nature of Hazard
Metal cyanide salts of sodium,
potassium, copper, silver and gold
Organic cyanide compounds
Metal sulfide salts
Organic sulfides and mercaptans
liberate HCN in the presence of
acids
liberate
acids
in the presence of
A5
Arthur D. Little, Inc.
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CLASS VI
Reactivity Characteristic -
Capable of detonation or explosion if strongly
initiated or if heated
Examples
Nature of Hazard
Lead Amide
Sodium Amide
Thallous nitride
Metal azides
Brominated organic compounds
Benzene diazonium salts
Ammonium picrate
Ammonium tetrachromate
Metal periodates
Parathion
Organic perchlorates
Isoamyl nitrite
Chloropicrin
Ammonium nitrate
Ammonium chlorate
explodes in hot water
explodes with shock, heat, or
exposure to water
explode with shock or heat
explode with shock or heat
explode with slight shock
explodes with shock or heat
explodes with heat
explodes with heat
explodes with heat
explodes with heat
explodes with heat
explodes with heat
explodes with heat
explodes with heat
A6
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CLASS VII
Reactivity Characteristic - Readily capable of decomposition or detonation
at STP
Examples
Nature of Hazard
Ammonium chlorate
Anisoyl chloride
Organic azides
Ammonium chlorate
Metal azides
Acetyl nitrate
Acetyl peroxide
Benzoyl peroxide
Sodium benzyl
Chloroacetone
Ethers
Hydrazine and derivatives
Peroxy acids
Dioxane
Tetrahydrofuran
unstable explosive decomposition
unstable, explosive decomposition
unstable, explosive decomposition
unstable, explosive decomposition
ignite in air, may explode
unstable, explodes with shock
unstable, explodes with shock
unstable, explodes with shock
ignites in air
polymerization, explodes with shock
flammable, form explosive peroxides
on ageing
ignites in air even when absorbed
out porous materials, may explode
explosive, shock sensitive
flammable, forms explosive peroxides
on ageing
flammable, forms explosive peroxides
on ageing
A7
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CLASS VIII
Reactivity Characteristic -
It is a forbidden explosive as defined in
49 CFR 173.51, or a Class A explosive as
defined in 49 CFR 173.53 or a Class B
explosive as defined in 49 CFR 173.88
Examples
Nature of Hazard
Forbidden Explosives
Diethylene glycol di-nitrate
Chlorate with ammonium or acid
metal salts
Unstabilized nitroglycerine and
nitrocellulose
Initiating explosives (see Class A
explosives below) if dry
Di-nitrosalicylic acid
Nitrogen tri-iodide
Chlorine dioxide
Perchloric acid >72%
spontaneous detonation, extremely
shock, heat and friction sensitive
(Transportation of these materials
is forbidden under DOT regulations)
Class A Explosives
TNT
PETN
Initiating explosives
Lead or silver styphnate
Silver tetrazene
Gold or mercury fulminate
Diazo dinitrophenol
Lead 2-4 dinitroresorcinate
High explosive, detonates readily
if initiated
Extremely shock and friction
sensitive if dry, must be transported
wet in small quantities
AS
Arthur D. Little, Inc.
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CLASS VIII (CONTINUED)
Examples
Nature of Hazard
Class B Explosives
Stabilized nitrocellulose
Stabilized nitroglycerin
Rocket propellants
Smokeless powder
Explosive combustion
but unlikely to detonate
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Arthur D. Little, Inc.
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APPENDIX B
EXAMPLES OF ALTERNATIVE TREATMENT TECHNOLOGY
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APPENDIX B - LIST OF EXHIBITS
Page
Class I A Treatment Matrix
Triethyl Aluminum
Triethyl Aluminum
Combustion
Storage
I C Treatment Matrix
Chronic Acid
Pechloric Acid
Sodium Chlorate
Reduction
Reduction
Reduction
Class II Treatment Matrix
dyoxal
Sulfuric Acid
Chlorosulfuric Acid
Glyoxal
Sulfuric Acid
Chlorosulfonic Acid
Acetic Anhydride
Acetic Anhydride
Chloracetone
Combustion
Neutralization
Neutralization
Storage
Storage
Storage
Hydrolysis/Neutralization
Storage
Combustion
Class III Treatment Matrix
Sodium
Sodium
Combustion
Storage
Class IV Treatment Matrix
Titanium Tetrachloride
Phosphorus Trichloride
Titanium Tetrachloride
Phosphorus Trichloride
Neutralization
Neutralization
Storage
Storage
Class V Treatment Matrix
Sodium Cyanide
Sodium Cyanide
Sodium Cyanide
Phosphorus Pentasulfide
Phosphorus Pentasulfide
Alkaline Chlorination
Peroxide Oxidation
Electrolytic Oxidation
Encapsulation/Landfill
Peroxide Oxidation
Bl
/IL Arthur D. Little, Inc
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Class VI
Treatment Matrix
Sodium Azide
Parathion
Ammonium Nitrate
Reaction with eerie
ammonium acetate
Incineration
Reaction with soda ash
1
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Class VII Treatment Matrix
Benzoyl Peroxide
Benzoyl Peroxide
Ethylene Oxide
Picric Acid
Combustion
Reduction
Combustion
Incineration
B2
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Chemical - Triethylaluminum
Waste Description: waste solutions of 100% triethylaluminum
Destruction Technology: Store in cylinder which protect the
triethylaluminum from.exposure to the
atmosphere and water. Cylinders should be
isolated in an explosion containment
building.
Evaluation Table
Criteria
Technical
Feasibility
Applicability
Chemicals &
Equipment
Operator
Requirements
Residual
Production
Advantages/
Disadvantages
Cost
Rating
Comments
Containment cylinders utilized
Applicable for temporary
storage
Requires explosion containment
structure
Unskilled labor is adequate
N.A.
Accumulate for batch/potential
explosion acccidents
Overhead for explosion containment
structure
B4
/1L Arthur D. Little, Inc
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m
^
Chemical - Triethylaluminum
Waste Description: waste solutions of 100% triethylaluminum
Destruction Technology:
Combustion, mix with excess soda ash,
place in iron pan, cover with combustible
material (i.e., wood, paper) and burn in open
area.
Evaluation Table
Criteria
Technical
Feasibility
Appicability
Chemicals &
Equipment
Operator
Requirements
Residual
Production
Advantages/
Disadvantages
Cost
Rating Comments
+ Simple procedure
0 Small batch operations
+ Common materials
Safety procedures must be
followed to prevent potential
explosions
None
Destruction/potential for
accidental explosions
Ralrtively inexpensive
B5
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B6
-------
Chemical - Perchloric Acid
Waste Description: unused perchloric acid - 60-70%
Destruction Technology:
Reduction, sodium bisulfite is a commonly
used agent, mix the bisulfite with perchloric
acid solution, acidify with H2SO, and .
after reduction is completed, neutralize.
Evaluation Table
Criteria
Technical
Feasibility
Applicability
Chemicals 4
Equipment
Operator
Requirements
Residual
Production
Advantages/
Disadvantages
Cost
Rating
Comments
Commonly used process
Batch or continuous operation
Readily available
Unskilled labor is adequate
None
Simple process/cost
Chemical cost
B7
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Chemical - Chromic Acid
Waste Description: unused chromic acid - 100% pure
Destruction Technology:
Reduction, commonly used reducing agents are
sodium metabisulfite, sodium bisulphite, and
sodium sulfite, hexavalent chrome is reduced
to the less hazardous trivalent form.
Evaluation Table
Criteria Rating
Technical +
Feasibility
Applicability +
Chemicals & +
Equipment
Operator +
Requirements
Residual 0
Production
Advantage/ +
Disadvantages
Cost 0
Comments
Commonly used process
Applicable in both a continuous
and batch mode
Readily available chemicals and
equipment
Unskilled labor is adequate
Aqueous solution of trivalent
chromium
Simple process/residual should
be treated
Chemical cost
B8
/ti Arthur D. Little, Inc
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Chemical - Sodium Chlorate
Waste Description: unused sodium chlorate - 99* pure
Detoxification Technology: Reduction, reduce with concentrated ,
sodium bisulfite solution, neturalize"
Evaluation Table
Criteria Rating
Technical +
Feasibility
Applicability +
Chemicals & +
Equipment
Operator +
Requirements
Residual +
Production
Advantage +
Disadvantage +
Cost 0
Comments
Commonly used process
Readily applicable
Common used chemicals and
processing equipment
Unskilled labor is adequate
None
Simple process
Need chemical reagents
Chemical cost is adequate
B9
Arthur D. Little, In<
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BIO
/1L Arthur D. Little, Inc.
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Chemical - Glyoxal
Waste Description: spent glyoxal solutions
Destruction Technology: Combustion, mix with vermiculite, burn in
open area.
1
i
T
i
Evaluation Table
Criteria
Technical
feasibility
Applicability
Chemicals &
Equipment
Operator
Requirements
Residual
Production
Advantages/
Disadvantages
Cost
Rating Comments
Simple procedure
Small batches
Readily available chemicals,
no special equipment
Unskilled labor adequate
Potential air pollutants,
absorbing agents
Low cost/potential air
pollution impacts
Relatively inexpensive
Bll
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I
I
1
1
Chemical - Sodium
Waste Description: unused sodium
Destruction Technology: Combustion, add to fire of oil soaked rags
in a dry steel pan.
Evaluation Table
Criteria
Technical
Feasibility
Applicability
Chemicals &
Equipment
Operator
Requirements
Residual
Production
Advantages/
Disadvantages
Cost
Rating Comments
+ Simple procedure
0 Small batches
+ Low technology equipment
+ Unskilled labor is adequate
0 Sodium oxide fumes
Low cost, simple procedure/
evolution of oxide fumes
Relatively cheap
B12
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Chemical - Acetic Anhydride
Waste Description: waste solutions of 100 acetic anhydride
Destruction Technology: Hydrolysis/neutralization, slowly add to
water, acetic anhydride will slowly
hydrolyse, neutralize acetic acid.
Evaluation Table
Criteria
Technical
Feasibility
Applicability
Chemicals &
Equipment
Operator
Requirements
Residual
Production
Advantages/
Disadvantages
Cost
Rating Comments
Well understood reaction
Small batch operation
Readily available chemicals and
equipment
Chemical technician level preferred
to run the reaction in controlled
state
Acetic acid which must be
neutralized
Simple procedure/hydrolysis can
generate large amounts of heat
and emit toxic fumes
Relatively inexpensive,
neutralization chemical required
B13
/k Arthur D. Little, Inc.
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Chemical - Acetic Anhydride
Waste Description: waste solutions of 100 acetic anhydride
Destruction Technology: Combustion, mix with sand and burn in
open area. '
Evaluation Table
Criteria Rating
Technical +
Feasibility
Applicability 0
Chemicals & +
Equipment
Operator 0
Requirements
Residual
Production
Advantages/
Disadvantages
Cost
Comments
Simple procedure
Limit to small batch
operations
Requires only sand
Safety cautions must be
practiced to prevent inhalation
of toxic fumes
None
Simple,' low cost material/
possible emission of toxic vapors
Relatively inexpensive
B14
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Chemical - Acetic Anhydride
Waste Description: waste solutions of 100 acetic anhydride
Destruction Technology: Store in glass jugs, aluminum containers
or stainless steel containers, isolate from
ignition sources, area should be cool and
well ventilated.
Evaluation Table
Criteria Ratin?
Technical
Feasibility
Applicability
Chemicals &
Equipment
Operator
Requirements
Residual
Production
Advantages/
Disadvantages
Cost
Comments
Stored by user industry
Should limit to short
term storage
Requires corrosion resistant
containers
Unskilled labor is adequate
N.A.
Store for batch applications/
increased overhead cost,
potential for accident
Expensive containers required,
overhead for storage area
B15
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Chemical - Triethylaluminum
Waste Description: waste solutions of 100% triethylaluminum
Destruction Technology:
Combustion, mix with excess soda ash, place
in iron pan, cover with combustible material
(i.e.. wood, paper) and burn in open
area. '
Evaluation Table
\
i
Criteria
Technical
Feasibility
Applicability
Chemicals &
Equipment
Operator
Requirement
Residual
Production
Advantages/
Disadvantages
Cost
Rating Comments
+ Simple procedure
0 Small batch operations
+ Common materials
Safety procedures must be
followed to prevent explosions
None
Destruction/potential for
accidental explosions
Relatively inexpensive
B16
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Chemical - Triethylalucinum
Waste Description: waste solutions of 100% triethylaluminum
Destruction Technology:
Store in cylinder which protect the
triethylaluminum from.exposure to the
atmosphere and water. Cylinders should be
isolated in an explosion containment
building.
Evaluation Table
Criteria Rating
Technical +
Feasibility
Applicability 0
Chemicals & -
Equipment
Operator +
Requirements
Residual
Production
Advantages/ -
Disadvantages
Cost
Comments
Containment cylinders utilized
by user industries
Applicable for temporary storage
Requires explosion containment
structure
Unskilled labor is adequate
N.A.
Accumulate for batch/potential
explosion accidents
Overhead for explosion containment
structure
I
i
B17
/k Arthur D. Little, Inc.
-------
i
I
i
1
Chemical - Acetic Anhydride
Waste Description: waste solutions of 100% acetic anhydride
Destruction Technology: Store in glass jugs, aluminum containers
or stainless steel containers, isolate from
ignition sources, area should be cool and
well ventilated.
Evaluation Table
Criteria Ratin?
Technical
Feasibility
Applicability
Chemicals &
Equipment
Operator
Requirements
Residual
Production
Advantages/
Disadvantages
Cost
1
1
Comments
Stored by user industry
Should limit to short term
storage
Requires corrosion resistant
containers
Unskilled labor is adequate
N.A.
Store for batch applications/
increases overhead cost, potential
for accident
Expensive containers required,
overhead for storage area
B18
/k Arthur D. Little, Inc.
-------
1
I
Chemical - Acetic Anhydride
Waste Description: waste solutions of 100% acetic anhydride
Destruction Technology: Combustion, mix with sand and burn in
open area. '
Evaluation Table
Criteria
Technical
Feasibility
Applicability
Chemicals &
Equipment
Operator
Requirements
Residual
Production
Advantages/
Disadvantages
Cost
Rating Comments
+ Simple procedure
0 Limit to small batch operations
+ Requires only sand
Safety cautions must be practiced
to prevent inhalation of toxic
fumes
None
Simple, low cost material/possible
emission of toxic vapors
Relatively inexpensive
B19
/L Arthur D. Little, Inc.
-------
Chemical - Acetic Anhydride
Waste Description: waste solutions of 100% acetic anhydride
Destruction Technology: Hydrolysis/neutralization, slowly add to
water, acetic anhydride will slowly
hydrolyse, neutralize acetic acid.
Evaluation Table
Criteria
Technical
Feasibility
Applicability
Chemicals &
Equipment
Operator
Requirements
Residual
Production
Advantages?
Disadvantages
Cost
Rating Comments
Well understood reaction
Small batch operation
Readily available chemicals
and equipment
Chemical technician level
preferred to run the reaction
in controlled state iv^-.-
Acetic acidjwhich must be
neutralized *- -V- >> -.- - -
Simple procedure/hydrolysis can
generate large amounts of heat
and emit toxic fumes
Relatively inexpensive,
neutralization chemicals required
B20
A Arthur D. Little, Inc.
-------
Chemical - Chloroacetone
Waste Description: contaminated or unused chloroacetone
Destruction Technology: Combust, mix with venniculite, soda ash, or
sand, and combustible trash, burn in
incinerator or open pit3
Evaluation Table
Criteria Rating
Technical +
feasibility
Applicability 0
Chemicals & +
Equipment
Operator +
Requirements
Residual
Production
Advantages/
Disadvantages
Cost +
Comments
Simple process
Small quantity applications
Open burn requires only readily
available chemicals
Unskilled labor is adequate
Possible emission of toxic gases,
contaminated bulk agent
Low cost/potential air pollution
problems
Relatively inexpensive method
B21
/k Arthur D. Little, Inc.
-------
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Chemical - Sodium
Waste Description: unused sodium
Detoxification Technology: Combustion, add to fire of oil soaked
rags in a dry steel pan.
Evaluation Table
Criteria
Technical
Feasibility
Applicability
Chemicals &
Equipment
Operator
Requirements
Residual
Production
Advantages/
Disadvantages
Cost
Comments
Simple procedure
Small batches
Simple equipment
Unskilled labor is adequate
Sodium oxide fumes
Low cost, simple procedure/
evolution of oxide fumes
Relatively cheap
B23
A Arthur D. Little, Inc.
-------
Checical - Sodium
Waste Description: unused sodium pieces
Destruction Technology: Store in sealed drums, away from water
sodium should be under liquids such as
kerosene which contain no oxygen
Evaluation Table
Criteria
Technical
Feasibility
Applicability
Chemicals &
Equipment
Operator
Requirements
Residual
Production
Cost
Advantage
Disadvantage
Rating
0
0
Comments
Containment technology available
Commonly practiced in industry
Containers and liquids are
readily available
Handling safety precautions in
handling must be observed
N.A.
Labor, storage
Can accumulate batches for
treatment
Need isolated safe storage,
potential for fire
B24
/L Arthur D. Little, Inc.
-------
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B25
A Arthur D. Little, Inc.
-------
1
i
Chenical - Phosphorus Trichloride
Waste Description: unused solutions of 100% PCI,
Destruction Technology: Pour on soda ash, mix with water,
neutralize.
Evaluation Table
Criteria
Technical
Feasibility
Applicability
Chemicals &
Equipment
Operator
Requirements
Residual
Production
Advantages/
Disadvantages
Cost
Rating Comments
Low technology procedure
Small batch applications
Readily availably chemicals
and equipment
Technicial level personnel
None
Destruction technique/possible
evolution of hydrochloric acid
vapor
Chemical cost could be
significant
B26
A Arthur D. Little, Inc.
-------
Chenical - Phosphorus Trichloride
Waste Description: unused solutions of 100% PCI,
Destruction Technology: Store in tightly closed containers in a cool,
dry area, protect from exposures to water.
Evaluation Table
Criteria
Technical
Feasibility
Applicability
Chemicals &
Equipment
Operator
Requirement
Residual
Production
Advantages/
Disadvantages
Cost
Comments
Stored by user industry
Successful storage history
Standard equipment
Unskilled labor is adequate
N.A.
Store for batch applications/
temporary containment only
Storage overhead
B27
/L. Arthur D. Little, Inc.
-------
Chemical - Titanium Chloride
Waste Description: unused titanium chloride
Destruction Technology: Pour on layer of sodium bicarbonate, mix,
continue to stir while spraying with GM
ammonium hydroxide, when smoke subsides cover
with ice, and neutralize.
Evaluation Table
Criteria
Technical
Feasibility
Applicability
Chemicals &
Equipment
Operator
Requirements
Residual
Production
Advantages/
Disadvantages
Cost
Rating Comments
+ Low technology procedure
0 Small batch application
+ Low technology equipment
Requires safety precautions,
some chemical handling knowledge
Ammonium chloride vapor
Destruction technology limited to
small batch operations, produces
off-gaseous
Chemical cost could be significant
B28
A Arthur D. Little, Inc.
-------
1
M
1
Chemical - Titanium Chloride
Waste Description: unused titanium chloride
Destruction Technology: Store in tightly sealed, heavy gauge
steel drums. Protect from exposure to
water.
Evaluation Table
1
Criteria
Technical
Feasibility
Applicability
Chemicals &
Equipment
Operator
Requirements
Residual
Production
Advantages/
Disadvantages
Cost
Rating Comments
+ Stored by user industry
+ Successful storage history
+ Standard equipment
+ Unskilled labor is adequate
N.A.
0 Temporary containment only
0 Storage overhead
B29
/ti Arthur D. Little, Inc.
-------
REFERENCES
»
1. NIH/EPA Chemical Information System (CIS), OIL and Hazardous
Materials Technical Assistance Data System (OHM-TADS), Chemical
Information Systems, Inc., 7215 York Road, Baltimore, MD, 21212.
i
2. Strauss, H.J., Handbook for Chemical Technicians, McGraw-Hill
Book Company, New York, 1976.
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B30 ^
/L Arthur D. Little, Inc.
-------
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B31
/ti Arthur D. Little, Inc.
-------
Chemical - Cyanide
Waste Description: concentrated sodium cyanide cleaning solutions
Destruction Technology:
Alkaline Chlorination - oxidation of
aqueous cyanide in a two-stage reaction
where cyanide is oxidized to cyanate in
stage one and cyanate is oxidized to
nitrogen and bicarbonate. Stage one is
run at a pH of 9-11 and stage two at a
pH of 8.5. Reaction time of each is
25-30 minutes.
\
Evaluation Table
Criteria Rating
Technical +
Feasibility
Applicability +
Chemicals & +
Equipment
Operator
Requirements
Residual
Production
Advantages/
Disadvantages
Cost
Comments
Widely used process
Applicable to batch or continuous
oxidation of cyanide
Chlorine gas and hypochlorite
oxidizers are readily available
Reaction tanks, pumps, monitors
are common equipment
Skilled operation of monitoring
instruments and observance of
safety procedures are necessary
No primary sludge; secondary
sludge (i.e., metal hydroxides)
may settle in reaction tanks
Flexible operation/heavy exper-
ience/requires special handling
precautions, ventilation
B32
Arthur D. Little, Inc.
-------
Chemical - Cyanide
Waste Description: concentrated sodium cyanide cleaning solutions
Destruction Technology: Peroxide oxidizes cyanide to cyanate. The
reaction is run in a batch mode at a pH of
9-10 and a temperature of 120° - 130°F.
Reaction time is approximately 1 hour.
Evaluation Table
I
i
l
1
Criteria
Technical
feasibility
Applicability
Chemicals &
Equipment
Operator
Requirements
Sludge
Production
Advantages/
Disadvantages
Rating Comments
Cost
Has been applied commercially
Applicable on small batch scale
Peroxide oxidation chemicals are
widely available as are reaction
tanks, pumps, and monitoring
equipment
Operation of monitoring instruments
and safety procedures for handling
procedures
None
Effective for oxidizing cyanides
which are completed with metal
Limited to batch mode; only
oxidizes cyanide to the less toxic
cyanate
Competitive with alkaline
chlorination
B33
A Arthur D. Little, Inc.
-------
w
Chemical - Cyanide
Waste Description: concentrated sodium cyanide cleaning solutions
Destruction Technology:
Cyanide is oxidized to cyanate then CO-,
nitrogen and ammonia in a high temperature
electrolysis process. This process is
limited to concentrated cyanide solutions
(range ) because low concentrations are
poor conductors of electricity. Aqueous
residual is usually subjected to further
treatment such as alkaline chlorination.
Evaluation Table
Criteria Rating
Technical +
feasibility
Applicability 0
Chemicals &
Equipment
Operator +
Requirements
Sludge +
Production
Advantages/ 0
Disadvantages
Cost +
Comments
Practical for concentrated cyanide
solutions
Equipment operation training
None
Low operating cost, requires min-
imal operator training
3.5 kwh electricity/lb. cyanide
oxidized
B34
/L Arthur D. Little, Inc.
-------
Waste - Sulfides
Waste Description: phosphorus pentasulfide production waste
" stream ( 6-7% phosphorus pontasulfide)
Containment Technology: Encapsulation followed by landfilling.J
j Cementation and lime-based pozzolanic
j encapsulation are two common waste
encapsulation techniques considered for
encapsulation. In cementation, a waste
i slurry is mixed with cement and allowed to
i set. In lime-based pozzolanic encapsulation
a waste slurry is mixed with lime and a
| pozzolanic material (i.e., fly ash), and
| water and allowed to set
f
Evaluation Table
I Criteria Rating Comments
Technical + Processes in U.S.
feasibility
Applicability + (ck. on actual process being used)
I Chemicals & Cement, lime pozzolanic material
1 " Equipment readily available, common process-
ing equipment which is readily
I available
Operator + Process does not require a high
Requirements level of operator skill
$
I Residual - Increases weight and volume of
Production waste by a factor of 2
' Advantages/ 0 Low cost materials, highly skilled
Disadvantages labor not needed, increases volume
and weight of waste, phosphate
i mould interfers with cement curing
A
Cost +
I
t
B35
A Arthur D. Little, Inc.
-------
Waste - Sulfides
Description:
phosphorus pentasulfide production waste
stream ( 6-7% phosphorus pontasulfide)
Hazard Reduction Technology:
Mix with,large excess of water,
oxidize. Hydrogen peroxide oxidizes
hydrogen sulfide (produced by reaction
of P.S, with water) to sulfur.
Evaluation Table
Criteria Rating
Technical +
feasibility
Applicability 0
Chemicals &
Equipment
Operator
Requirements
Residual
Production
Advantages/
Disadvantages
Cost
Comments
Hydroperoxide oxidation processes
in use
Batch operation suitable for small
amounts/No applications specific
to this waste were found
Chemicals (H-Oj) readily available
as well as the reaction tanks,
pumps, etc.
Operator skill requirements are not
highly specialized
sulfur
Batch operation, familiar tech-
nology/cost of hydrogen peroxide,
residual disposal
Hydrogen peroxide is relatively
expensive
B36
Arthur D. Little, Inc.
-------
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Chemical - Sodium Azide
Waste Description: unused sodium azide, 100% pure
Destruction Technology: React with excess aric ammonium acetate,
mix and cool the.reaction, residual can be
routed to sever.
Evaluation Table
Criteria
Technical
Feasibility
Applicability
Chemicals &
Equipment
Operator
Requirements
Residual
Production
Advantages/
Disadvantages
Cost
Rating Comments
Low technology procedure
Small batch applications
Readily available chemicals
and equipment
Unskilled labor is adequate
None
Simple procedure, no residuals
B38
/k Arthur D. Little, Inc.
-------
Chemical - Parathior
Waste Description: unused parathion
Destruction Technology: Mix with sand and limestone, incinerate in
hazardous waste incinerator with after burner
and alkaline scrubber.
Evaluation Table
Criteria Rating Comments
Technical + Proven technology
Feasibility
Applicability +
Chemicals & - Incinerator is required
Equipment
Operator 0 Skilled operator
Requirements
Residual 0 Scrubber sludge
Production
Advantages/ 0 Destruction techniques/expensive
Disadvantages
Cost - Expensive
T1OQ
~ Arthur D. Little, Inc.
-------
Chemical - Amnoniun: Nitrate
Waste Description: unused ammonium nitrate, 100%
Destruction Technology: dilute with water, react with excess soda
ash, neutralize.
Evaluation Table
Criteria Rating
Technical +
Feasibility
Applicability +
Chemicals & +
Equipment
Operator +
Requirements
Residual
Production
Advantages/ 0
Disadvantages
Cost 0
Comments
Low technology
Limit to small batches for
safety precaution
Common chemicals and processing
equipment
Unskilled labor is adequate
Sludge - dispose in landfill'
Destruction (sample process)/
residual production
Chemical cost, residual
disposal
B40
A Arthur D. Little, Inc.
-------
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-------
Chemical - Benzoyl Peroxide
Waste Description: small lots - 1 Ib container-waste laboratory
reagent
Destruction Technology: Reduction (Lodide reagent) , mix with
excess reducing agent, neutralize excess
agent and discharge.
Evaluation Table
Criteria
Technical
feasibility
Applicability
Chemicals i
Equipment
Operator
Requirements
Residual
Production
Advantages/
Disadvantages
Cost
Rating Comments
0 Laboratory analysis technique
Batch runs with small quantities
Reducing agents and processing
equipment are readily available
Skilled chemical lab technician
required
None
Only small quantities can be
processed, skilled operator
required
BA2
/L Arthur D. Little, Inc.
-------
Chemical - Ber.zoyl Peroxide
Waste Description: small lots -1 Ib container-waste reagent
Destruction Technology: Combust, mix vermiculite or lime, mix with
trash and burn
Evaluation Table
Criteria Fatins
Technical
feasibility
Applicability
Chemicals &
Equipment
Operator
Requirements
Residual
Production
Advantages/
Disadvantages
Cost
Comments
Simple process
Small to medium batches readily
other waste materials
No special skills required
Possible emission of incomplete
combustion products to the air
Low cost/potential air pollution
problems
Relatively low
BA3
A Arthur D. Little, Inc.
-------
Chemical - Ethylene Oxide
Waste Description: Spent Ethylene Oxide
Destruction Technology:
Incineration, dissolve in alcohol and incin-
erate; Peroxides may be present in aged
ethylene oxide in which case it should be
moved (carefully in padded containers) to an
isolated where it can be ignited from a safe
distance.
Evaluation Table
Criteria Rating
Technical +
feasibility
Applicability 0
Chemicals &
Equipment
Operator
Requirements
Residual
Production
Advantages/
Disadvantages
Cost
Comments
Process is well understood
Readily applicable to small
batches which have not been in
containers for extended periods
of time
Common chemicals and equipment
Special care is necessary because
of detonation possibility if
peroxides are present
None
No residuals/safety hazards,
skilled operators required
B44
/ti Arthur D. Little, Inc.
------- |