FINAL REPORT
EVALUATION OF TREATMENT,
STORAGE AND DISPOSAL TECHNIQUES
FOR IGNITABLE, VOLATILE
AND REACTIVE WASTES
September 10, 1980
Prepared for:
U.S. Environmental Protection Agency
Office of Solid Waste
Contract No. 68-01-5160
Marc Turgeon - Project Officer
Prepared by:
JRB Associates, Inc.
8400 Westpark Drive
McLean, Virginia 22102
Co-Project Managers: Karen Slimak and Roger Wetz
Contributing Writers: Jim Hairanelman
Charlie Kufs
Phillip Lotrakul
Jackie Rams
Claudia Wiegand

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NOTICE
This report has been reviewed by EPA. The contents do not
necessarily reflect the views and policies of the Environmental
Protection Agency, nor does mention of trade"names or corniercial
products constitute endorsement or recommendation for use.

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LIST OF TABLES
Table	Page
1.1 Sumnary of Treatment, Storage and Disposal Practices	1-3
3.1	Comparison of Estimated Emission Using Best Available
Techniques and MATES	3-3
3.2	VCM Concentrations Found in PVC Sludges	3— L8
3.3	Summary of Treatment, Storage and Disposal Technology
for Water Pollution Control Sludge from PVC Production	3-22
3.4	Vinyl Chloride in Wastewater Treatment Sludge	3-42
3.5	Nitrobenzene in Waste Tars	3-51
3.6	Chlorobenzene in Distillation Residue	3-62
3.7	Costs Associated with Stripping of Nitrobenzene Wastes	3-71
3.8	Nitrobenzenes in Column Bottoms	3-73
3.9	Crude Oil Processing Capacity of U.S. Refineries	3-75
3.10	Major Petroleum Products Produced by U.S. Refineries
in 1974	3-79
3.11	Comparison of Refinery Waste Disposal Methodologies
Used in 1973 with Those Projected for 1983	3-83
3.12	Generation Rates and Volume Distribution of 17 Waste
Streams From the Petroleum Refining Industry	3-84
3.13	Water Quality Estimates of Typical Effluents Sent to
DAF Systems from API Separators	3-89
3.14	Oil Concentrations and Removal Efficiencies for 14 DAT
Systems	3-90
3.15	Percentages of Oil, Water, and Solids in DAF Float	3-93
3.16	Calculation of Specific Gravity of DAF Float	3-94
3.17	Concentrations, Generation Rates, and Minimum Toxicity
Levels of 28 Elements Found in DAF Scum	3-95
3.18	Comparison of Daily Generation Rates for 28 Elements
in DAF Float With Their MATE Values	3-97
3.19	The Hazards of 27 Chemicals Found in DAF Influents	3-98
3.20	National Fire Protection Association Indices for
Hazards of 27 Chemicals Found in DAF Influents	3-99
3.21	Treatment/Disposal Strategies for DAF Float at Eight
Petroleum Refineries	3-101
3.22	Current and Projected Percent Use of Several Methods
for Managing DAF Scum	3-105

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List of Tables (Continued)
Table	Page
3.23	Summary of the Data From a Study of the Effects of
Land Treatment API Separator Sludges	3-110
3.24	Summary of Environmental Effects of Disposal Methods
for DAF Float	3-120
3.25	Summary of Potential Emission Levels from Disposal
Methods for DAF Float	3-121
3.26	Summary of Costs of Disposal Methods for DAF Float	3-122
3.27	Production of Water Pollution Control Sludge From the
Electroplating and Metal Finishing Industry (Job Shops) 3-126
3.28	Metal Hydroxide Wastes in Water Pollution Control Sludges
From the Electroplating Industry (1975)	3-126
3.29	Criteria for Public Water Supplies	3-129
3.30	Summary of Treatment, Storage, and Disposal Technology
for Water Pollution Control Sludge From the Electro-
plating and Metal Finishing Industry	3-130
3.31	Treatment Methods Used by Fifty Job Shops to Separate
Solids From Treated Wastewater	3-131
3.32	Estimated Centrifuge System Capital and Operating Costs
for Three Different Size Electroplating and Metal
Finishing Model Plants	3-134
3.33	Sunnnary of Estimated Contractor Hauling, Treatment, and
Disposal Charges for Electroplating and Metal Finishing
Waste Destined for Land Disposal	3-139
3.34	Cyanides in Wastewater Treatment Sludge	3-142
3.35	Chromium in Wastewater Treatment Sludge	3-143
3.36	Comparison of Plating Sludge Metallic Constituents
With State of Illinois Criteria	3-144
3.37	Waste Streams Generated by Typical Woven Fabric
Dyeing and Finishing Plant	3-147
3.38	Woven Fabric Dyeing and Finishing Sludge Chemical
Composition	3-150
3.39	Drinking Water Limit for Metals and Chlorinated
Organics	3-152
3.40	Summary of Treatment, Storage, and Disposal Technology
for Wastewater Treatment Sludge from Woven Fabric
Dyeing and Finishing Operations	3-154
3.41	Estimated Installed Costs for Various Types of Pond
Liners	3-157
3.42	Summary of Major and Minor Elements in Sludge	3-161

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List of Tables (Continued)
Table	Page
3.43	Chlorinated Organics in Wastewater Treatment Sludge	3-162
3.44	Comparison of Wastewater Treatment Sludge with State
of Illinois Criteria	3-163
3.45	Typical Formulation Changes to Achieve a Variety of
Coatings	3-167
3.46	Paint and Coatings Manufacture Summary of Total
Wastes in 1974	3-168
3.47	Estimated Pigment Usage by Paint Industry, 1972	3-172
3.48	Estimated Resin Usage by Paint Industry, 1972	3-175
3.49	Estimated Drying Oil Usage by Paint Industry, 1972	3-176
3.50	Estimated Solvent Usage by Paint Industry, 1972	3-177
3.51	Estimated Miscellaneous Materials Usage, 1972	3-178
3.52	Toxicity of Raw Materials Used in Surveyed Paint Plants 3-179
3.53	Process Liquid Wastes from Solvent-Thinned Trade Sales
Paint Manufacture	3-185
3.54	Contents of Li-SO^ Battery	3-188
3.55	Potential Air Releases from Li-S02 Battery Disposal	3-190
3.56	Comparison of Hazardous Nature of Li-SO^ Cell Components 3-193
3.57	Cost Estimates for Various Disposal Methods	3-201
3.58	Cost-Benefit Comparison of Landfill With and Without
Prior Incineration	3-203
3.59	Li-S02 Scrap Cell Treatment and Disposal	3-204
4.1	Typical Solvents and Selected Properties	4-3
4.2	Solvent Consumption by Selected Industries	4-4
4.3	Charges Levied for Treatment and Disposal of Wastes,
Oils and Chemicals in Denmark	4-16
4.4	SOCMI Secondary Emission Sources and Estimated Emissions 4-19
4.5	Applicable Control Methods	4-27
4.6	Secondary VOC Eta ission Reductions by Various Control
Techniques or Methods	4-29
5.1	Percentage Distribution of Commercial Explosives Use	5-3
5.2	Examples of High and Low Explosives	5-6
5.3	Common Ingredients of Dynamite	5-7
5.4	Typical Composition of Dynamite	5-13
5.5	Waste Waters Generated in LAP Operations	5-35

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List of Tables (Concluded)
Table	Page
5.6	Nitrate Treatment Methods	5-40
5.7	Bulk PEP Sold to Commercial Users	5-58
6.1	Summary of Contacts with Selected State Agencies	6-10
6.2	Summary of Telephone Contacts with Selected IRV
Waste Disposers	6-11
A.1 Damage Incidents Involving Land Disposal of Volatile
Wastes	x	A-2
A.2 Definitions of Volatility, Ignitability and Reactivity
Used In This Report	A-4
A.3 Comparison of Vapor Pressures and Toxicities of
Selected Chemicals	A-7
C.l Waste Streams Chosen for Study	C-4

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Table of Contents (Concluded)
Page
APPENDIX C
APPENDIX D
c
Selection of Ignitable, Reactive and
Volatile Waste Streams
C-l
C.l
Method for Selection of Waste Streams
C-l
C.2
Waste Streams for Further Study-
C-3
C.2.1
Organic Chemicals and Plastics Manufacturing
C-5
C.2.2
Petroleum Refining
C-5
C.2.3
Electroplating and Metal Finishing
C-5
C.2.A
Textile Manufacturing
C—6
C.2.5
Paint Manufacturing
C—6
C.2.6
Primary Batteries
C-6
C.2.7
Commercial Explosives
C—6
C.2.8
Military Explosives
C-7
D
Updating Costs
D—1

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1.0 EXECUTIVE SUMMARY
1.1 PROGRAM OBJECTIVE
Section 3004 of the Resource Conservation and Recovery Act of
1976, required EPA to issue regulations establishing standards for the
operation of hazardous waste treatment, storage and disposal facilities.
The purpose of this project is to begin to develop an information
base to support development and implementation of methods for treat-
ing, storing and disposing wastes exhibiting the characteristics of
ignitability, reactivity and volatility.
Information contained in this report is intended as input to the
initial set of regulations due to be issued in April 1980 by the EPA
Office of Solid Waste, and to subsequent fine tuning and closing of gaps
in the regulations. Input is also provided for post-regulatory activi-
ties such as writing permits for hazardous waste sites and enforcing
the regulations.
The project was directed toward identification of best available
treatment, storage and disposal alternatives for waste streams selected
for their ignitability, reactivity or volatility, or combination of all
three. Further criteria included toxicity, volume of waste generated,
originating industry and waste form.
Ignitable, reactive and volatile wastes create special problems
such as fires, explosions and harm to human life and the environment dur-
ing handling and disposal, and in the post-disposal environment. The
properties of ignitability, reactivity and volatility overlap so that
most wastes investigated had more than one of the properties, and some
had all three. A significant proportion of hazardous wastes listed in
Section 3001 regulations have these properties, although data has not
been developed to determine the actual quantity of ignitable, reactive
and volatile wastes produced.
For this study, alternatives for each waste stream were identi-
fied, primarily by a review of current industrial practices, to determine
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Che average and best techniques in use for disposing of each one. Final
determination of best available technologies vere based on the following
criteria:
•	Proven technology
•	Relatively low operation and maintenance cost
•	Potential for recovery of valuable materials
•	Overall cost and effectiveness.
Thirteen waste streams were selected as representative of all
lgnitable, reactive and volatile wastes. A summary of treatment,
storage and disposal practices identified in the Investigations for
these 13 waste streams is shown in Table 1.1. Landfill is the current
practice most often employed, while incineration with land disposal of
residue is the best technology most often used. The cost of using incin-
eration on the plant site would be about four times that of simple land-
fill for most of the wastes investigated. However, the cost of inciner-
ation can be significantly reduced, in many cases, by having wastes
incinerated by off-site waste disposal contractors. Avoiding financial
burden of purchasing and operating an incinerator will mandate consider-
ation of off-site contractor disposal of waste, particularly for small
plants.
1.2 APPROACH
Tasks performed in conducting the project follow in chronological
order:
•	Development of a working definition of volatility
•	Assembly of a list of ignitable, reactive and
volatile waste streams, and selection of waste
streams for study
•	Studies of waste streams to determine current and
best treatment, storage and disposal methods
•	A study of solvent use and recovery in industry
•	A study of treatment, storage and disposal of
wastes from explosives manufacture
•	Evaluation of options for regulating ignitable,
reactive and volatile wastes.
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Table 1.1 Summary of Treatment, Storage and Disposal Practices
Waste Streams
Current Practices
Best Available Technology
Most Environmentally Sound
Practice
Wastewater treatment
sludge from polyvinyl
chloride production
Landfill
Incineration with HC1 recov-
ery, lgnd disposal of residue
Salt deposit disposal
Chlorobenzene still
bottoms
Landfill
Incineration with HC1 recov-
ery, land disposal of residue
Chlorinolysis
Nitrobenzene still
bottoms
Disposal in
sealed steel
drums in
landfill
Rotary kiln incineration with
NO control and heat recovery
Land disposal of residue
Steam distillation, alkali hy-
drolysis followed by catalytic
reduction. Disposal of nitro-
phenols in landfill
Tars from aniline
production
Land application of
sludges from bio-
logical treatment
of combined plant
wastes
Rotary kiln or multiple
hearth incineration with NO
control and land dispoal of
residue. Heat recovery po-
tential is good
Steam stripping followed by in-
cineration of product. Biologi-
cal treatment of bottoms
Sulfur sludge from
parathlon manufacture
Rotary kiln or mul-
tiple hearth incin-
eration with SO
scrubbing. Lan3
disposal of stabil-
ized scrubber
sludge and inciner-
ation residues. Po-
tential for heat
recovery
Same as current practice
Sulfur recovery, composting
organophosphates with lime
DAF skimmings from
petroleum refining
Landfill
RereEin&ng
Rerefining

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Table 1.1 Summary of Treatment, Storage and Disposal Practices (Continued)
Waste Streams
Current Practices
Best Available Technology
Most Environmentally Sound
Practice
Process liquid vastes
from solvent-thinned
trade sales paint
manufacture
Landfill
Recovery with land disposal
or incineration of residue
More complete recovery with land
disposal or incineration of
residue
Wastewater treatment
sludges from woven
fabric dyeing and
finishing in the tex-
tile Industry
Discharge to un-
lined lagoon
Sludge dewatering, disposal
in approved landfill
Encapsulation, disposal in
secure landfill
Wastewater treatment
sludge from electro-
plating
Landfill
Sludge dewatering disposal
in landfill
Sludge dewatering, encapsulation
disposal in secure landfill
Lithium-sulfur diox-
ide battery
Landfill
Mechanical disassembly with
incineration; SO ,N0 scrub-
bing, and disposal of resi-
due
Disassembly, recovery of com-
ponents for reuse
Red water from TNT
production
Open burning
Concentration/incineration
with caustic scrubbing and
land disposal of ash
Same as best available
Bulk propellents, ex-
plosives, pyrotechnics
Open burning
Incineration with caustic
scrubbing and land disposal
of aBh
Same as best available
Pink water from load,
assemble and pack
operations
Carbon adsorption
evaporation,
burning
Incineration with caustic
scrubbing and land disposal
of ash
Same as best available

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1.3 CONCLUSIONS
The definition of volatility was developed early in the project
and used throughout. Further consideration of vapor pressure cutoff
points should be made to reflect how the definition is likely to be
applied. If it is ultimately used to determine the methods for disposal
of a substance, then the basis for the cutoff points should be streng-
thened, and application of the definition to mixed wastes should be
further investigated.
The 13 waste streams studied are indicative of all ignitable,
reactive and volatile waste streams generated. The best available tech-
nologies are expected to have little environmental impact, but may pose
a significant financial burden on Industry. Emissions are estimated
for implementation of each best available technology and are compared
with Minimum Acute Toxicity Effluents (MATE's) for the critical chemical
constituent of each waste stream (Cleland and Kingsbury, 1977). Best
available technologies meet draft 3004 regulations and would result in
emissions meeting the MATE goals for pollutant concentrations for pro-
tection of human health and the disposal environment.
Recovery is the most environmentally sound technique for handling
waste solvents. Recovery is generally applicable for solvents as long
as an economic incentive exists.
While much research and development effort to control environmental
emissions at explosive manufacturing facilities has been made by the
military, implementation by military or commercial manufacturers has
not occured. Open burning is commonly practiced for disposal of many
explosive wastes and, although It is not an environmentally sound prac-
tice, practical alternatives have not yet been developed.
Recommendations for further study are given in Chapter 2.
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2.0 RECOMMENDATIONS
The objectives of this project were to study ignitable, volatile
and reactive wastes and identify treatment, storage and disposal
technologies and recommend best available practices where the data and
analysis support such recommendations. From these analyses, recommenda-
tions for regulating these wastes were devised. Additional studies of
treatment, storage and disposal methods were performed for explosives
and solvents, while a definition of volatility was developed and used
for this project. Coupled with the definition of ignitability and
reactivity previously proposed by the EPA Office of Solid Waste, these
definitions formed the basis for determining whether a waste stream was
ignitable, volatile, or reactive.
Very specific waste streams, such as chlorobenzene still bottoms,
were chosen for study so that specific technologies could be identified,
which allowed a more detailed evaluation of costs and environmental
impacts.
Technologies for each waste stream were classified into one of
three most prevalent categories: current practices; best practices as
used by at least one operating facility; and most environmentally sound
practice. Most environmentally sound practice for a given waste was
chosen by identifying developing technologies and technologies being
used for similar wastes and assessing feasibility and cost for
implementing the technology and environmental releases associated with
its use.
2.1 REGULATORY APPROACH
Once this study was underway, it became apparent that regulating
these wastes would be more difficult than originally thought. JRB devel-
oped some ideas for regulation in the course of the study. Although this
activity was not part of the study, these ideas are offered for EPA con-
sideration.
Some general approaches may be suggested for regulating the treatment,
storage and disposal of ignitable, volatile and reactive wastes. Some of
the problems that have made regulating these wastes difficult are:
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•	Developing definitions for ignitability, reactivity and volatil-
ity that are precise enough to be used for regulatory activities,
while retaining meaning that reflects its hazard or nonha2ard
in treatment, storage and disposal scenarios.
•	Developing quantitative levels at which wastes are proven to be
hazardous or nonhazardous.
•	Lack of accurate quick and inexpensive means for testing actual
waste streams.
•	Diversity of waste specific technologies applicable to these
wastes.
Since ignitability, reactivity and volatility are properties of wastes
they describe how wastes behave under given conditions. Much research
has been and is being done to describe waste behavior and to promote a
better understanding of what makes wastes hazardous during and follow-
ing treatment, storage and disposal.
However, many of these conditions are site- or process-specific,
increasing the difficulty of thorough analysis of waste behavior.
Additionally the properties of ignitability, reactivity and vola-
tility overlap, further increasing the difficulty of setting limits ex-
clusively for each property to determine whether or not a waste should
be handled or disposed in a particular manner. However, once each prop-
erty is defined and acceptable levels for each are established, any
one level is envisioned to be cause for violation. Therefore, if a
waste is either ignitable or volatile or reactive according to estab-
lished definitions, then the waste would be subject to regulation.
A summary of the regulatory approach recommended by JRB as a re-
sult of this study is as follows:
•	A dollar per quantity tax on generators of these wastes.
•	Storage of IRV wastes, as long as the purpose is to stockpile
wastes to decrease unit costs of recovery; decrease unit costs
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of transporting wastes to a treatment, storage or disposal
facility, or wait for more favorable short term market condi-
tions of wastes or recovered components or products.
•	Cutoff levels for ignitability, reactivity and volatility to
determine appropriate means for handling wastes. For example,
for levels below the cutoff level, landfill, land treatment or
lagoon disposal would be allowed.
•	Setting volatility cutoff levels which incorporate vapor pressure
and toxicity.
•	Setting ignitability levels as determined by flash point.
•	Defining reactivity by known constituents of wastes or lacking
this information, the production process which uses reactive raw
materials or produces a reactive product.
•	For wastes with combinations of these properties, consider using
a combination of each level for determining appropriate handling
and disposal.
The purpose of this approach is to emphasize removal of ignitable,
reactive and volatile properties of wastes by the generator and de-
emphasize the activities required of disposal site owners and operators
to ensure environmentally adequate disposal of these wastes.
2.1.1 Proposed Tax on Generators
The EPA regulatory program should address the following in its
initial stages:
•	Do these wastes have value?
•	Can they be partially reused in the generating process?
•	Can increasing process control and generally tightening the
generating process substantially eliminate generation of wastes
with these properties?
More than half of the studied waste streams had a component or
components that appear to be worth recovering and reusing or converting
into useful products. Other studied wastes probably would be recovered
if a higher value were placed on their ignitable, volatile and reactive
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components. Therefore one regulatory approach would be to assign a
negative value or "tax" in dollars per unit to wastes having these
properties which leave the generating process for disposal. Conversely,
a tax incentive could be offered to processes who now generate these
wastes, but who make process changes to reduce or eliminate such dis-
charges .
This approach would have several favorable aspects:
•	It would encourage efforts by industry to find ways to reuse
these wastes.
9 It would provide incentive to industry to handle these wastes
in a manner that is both environmentally sound and cost effective.
•	It would provide rules that could be applied evenly to all waste
generators.
An example of a tax on generators would be a base charge of so much
per pound of waste with additional charges for ignitability, volatility
and reactivity, which is similar to user charges levied.on industrial
facilities by municipal sewer authorities.
2.1.2 Storage
Implementation of the tax on generators may create the need for
storage of wastes or recovered waste components. Although we recognize
that storage of wastes has created some problems due to improper storage
in the past, we feel that a tradeoff is needed to allow industry some
leeway in determining the most economic method for handling their
wastes. The problem arises because of the many low volume and inter-
mittent wastes, such as still bottoms and tank cleanings, that may not
justify immeidate treatment or recovery. This is due to the high costs
for purchasing process equipnent with the capacity to treat the waste
in a short time period and then allowing the equipment to stand idle
until another batch of waste is ready for processing. Storage of
wastes is currently regulated under RCRA Section 3004 which requires
that facility owners or operators who store wastes for longer than 90
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days must comply with RCRA Section 3010 notification and Section 3005
permit application requirements in order to qualify for interim status
as a waste treatment, storage or disposal facility. No change in these
requirements would be necessary to carry out this approach.
Although storage of many reactives such as explosives may not be
feasible, storage or most ignitables and volatiles can be performed in
an environmentally safe manner. Storage may allow a generator to:
•	plan the continuous utilization of waste processing equipment,
•	decrease unit costs of transporting wastes, because partial
loads of each waste batch are eliminated,
•	recover and store waste components until market conditions are
more favorable.
Means of monitoring these practices may include agreement on a maximum
time limit for storage between EPA and the generator, leaving open the
possibility of extending the storage period beyond the 90 day llmitatloi
currently in the regulations subject to notification and permit appli-
cation requirements mentioned previously, if the generator can demon-
strate good faith to EPA's satisfaction. The hazardous waste manifest
system will serve as a check to determine when and if the waste is
transported.
2.1.3 Summary and Example
These recommendations are given to suggest a possible approach for
regulating these wastes. An example may help illustrate the recommendec
approach.
One type of waste studied in this report was still bottoms from
production of several organic chamicals. This type of waste may be
ignitable, volatile, reactive or combinations of all three depending
on many parameters such as:
•	materials used in the process
•	operating conditions of temperature, pressure, feed rate
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•	maimer in which waste is removed (determines whether waste is
liquid, semisolid or solid)
•	purity of raw materials
•	direct vs. indirect heating.
Wastes may be removed periodically, such as during plant shutdown.
If the recommended regulatory approach is followed, the generator must
decide whether to pay the tax or remove or recover waste constituents.
However, if the tax on generators were promulgated, the generator would
probably first investigate alternatives which would reduce the tax on
his waste. Some of these alternatives may include:
•	substituting feedstock materials that are not ignitable, volatile
or reactive
•	altering operating conditions such as temperature pressure and
feed rate to reduce levels in wastes
•	optimizing waste removal operation for reduction in these
properties.
•	increasing the purity of raw materials in the process to decrease
wastes
•	decreasing purity of the product to decrease wastes
o using indirect heating to prevent waste caused by degrading
the product due to overheating.
Once the generator has reduced his tax by altering the proces, he
then has the option to use recovery methods to further decrease the
tax. Some of the alternatives he may consider would be the following:
•	solvent extraction to recover a portion of the waste that is
reusable in his process
•	exchange with another generator whose waste may be more easily
recovered
•	set up central treatment or recovery process in conjunction
with other generators.
After the previous options are considered, he may still have a
tax on his waste, though it may be substantially reduced. Disposal of
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the waste in a relatively inexpensive manner such as in a sanitary land-
fill is likely to be an acceptable alternative based on previously
established cutoff levels for volatile, ignitable and reactive constit-
uents in wastes destined for landfill, which are further discussed in
Section 2.2. If the wastes do not meet landfill criteria, then means
such as thermal pretreatment may be used to allow acceptance in a
landfill.
The example is only for illustration purposes. Many approaches may
be feasible with other types of waste.
We feel that the approach outlined in this section would encourage
recovery and reuse of wastes without unduly penalizing industry. It
allows even-handed treatment of all facilities, using procedures that
are relatively simple. It also allows EPA to set standards that are
restrictive enough to prevent environmental damage, while not too
restrictive to force facilities to close without having a reasonable
chance to successfully handle their own ignitable, volatile and
reactive waste problems.
2.2 CUTOFF LEVELS FOR IGNITABILITY, VOLATILITY AND REACTIVITY
The following discussion stems directly from the evaluation
performed in this report. Although the purpose of the study was not
to set cutoff levels or to derive them from the data presented in this
report, We feel that cutoff levels are a viable approach for regulating
these wastes and we recommend that cutoff levels be established for
these wastes. The data presented herein may provide an information
source which would aid In such future regulatory activities.
2.2.1 Cutoff Levels for Ignitability and Volatility
Cutoff levels are recommended as a means of determining whether
or not a waste may be allowed in a landfill, land treatment facility
or lagoon. These may be similar to the one for ignitability, which
has been set at a flash point of 60°C (140°F). If the proposed tax
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on generators Is implemented, it is believed that less pressure will be
placed on owners and operators of waste facilities to take the initiative
in removing ignitability and volatility properties from waste.
Based on the development of the working definition of volatility
used in this report, we recommend that a cutoff level for volatile wastes
be based on volatility and toxicity. Toxicity levels may be based on the
EPA extraction procedure. Volatility levels may be based on vapor pres-
sure. Although we recognize that vapor pressure does not describe all
of the mechanisms for release of volatile substances, it does provide a
relatively simple means for testing and evaluating wastes, while approxi-
mating simple release mechanisms. Vapor pressure is a property that can
be measured by generators, transporters, disposers and the EPA. Addi-
tional parameters such as solubility or molecular weight may be justified
for disposed site evaluation purposes. As part of developing the working
definition of volatility for this report, cutoff levels were set. How-
ever, additional research is required before use of these cutoff levels
is made in activities outside the scope of this report.
2.2.2	Reactivity
Reactivity is difficult to define as precisely as other properties
of wastes, such as ignitability. Therefore, we recommend that reactivity
of a waste be determined by the presence of reactive work constituents,
if they are known. Reactive materials may be listed by groups, such as
explosives, strong oxidizing agents and alkali metals, for determining
reactivity of a waste. Alternatively, wastes from production processes
using reactive raw materials or producing a reactive product may be
considered reactive unless the waste was produced with no contact with
reactive materials.
Reactive wastes may require evaluation on a case-by-case basis to
insure safe disposal.
2.2.3	Combinations
Many wastes studies in this report were found to have properties
that were combinations of ignitable, volatile and reactive. Few had
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only one of these properties. Therefore, a means of taking into consid-
eration each of these properties and applying criteria that reflects
actual potential for hazard due to all three properties may be needed.
A means for accomplishing this may be to use the tax on generators
with additional charges for ignitability, volatility and reactivity.
2.3 RECOMMENDATIONS FOR FUTURE STUDY
The following recomnendations stem directly from the work done. In
the course of conducting this study, some areas were identified which
appeared to deserve greater attention than was possible within the broad
scope of this study. These areas fell into two general categories.
First there were those that required further research such as sampling
and analysis or visits to industry to develop data that would serve to
bring those technologies identified as most environmentally sound into
greater usage. The following are descriptions of possible future re-
search areas that fall into these categories.
2.3.1 Data Development
Detailed data on properties of waste streams were not always avail-
able and development of this data was not within the scope of this pro-
ject. The waste streams studied are complex and are usually made up
of one or more subwaste streams, each with differing properties. In
most cases, information on general characteristics of wastes are avail-
able. For example, it has been reported that distillation residue from
chlorobenzene manufacture is made up of 10 percent chlorobenzene, 89 per-
cent polychlorinated resinous material, and less than 1 percent di-
chlorobenzene. A further analysis of polychlorinated resinous material
would have been necessary to provide a more accurate reading of waste
stream properties which would help identify more precisely potential
problems that could result from treatment, storage and disposal of this
waste. However, future studies are recommended to not just characterize
waste streams, but to develop data for properties that could help deter-
mine whether problems will be encountered with specific treatment,
storage and disposal techniques. Some of the properties of waste streams
2-9

-------
may include flash points, vapor pressures, toxicities and reactivities.
For some wastes, detailed costs for treament, storage and disposal
were not available din literature. It is recommended that initial capital
requirements and annual costs (such as financing, taxes, insurance,
operations and maintenance) be developed by such means as contacting
equipment vendors and industry where detail is lacking.
Further contact with waste generating Industries is recommended to
help identify process changes, equipment cleanup and housekeeping prac-
tices, effects of production start-up and shut-down and production of
off-specification products. Once these are identified, in-process changes
could be recommended to reduce waste quantities or hazards associated
with the waste.
A working definition of volatility was developed to attempt to re-
late a physical property of wastes to release mechanisms encountered in
treatment, storage and disposal facilities. The working definition was
used in this study to define volatile wastes. The definition and infor-
mation describing the basis for its development is given in Appendix A.
Resource limitations prevented development of a means for applying the
definition to mixed wastes and laboratory procedures for testing it.
Further investigation is recommended to complete the definition.
Quantification of expected environmental releases from disposal
facilities was attempted using minimum acute toxicity effluent (MATE)
values developed under a recent EPA study (Cleland and Kingsbury, 1977).
Though this was a first-cut attempt, it appears that a marked improvement
in this approach can be made only by modeling facilities. Although many
models exist, using this approach was not within the scope of this study.
The first need would be the ability to model a treatment, storage or
disposal facility to the degree that releases could be estimated from
disposal of a particular waste. The next need would be the ability to
model the release mechanisms of substances from a mixed waste stream so
that release estimates of different compounds from the same waste
stream could be made. Finally, the ability to model interactions between
mixed wastes, including compatibility, would have to be developed.
2-10

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Incineration is one of Che best available techniques for many of the
waste streams studied. However, two waste streams, stack gases and resi-
dues are produced during incineration. Specific technologies have been
recommended in this report for scrubbing stack gases resulting from in-
cineration of each waste. Removal of pollutants in stack gases necessi-
tates disposal of collected material. Specific Information on disposal
of this waste as well as residues from incineration were not found for
the waste streams studied. Further data development efforts may be
necessary to fully assess potential impacts of these wastes.
Some waste streams were found to be treated, stored or disposed
some distance from where they were generated. In general, waste disposal
contractors were employed for this purpose. In many cases, tracking the
specific waste streams to offsite disposal contractors and identifying
particular treatment, storage and disposal techniques used there for each
waste stream was very difficult. Reasons are that specific waste streams
are frequently mixed with other specific waste streams and with general
plant wastes such as waste paper and wood before being sent to an offsite
disposal contractor. Offsite contractors typically use their own analyt-
ical laboratories to determine appropriate treatment, storage and dis-
posal methodologies. Therefore, the waste stream's origin as used to
denote waste streams in the bulk of this report may not have much meaning
to an offsite contractor. This problem is being addressed in an ongoing
EPA project to subcategorize wastes by the physical and chemical char-
acteristics that will be meaningful for offsite disposal contractors and
further evaluate exemplary disposal techniques and their costs.
2.3.2 Increasing Acceptance of Most Environmentally Sound Technologies
Further investigation of the refining of scum oils from dissolved
air flotation of oil refinery wastes may help identify ways for reusing
a larger portion of this waste stream in the production process. Further
identification of chemical and physical properties of residues from dis-
solved air flotation may help identify specific alternatives for dis-
posal.
2-11

-------
r
Investigation of in-process changes for solvent-thinned trade sales
paint manufacture may increase the reuse of spills, and out-of-date and
off-specification paints in the production process, reduce solvent con-
sumption and increase solvent recovery. Each of these practices could
result in dollar savings to the manufacture as well as decrease negative
impacts to the environment from disposal of these substances.
The process of chlorinolysis has been used for many years to convert
chlorinated hydrocarbon wastes, especially from pesticide manufacture,
to saleable products such as carbon tetrachloride. This process has not
been applied to distillation residue from chlorobenzene manufacture.
However, further investigation would lead to a determination of the
feasibility of recovering carbon tetrachloride from this waste stream.
Investigation of the separation and reuse of nitrobenzene contained
in column bottoms from its manufacture may result in savings to the
manufacturer from both recovery of the nitrobenzene product and reduction
of volume and hazard associated with the column bottom waste stream. A
three-step stripping procedure Involving steam distillation, alkali
hydrolysis and catalytic reduction is recommended for further study.
In the past, concentrated red water from trinitrotoluene (TNT) pro-
duction has been reused by a few paper manufacturers as a source of sul-
fite liquor. Further investigation of this practice may help identify
further markets for this waste and allow economic comparison with other
alternatives such as incineration.
These specific recommendations and recommendations for future study
represent JRB's overall assessment based on studies of specific waste
streams. Although this study was meant to be a technical assessment,
it is believed that portions of the study may provide information for
future regulation and permitting activities. The study may also provide
information for study of other similar industrial wastes.
2-12

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3.0 WASTE STREAM STUDIES
This chapter presents the results of the studies of 10 waste
streams. For each waste the studies included analysis of the litera-
ture and an evaluation of treatment, storage and disposal techniques.
The discussion below includes a short description of production processes
and waste stream characteristics, a description of current, best avail-
able, and most environmentally sound treatment, storage and disposal
techniques, and an assessment of the technological, cost and environ-
mental impact associated with implementation of the best available .technol-
ogy for each waste stream. Three additional waste streams are part of
the explosives study in Chapter 5.
Information on production processes and waste stream characteris-
tics was obtained from the current literature, through discussions with
knowledgeable plant personnel, and from regulatory agencies.
Treatment, storage and disposal alternatives were .then identified.
Current and best available practices were defined as those currently
being used by waste stream generators, with current practice being the
one most often used. The most environmentally sound practice given
usually involved transferring technology used in other Industries. In
some cases, practices that have been proposed, but not yet implemented
by industry, have been given as most environmentally sound. Where
techniques used off the plant site differ from those used by plants to
handle their own wastes, the differences are discussed. In almost all
cases, techniques used on a plant site were found to be the same as
those used by disposal contractors. Further discussion of contract
waste disposal sites, and a listing of sites contacted, is given in
Chapter 6.
Assessments of engineering feasibility, cost analysis and environ-
mental impact were made for the method determined to be the best avail-
able technique for treating, storing and disposing of each waste stream.
Nearly all techniques determined to be the best available are currently
in use in at least one waste-generating facility.
3-1

-------
Environmental impact of implementing best available treatment,
storage and disposal techniques was assessed by comparing estimated
emissions of air, water and land to corresponding minimum acute toxi-
city effluents (MATE's) given In Cleland and Kingsbury, Multimedia
Environmental Goals for Environmental Assessment, 1977. Table 3.1
compares estimated emissions from Implementing best available tech-
nologies for the 13 specific waste streams. MATE's are concentration
levels of specific pollutants. These concentrations were judged to be
appropriate for preventing certain negative effects on the environment
or determined to represent limits achievable through technology. In
many cases, a MATE value was not given for a component of the waste
stream. Therefore, only estimates of low, medium or high emissions
could be given with a corresponding dash mark where the MATE value
would normally appear.
In most cases, properties of key chemical constituents in the
waste stream were used to estimate emissions. For example, a key
constituent for determining waterbome emissions from landfill dis-.
posal of chlorobenzene still bottoms was the solubility of chloroben-
zene, which is 0.0488g in lOOg of water at 30°C. Therefore, even though
solubility will increase with increasing temperature, it is estimated
that roughly 49 mg can be dissolved in 0.1£ of water at 4°C, or about
490mg/JL This establishes an emission of chlorobenzene to water for
estimating purposes.
3.1 SULFUR SLUDGE FROM CHLORINATOR UNIT IN PARATHION MANUFACTURE
Production of parathion, an Insecticide, is included in the
Standard Industrial Classification Manual, 1972 (SIC 2879) as part
of agricultural chemical manufacturing. The total amount of parathion
produced annually is not known. What is known is that approximately
117,621 x 10^ pounds of cyclic organophosphorus insecticides are
produced annually, of which parathion is the most widely used. How-
ever, 10 percent of the amount produced is sulfur sludge.
3-2

-------
Table 3.1 Comparison of Estimated Emissions Using Best Available Techniques and MATES
(Cleland and Kingsbury, 1977)
Waste Streams
Component
of Major
Interest
Best Available
Technology
Em.
Fo
Co
lsslons
r Major
mponent
MATES For Major Component
Air, Mg/m Water, Mg/£ Land, pg/g
Wastewater
treatment
sludge from
PVC productlor
Vinyl
Chloride
Incineration with
HC1 recovery, land
disposal of resi-
due.
Air -
Mft/m
Water
mil
Land
yg/g
Health
Ecology
Health
EcoIorv
Health
Ecology
2.6

38
>100
76
200
.02
<38
<76
Chlorobenzene
still bottoms
Chloro-
benzene
Incineration with
HC1 recovery, land
disposal of resi-
due.
0.001
<488
<0.2
350

5.3 x
106
100
11,000
0.2
Nitrobenzene
still bottoms
Nitro-
benzene
Rotary kiln Incin-
eration with NO
control and hea£
recovery. Land
disposal of resi-
due.
<5.0
<1.0
<2.0
5.0

75
1.0
150
2.0
Tars from
aniline pro-
duction
Nitro-
benzene
Rotary kiln or
multiple hearth
incineration with
N0X control and
land disposal of
residue. Heat
recovery potential
is good.
<5.0
<1.0
<2.0
5.0

75
1.0
150
2.0












Continued

-------
Table 3.1 Comparison of Estimated Emissions Using Best Available Techniques and MATES
(Cleland and Kingsbury, 1977) ^ Continued
Waste Streams
Component
of Major
Interest
Best Available
Technology
Era
Fo
Co
isbions
r Major
mponent
MATES For Major Component
Air, Mg/m Water, Mg/£ Land, pg/g
Sulfur sludge
from parathion
manufacture
Sulfur
Organo-
phosphates
Rotary kiln or mul-
tiple hearth incin-
eration with SO
scrubbing. Lanl
disposal of stabil-
ized scrubber
sludge and inciner-
ation residues.
Potential for heat
recovery.
Air .
Mr/hi
Water
Mr fl
Land
PR/a
Health
Ecology
Health
Ecoloev
Health
EcoIory






Low
Low
Low
Low
Medi-
um
Medi-
um
DAT skimmings
from petro-
leum refining
Low speci-
fic grav-
ity oils
Rerefining
Low
Low
Low
.
_

__


Process liquid
wastes from
solvent-thinne<
trade sales
paint manu-
facture
Solvents
and p'ig-
ment
residues
Recovery with land
disposal or incin-
eration of residue.
Medi-
um
Medi-
um
Medi-
um


















Continued

-------
Table 3.1 Comparison of Estimated Emissions Using Best Available Techniques and MATES
(Cleland and Kingsbury, 1977), Continued
Waste Streams
Component
of Major
Interest
Best Available
Technology
Em.
Foi
Co
Lssions
r Major
nponent
MATES For Majc
3
Air, Mg/m Watei
»r Component
•, Mg/£ Land, yg/g
Wastewater
treatment
sludges from
woven fabric
dyeing and
finishing in
the textile
industry
Chlori-
nated
organics
and
heavy
metals
Sludge dewatering,
disposal in ap-
proved landfill.
Air _
Mj>/m
Water
Mr ft
Land
ur/r
Health
Ecology
Health
Ecology
Health
Ecology






Low
Low
Medi-
um
Wastewater
treatment
sludge from
electroplat-
ing
Cyanide
Chromium
Sludge dewatering
disposal in steel
drums in approved
landfill.
<5.0
<0.001
<0.5
< 0.25
<0.02!
<0.5
5.0
0.001

0.5
0.25
0.025
0.25
1.0
0.5
0.05
0.5
Lithium-
sulfur dioxide
battery
Lithium
metal
Mechanical dis-
assembly with
incineration; S0X,
N0X scrubbing,
and disposal of
residue.
<1
<1
<1
0.022

0.33
0.38
0.7
0.75
Red water from
TNT production
Alpha
TNT
Concentration/in-
cineration with
caustic scrubbing
and land disposal
of ash.
Low
Low
Low
-
-
-
-
-
-
Continued

-------
Table 3.1 Comparison of Estimated Emissions Using Best Available Techniques and MATES
(Cleland and Kingsbury, 1977), Continued
Uaste Streams
Component
of Major
Interest
Best Available
Technology
Em
Fo
Co
Issions
r Major
piponent
MATES For Major Component
Air, Mg/m Water, Mgft Land, pg/g
Bulk propel-
lents, explo-
sives, pyro-
technics
Many
explosive
composi-
tions
Incineration with
caustic scrubbing
and land disposal
of ash.
Air -
Mjj/m
Water
Mr/1
Land
Vr/r
Health
Ecology
Health
EcoIokv
Health
Ecoloev






L6w
Low
Low
Pink water
from load,
assemble
and pack
operations
Spent
Activated
Carbon
Incineration with
caustic scrubbing
and land disposal
of ash.
Low
Low
Low

-------
3.1.1 Manufacturing Process and Waste Stream Characterization
Parathion (o,o-diethyl, o-4-nitrophenyl, phosphothionate) is an
insecticide manufactured under several trade names, and by several
different manufacturers. Monsanto and American Cyanamid produce the
greatest amounts (Noyes, 1977). Parathion is manufactured by combining
phosphorus pentasulfide with ethanol to form diethyl-diethio-phosphoric
acid, which is chlorinated to form parathion. The reaction product
from the mixing of phosphorus pentasulfide and ethanol is processed
through a chlorinator. In the chlorinator, sulfur forms microspheres;
these can encapsulate both the starting material and the chlorination
product. The simple schematic shown in Figure 3.A illustrates the
manufacturing process (Process Research, Inc., 1977).
Air Pollution Control Device
^2
J2
Fljare
>S
SO,
i2
Incinerator
E
ROH
t
p St — Reactor ~ Dialkyl S
2 3 	'		Ether
IT
ci.
Sulfur Sludge
t
Chlorinator
Partial
Recovery
Chloridithionate
NaOC^NO,	~-
*
Parathion
Unit
l**0™ Recovery
A t
~Parathion
Na2C03-
Biological
Waste Treat-
ment Plant
City sewer
Figure 3.A Parathion Manufacturing Process
3-7

-------
There are two manufacturing by-products of parathion: Hydrochloric
acid (HC1) from the chlorinator unit, and sulfur dioxide (SO2) from both
the reactor and the chlorinator. At some facilities, HC1 from the chlo-
rinator is partially recovered for reuse: what is not recovered becomes
part of the aquatic waste stream. Recovery of SO2 as elemental sulfur
from gaseous waste streams is widely practiced in industry. Recovery of
SO2 from the parathion manufacturing process is probable although no in-
formation was found to verify the practice.
Segregatable waste streams include the following:
1.	Sulfur sludge from chlorinator unit. Ihis waste stream is
normally incinerated.
2.	Hydrochloric acid from the chlorinator unit. This by-product
is normally recovered using quench tanks. Unrecovered HC1 is
mixed with the other plant waste streams prior to biological
pretreatment.
3.	Sodium chloride waste from parathion unit. This waste stream
is mixed with the other aqueous process wastes for biological
pretreatment prior to disposal in municipal sewers*
4.	Scrubber effluent from reactor process. If SO2 recovery is
not practiced, hydrogen sulfide (H^SHrom the reactor is
incinerated and emitted as SC^. To meet air pollution stan-
dards, an air pollution control device, such as a wet scrubber,
is used to collect the SC^. Scrubber effluent is an aqueous
waste
-------
Sulfur sludge from the chlorinator unit contains approximately 93
percent sulfur and 7 percent organophosphates. Precise identification
of the organophosphate constituents is not available in literature.
However, it can be estimated that the organophosphate contains:
S
n
unreacted Z^H^O^PSH
S
n
and residual 2(02^0) jPCl
Another probable intermediate product is:
S
a
2(C2H50)2PSC1.
In the chlorinator, elevated temperature and pressure contribute to
the formation of numerous intermediate products, but instability of the
products outside the chlorinator makes them of little consequence in
waste streams.
Organophosphates are highly toxic compounds, and sulfur has a
flashpoint of approximately 66° C (Merck, 1976). The potential toxicity
of the waste stream led to its inclusion in this study. Parathion is
highly toxic, with an	°f 3.6-13 mg/kg, and it is possible that
the organophosphates in the sludge might contain similar toxic pro-
perties (Merck, 1976). There is no information currently available
on the toxicity, stability, or volatility of these intermediate products.
Using general information on the product and the individual elements can
allow for estimating the intermediate properties. Organophosphates
are generally considered to be quite volatile compounds.
3.1.2 Treatment Alternatives
Parathion manufacturers and the organic chemicals industry in
general are reluctant to divulge any information concerning their
hazardous waste disposal methods. Information is available concerning
3-9
-------
the methods currently used for disposal of parathion sulfur sludge, but
it is not known whether treatment is performed on-site or off-site.
American Cyanamid, for Instance, incinerates some of their process
wastes on-site. The remainder of their wastes are incinerated off-
site, and we have been unable to identify which of these wastes contain
parathion sulfur sludge (American Cyanamid, personal communication, 1979).
The present method for treatment of parathion sulfur sludge is
incineration (PR1, 1977). Incinerators for the treatment of sulfur
sludge can be either a rotary kiln type or a multiple hearth incinerator.
Uiey are equipped with air pollution control devices such as wet gas
scrubber systems to cut down the otherwise high emissions of SO^. SO^
control during the incineration is often difficult and expensive. It
is difficult to control the SO2 emission in an environmentally acceptable
manner, even with a wet gas scrubber. Incineration is very efficient in
reducing the volume of waste to be disposed and will reduce the toxicity
of the waste by oxidation. A major disadvantage to use of incineration
as a treatment method for sulfur sludge is the high quantity of energy
required to maintain complete combustion of waste products. S + ^ SC^
is an exothermic reaction; however, a large quantity of heat is still
required to maintain consistently high temperatures for the period of
time necessary to completely break down the waste. Energy could be
recovered from the incinerator in the form of heat or steam, lowering
net energy requirements. No evidence of this practice was found.
Another disadvantage to incineration of sulfur sludge is that sul-
fur emissions mandate use of extensive air pollution control technology
for SO2 removal. Typical air pollution control devices are lime/limestone
scrubber systems, which meet current standards, but generate considerable
calcium sulfite containing waste requiring stabilization prior to dis-
posal as landfill.
Incineration represents the best available technology for this
waste stream. From an environmental and engineering standpoint incin-
eration (combined with air pollution control equipment) is an acceptable
means of disposing of this sulfur sludge.
3-10
-------
3.1.3	Disposal Alternatives
Sulfur recovery from the sludge is less energy intensive and more
regenerative than incineration (PRI, 1977). This process is a con-
ceptual design only and to our knowledge has not been implemented at an
existing plant. This alternative is a five-step process which separates
sulfur for recovery, then detoxifies the organophosphates for ultimate
disposal. The first step involves taking sludge from the chlorinator
unit to a steam heated sedimentation tank operating at 125°C (12°C
above the melting point of sulfur). This treatment melts the sulfur
component of the waste stream and decants the insoluble organophosphate
compounds in the stream. The sulfur stream then proceeds to the ultra-
filtration unit, a membrane separation system which removes organic
compounds with a molecular weight of 150 or greater from the sulfur
stream. The sulfur passes through the membrane at a hydrostatic pres-
sure up to 10 atmospheres. The organophosphates removed in the first
step are cooled to ambient temperature, then refiltered with a cartridge
filter to remove any sulfur retained in the phosphates. The molten sul-
fur is cast into solid, pure bricks which are cooled and then are ready
to be sold. Organophosphate material is mixed with lime, which partially
detoxifies the phosphates, and is composted for final disposal. Detox-
ification of the organophosphates is further accomplished, in time, by
bacterial degradation. Figure 3.1 illustrates the recovery process.
In addition to having recovered a salable product, sulfur recovery
reduces the total volume of waste for disposal by 93 percent and elimi-
nates expensive incineration as a disposal mechanism.
It is not known whether incineration is performed on-or off-site,
nor is there information as to the feasibility of sulfur recovery being
performed on- or off-site. Consequently, methods of treatment discussed
previously apply to both on-site and off-site treatment.
3.1.4	Storage Alternatives
Current information available concerning the treatment, storage
and disposal of parathion sulfur sludge provides no insight into the
use of storage in handling this waste stream. It is presumed that none
3-11
-------
ORCAKO - PHOSPHOROUS
COMPOUNDS
DECAHTED
CRCAHO-PHPS COMPOS
SULFUR SLUDGE
SULFUR
(PlLfBR KACK-WAfiH}
YEAR
937 S01FUR
1% ORCAMOPHOSPHORUS
COMPOUNDS
ULTRAFILTRATION
SYSTEH
CABTSIPCg ULTRATIOH
STVTEH
ORCAMO - PHOSPHOROUS
COMPOUNDS
OKGAKO - PHOSPHOROUS COHPOUKBS
160 TSS
TEAS
RECOVERED SULFUR
TO SALE
2140
SEATED
SEDIMENTATION
TANK
»««« 3.1 £«.„	„f s.If„ «r„ Chl„„„.tlor, „„lt Sulfut sl„dge	p.„,Mon ^ufMttice
* Eesign Figure
-------
of the waste streams are stored for longer than 90 days, other than the
sludge that is collected from chlorination and transported directly to
the Incinerator without significant storage periods. Should a sulfur
recovery system be employed, it would presumably operate on a contin-
uous feed basis, thereby providing only for emergency storage. If
the sludge was stored temporarily, sealed vessels would be necessary.
Other than disposal of residues from incineration, direct disposal
without incineration is not practical for this waste stream.
3.1.5	Recommended Techniques
Sulfur recovery of parathion sulfur sludge is the recommended
treatment technology for handling this waste stream since the only bur-
den it places on the environment is composting the organophosphates. It
also eliminates the energy and air pollution burden of incineration, which
is the best available technology and is the treatment currently in use.
Sulfur recovery has a low functional energy demand, a marked contrast to
incineration. However, additional research is necessary for implemen-
tation of this technology as further discussed in the following section.
We recommend that an industry or expert review be conducted on this tech-
nology.
3.1.6	Engineering, Cost and Environmental Evaluation of Sulfur Recovery
from Parathion Sulfur Sludge
The following equipment would be required for sulfur recovery of a
typical parathion sulfur sludge waste stream:
•	Sludge pump - 3 -d/min
•	Sedimentation tank - 6,000 t
»	Sulfur pump - 9 -£/min
•	Ultrafiltration system - 10 £/min
•	Organophosphorus pump - 2 £/min
•	Sulfur pump - 8 -£/min
•	Cartridge filter - 2 ^/min
•	Sulfur conveyors - 900 kg/hr
•	Organophosphorus storage tank - 2,500 I
3-13
-------
Although the system described for using sulfur recovery technology
appears to be feasible, it has not been tested in either a working or
pilot study situation.
Currently, we have been unable to determine the willingness of
industry to accept sulfur recovery. If the system is easily operable and
cost effective, there is reason to believe that the process would be
accepted by the four parathion manufacturers. Marketability of sulfur
would play a large part in determining acceptability.
The following is a cost evaluation of sulfur recovery (PRI, 1977):
1. Estimated Installed Capital Cost
Basis: 7.67 kkg/day of sulfur sludge
Equipment Item
Capacity
Estimated Cost
Sludge Pump
Sedimentation Tank
Sulfur Pump
Ultrafiltration System
Organophosphorus Pump
Sulfur Pump
Cartridge Filter
Sulfur Conveyors
Organophosphorus Storage
3 ttmin
6,000 I
9 £/min
10 l/mln
2 £/min
8 -£/min
2 £/min
900 kg/hr
2,500 I
$ 14,600
45,700
8,900
4,400
13^100
8,900
13,100
44,000
14,600
Tank
Subtotal
Engineering @10 percent
Contingency Including freight @ 20 percent
$167,300
16,700
33.400
Total
$217,400
3-14
-------
2. Annual Fixed Charges
Depreciation
Interest
Insurance and Taxes
Total Annual Fixed Charges
$217,400 (? 10%/yr
$217,400 
-------
of the waste stream, there will be no resultant variability of the
environmental impact due to the sulfur recovery system.
MATE values were not available for sulfur or organophosphorous
portions of the waste stream. Low air emissions from incineration will
occur, based on the high temperatures and long retention times provided
by rotary kiln or multiple hearth incineration. SO^ is efficiently
removed by wet lime/limestone scrubbing. Medium values for water and
land emissions will occur, based on the high volume of sludge which must
be stabilized and disposed. Although sludge components are not highly
toxic, the high volume generated is expected to have some environmental
impact on water and land in the disposal area.
Estimated emissions from sulfur recovery are based on limited
information which indicates at most a slight impact on land and water
from composting of the organophosphorus portion of the waste stream.
In summary, we feel that controlled incineration is an acceptable
treatment for sulfur sludge, but the associated environmental burdens
make it less desirable than sulfur recovery. Sulfur recovery is heavily
dependent upon the salability of elemental sulfur. Therefore, further
testing and research is needed to determine the sulfur market and
engineering feasibility of the recovery system.
Our discussions with Monsanto and American Cyanamid proved unsuccess-
ful in discovering why they do not recover sulfur or reveal their views
on the recovery technology. Sulfur disposal is a major problem, which
leads one to conclude that recovery should be an encouraging option to
the industry.
3-16
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3.2 WASTE WATER TREATMENT SLUDGE FROM POLYVINYL CHLORIDE PRODUCTION
Production of polyvinyl chloride, a plastic, is included in SIC
282.
3.2.1 Manufacturing Process and Waste Stream Characterization
Polyvinyl chloride (PVC), which consists predominantly of the
repeating structure (CH^-CHCl-), is produced from vinyl chloride mono-
mer (VCM). All polymerizations in the United States are batch opera-
tions. PVC is currently manufactured by four basic processes: suspen-
sion, emulsion, bulk and solution polymerization. Each process has
different discharge characteristics.
Total annual PVC production in 1976 was about 2.34 x 10^ kkg
(2.56 x 10^ tons). Total 1976 vinyl chloride waste from the PVC
manufacturing industry was about 554.9 kkg (611.8 tons) (EPA, 1978b).
Table 3.2 illustrates the processes used and the total estimated vinyl
chloride process waste generated from each polymerization technique.
Of the four major polymerization processes available, the suspen-
sion process accounts for 79 percent of total production. The process
flow is shown schematically in Figure 3.2.
In the suspension method, VCM is dispersed as small droplets
into a stabilized suspending medium consisting of water and small
amounts of proprietary suspending agents. The suspension is then
heated in the presence of catalysts (such as organic peroxides).
After the desired degree of polymerization is achieved, the suspension
is stripped free of monomer, blended with other batches, washed,
centrifuged, and dried. Some plants strip within the reaction vessel,
therefore high pressures and moderate temperatures will be experienced.
The effluent stream from centrifugation contains the majority of the
plant wastes, including significant amounts of very fine polymer.
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Table 3.2 VCM Concentrations Found in PVC Sludges
No.
FVC Sludge
Identification
Weight
Percent Solids
As
Collected
After
Filtration
VCM
Concentration,*
ppa bv weight
Wet	Dry
Sludge Solids
1
2
3
4
Freshly centrifuged sludge*
Fresh combination Bludge++
Sludge from full truck*
Sludge freshly dischared
from truck?
Sludge after disposal and
doze
Plant 1
34
35
34
36
42
55
41
42
41
150
210
520
90
90
360
3B0
1260
200
200
Sludge collected during
discharge from truck?
Plant 2
17
40
20
Sludge collected during
discharge from truck?
Plant 3
30
60
90
130
* VCM analysis of wet (filtrated) sludge by GC-FID analysis of THF extract.
Also calculated on a dry solids basis. 360 ppm ** 360 ng/g ° 0.36 tag/g °
0.036 weight percent,
t Sludge collected at PVC plant directly from centrifuge discharge cube,
tv Sludge collected at PVC plant from partly filled truck loader,
x Sludge collected at PVC plant from full truck loader,
y Sludge collected during landfill disposal.
3-18
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Vinyl Chloride Monomer
Aqueous
Suspending Medium
^ Wastes
Wastes
Reactor
Stripper
Blending
Tank
Dryer
Centrifuge
Polyvinyl
Chloride
Dispersing
Tank
Vinyl Chloride
Recovery Still
Figure 3.2 Suspension Process for Polyvinyl Chloride Production
3-19
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r
The typical PVC manufacturing plant includes the following opera-
tions, common to all four production processes:
•	receiving and storing of VCK and catalysts
•	polymerizing of VCM, which includes measuring, charging
and reacting
•	stripping and recovery, which includes reactor blowdown
and recovery, and slurring handling and storage
•	centrlfugation or filtation
•	drying
•	pneumatic conveying and storage of the product
•	packaging and shipping
•	blending
•	wastewater treatment.
Centrlfugation and wastewater treatment in the PVC production
process results in by-product wastes containing suspended solid matter
and vinyl chloride monomer (VCM) . The effluent stream from centrlfuga-
tion contains the majority of the contaminants from the process. Impur-
ities in the effluent stream consist of small amounts of various poly-
merization processing aids, such as suspending agents, surface-active
agents, free radical catalysts or initiators, unreacted monomer and
significant amounts of very fine particles of the polymer product. In
addition to these contaminants, there may be small amounts of phenol,
sodium phenolate, and sodium hydroxide, which could come from purifi-
cation of the monomer. It is possible that chlorinated organic solvents,
such as carbon tetrachloride and chloroform, which are included in the
starting mixture to arrest the polymerization at any desired point, also
-may find their way into the effluent streams. Nevertheless, the entrapped
VCM In the waste treatment sludge is of primary concern in this study.
Suspension polymerization is the most widely used method for the
manufacture of PVC. However, for production of co-polymers, emulsion
and solution polymerization are employed to a significant extent.
There has been little change in vinyl resin manufacturing methods and
technology over the past 20 years, and no drastic changes are antici-
pated in the foreseeable future. Therefore, characteristics of the
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waste stream may not be expected to change to any significant degree
in the future. Wastewater and resulting treatment sludge volumes may
increase with an anticipated increase in total U.S. production of
vinyl resins in the near future.
3.2.2 Treatment Alternatives
Levels of treatment, disposal and storage technology which are,
or may be, applicable to the water pollution control sludge waste
stream generated by PVC production"are summarized in Table 3.3- The
most prevalent current technology for water pollution control sludge
is contractor disposal in off-site landfills. It is practiced by about
85 percent of the industry. The best available technology currently
in use is rotary kiln incineration. Best available technology sugges-
ted by related industries is incineration with recovery of by-products,
which are heat and HC1.
The technologies applicable to water pollution control sludge
are employed by both industry and waste disposal contractors.
3.2.2.1 Current Practices
As stated previously, most FVC manufacturers currently dispose
of the stripped sludge in off-site landfills, which involves no treat-
ment. However, controlled incineration is being used at some plants.
Controlled incineration represents a technology that is univer-
sally practiced in the plastics Industries. The two areas of concern
related to vinyl chloride waste incineration are incinerator air
pollution and incinerator and gas scrubber corrosion. Hydrogen chlor-
ide is the major toxic material released when vinyl chloride waste is
burned, and it is also a main factor in corrosion of firebox and
pollution control equipment. These problems may be overcome by proper
design and operation and by equipping the incinerator with an emission
control device such as one of the following: an electrostatic precipi-
tator, a baghouse, or a catalytic or thermal afterburner. Presently,
state regulations are such that monitoring and control are the rule
on all incineration equipment. PVC plants still lacking in these
3-21
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Table 3.3 Summary of Treatment, Storage and Disposal Technology for Water Pollution Control Sludge from
PVC Production

Current Practices
Best Available Technology
Technology Suggested
by
Related Industries
Treatment

Rotary kiln incineration
Incineration with
recovery of heat and
HC1
Storage
Steel drums, storage tanks
Waste container with safeguard
Encapsulat ion,
cementation
Disposal
Landfills, burial operations
Secured landfills
Salt deposit
-------
features anticipate equipping or replacing their equipment to meet air
pollution standards.
3.2.2.2 Best Available Technology
Rotary kiln incineration was selected as best available technology
because of potential broad applicability, demonstrated performance and
ability to handle a variety of physical forms of waste. It can incin-
erate combustible solids, liquids, gases, sludges and tars. With the
addition of highly efficient secondary abatement equipment such as
scrubbers and precipitators, rotary kiln Incineration would be a very
useful method for disposing of highly volatile waste such as PVC
sludge. The basis for use as best available technology was the des-
truction of PVC waste sludge in a test study performed at the 3M Com-
pany Chemolite plant (EPA, 1977a). The sludge selected for this study
contained 42 percent water and 26 percent solids, primarily vinyl chlo-
ride. The waste was found to contain 220 ppm of residual VCM and insig-
nificant quantities of other organic compounds on a wet weight basis.
No trace elements were found at concentrations high enough to cause con-
cern about emissions of toxic metals at the feed rates used in the tests.
The incinerator was operated at[full capacity (about 1 ton/hr)
and achieved a combustion efficiency of 99.9 percent. The gaseous
emission rates of chlorinated organics for these tests were determined
to be 0.02 mg per cubic meter of effluent gas. This compares to a
3
federal EPA emission standard for PVC manufacturing processes of 33 mg/m
(10 ppm by volume). Evidently, incineration of PVC would not present
an environmental hazard when combustion efficiency is maintained rela-
tively high (99.9 percent).
The 3M Company Chemolite incinerator system consists of a rotary
kiln primary chamber, a secondary combustion chamber and a wet scrub-
bing system for air pollution control. The plant facility has a rated
capacity of 23 million Kcal/hr (90 million BTU/hr). A schematic of a
rotary kiln"facility is shown in Figure 3.3.
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Secondary
Combustion Chamber
Secondary
Air
Water
Quench Chamber
Water
Burner Tanks
Stack
Pumpable
Drummed
Non-Pump
Rotary Kiln
»~Fly
Ash
Venturl
Throat
	Induced DraM Fan
Water
Water
Water/Ash
Sieve Tower (Oemister)
Water/Ash
Ash/Drums
Figure 3.3 Schematic of Rotary Kiln Facility (EPA, 1977a)
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The rotary kiln is fired with liquid waste fed through a burner
at the front of the kiln. Non-pumpable wastes are left in drums and
fed into the rotary kiln by the drum feed system. The rotary kiln is
normally operated at a temperature range of 815-870°C (1300-1600°F).
The average solids detention time of combustion gases within the kiln
is rougjhly two seconds. The rotational speed of the kiln is usually
set at 0.2 to 0.3 rpm. At the downstream end of the kiln, an ash
handling system quenches and collects ash and burned-out drums from
the incinerator which are loaded together into trucks and transported
to an on-site landfill.
Gases from the kiln flow through a mixing chamber to the secondary
combustion chamber. The secondary combustion chamber is designed to
burn uncombusted gases and particulate matter from the rotary kiln. It
is fired with pumpable PVC waste and/or No. 2 fuel oil, depending on the
characteristics of the PVC waste being incinerated in primary combus-
tion. The secondary combustion chamber is generally operated at 980°C.
Gases from the secondary combustion chamber are cooled with water
in the quench elbow and quench chamber. They then follow through a
high energy Venturi scrubber where particulates are removed. A demis-
ter removes entrained water particles from the combustion gases which
then flow through an induced draft fan and are exhausted to the atmos-
phere through the stack.
Water streams discharged from the scrubber system, demister and
ash handling system are combined into a single wastewater stream. The
wastewater is acidic, and is neutralized with an alkali and sent to a
central wastewater treatment system.
3.2.2.3 Methods Suggested by Related Technology
Thermal oxidation processes have been used to treat gaseous
emissions from incineration of PVC wastes for some time. Other
methods are activated carbon adsorption and the scrubbing (usually
wet) of waste gas streams, techniques that are generally uneconomical
3-25
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and inefficient (Moore, 1975). Oxyphotolysis of vinyl chloride has
been studied but not yet proven in a commercial application. When
the volume of waste gas streams is low, refrigerated vent coolers have
been found useful for limiting emissions, but this approach entails
high operating costs and is not very efficient (Gothesman, 1974). A
thermal oxidation process developed by Nittetu Chemical and Engineer-
ing, Ltd., of Tokyo, Japan, not only can control vinyl chloride emissions,
but also can recover energy and by-product HC1 (Ezaki, 1971; Santoleri,
1973). The Nittetu process is based on the thermal sub-X (submerged
exhaust) system for quenching the exhaust gases by direct contact of
the gas with liquid. The submerged exhaust system quenches hot gases
without the need for a heat exchanger surface (Naidel, 1973). Figure
3.4 shows a process which disposes of chlorinated hydrocarbons with
recovery of up to 20 percent hydrochloric acid, which can be further
concentrated for sale or reuse.
The waste sludge, together with combustion air and auxiliary fuel
(if required^ are introduced into the oxidation chamber by an externally
atomized nozzle, horizontally fired by a vortex burner. Hot oxidation
chamber exhaust gas is then discharged through an alloy downcomer tube
into an acid-brick lined steel tank (sub-X quench tank). Gas is cooled
to saturation temperature and then discharged into the scrubbing towers
for hydrogen chloride or chlorine removal. Up to 20 percent HC1 can be
recovered with or without the heat exchanger. Exhaust from the tower,
saturated with water vapor and almost free of hydrogen chloride, can
be discharged directly into the atmosphere. However, there are also
traces of hydrogen chloride vapor and chlorine which pass through the
tower and require further scrubbing. The gases are scrubbed by an alka-
line solution in a tower placed directly above the absorption tower
before they are discharged,to the atmosphere. This scrubbing tower is
also packed with the Tellcrettle material. Stack gases contain less
than one part per million by volume of HC1 and 10 parts per million by
volume of chlorine. This is well within existing pollution codes.
A system utilizing heat recovery is shown in Figure 3.5.
3-26
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CLEAN EXHAUST GAS
SCRUBBING
WATER
-CAUSTIC
SOLUTION
VCM
WASTE
SLUDGE
CAUSTIC
SCRUB-
BING
TOWER
COOLING
WATER/
OXIDATION
CHAMBER
HEAT
~P>) EXCHANGER
AUXILIARY
FUEL
SCRUBBING
- TOWER
COMBUSTION.
AIR
SUB-X QUENCH
TANK
SALT
SOLUTION
UP TO 20%
HYDROCHLORIC ACID
Figure 3.A Sub-X Type VCM Waste Sludge Cleaning and Acid Recovery System (Kainey, 1976)
-------
CLEAN EXHAUST GAS
STEAM
FEED WATER
SCRUBBING AND
QUENCH WATER
-CAUSTIC
SOLUTION
VCM
WASTE GAS
SCRUB-
BING
AND
QUENCH
TOWER
CAUSTIC
SCRUB-
BING
TOWER
OXIDATION
CHAMBER
AUXILIARY.
WATER
WASTE HEAT
BOILER
COMBUSTION
AIR
DILUTE
SALT
HYDROCHLORIC ACID	SOLUTION
Figure 3.5 VCM Waste Sludge Cleaning and Heat Recovery System (Kainey, 1976)
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3.2.2.4 Methods Suggested by Related Technology
If permanent storage Is required, encapsulation and cementation are
two related techniques which could be applied to storage of vinyl chlo-
ride sludge. Encapsulation involves permanent sealing of a material
and its container in another impervious container of plastic, glass,
or other material unaffected by the waste material. This container may
in turn be sealed within a durable container made of steel, plastic,
concrete, or other material of sufficient thickness and strength to
resist physical damage during and subsequent to burial. It may also
involve the use of above ground silos.
Cementation involves fixation or immobilization of toxic materials
to permit easier handling and reduce the possibility of leaks. Examples
of the cementation processes which have been developed and are appli-
cable for storage in a permanent disposal facility are discussed in the
following.
Weismantel reports that Chemfix, Inc. (Pittsburgh, Pennsylvania)
and Crossford Pollution Services, Ltd. (Sole, England) have each devel-
oped processes that are now being used commercially to harden residues
into inert rock-like materials said to be safe for use in landfill.
The Chemfix process uses soluble silicates to fix the wastes. The
Crossford process converts the waste into a monomeric mixture which
polymerizes at the landfill site within three days to a rock-hard solid.
TRW, Inc. (Redondo Beach, California) is also reported to be working
on a polymeric sludge solidification scheme (Weismantel, 1975).
A process developed by K. Tuzaka is designed to convert indus-
trial waste such as sludges and cyanide-containing waste to innocuous
solid blocks. This is done by incorporating a coagulant into such
industrial wastes, kneading the mixture, press-shaping the kneaded
mixture, sealing the outer periphery of the shaped article by means of
concrete coating, and aging and solidifying the sealed block. The
resulting innocuous solid blocks may be utilized for reclamation or
construction.
3-29
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J. R. Connor has developed a process In which an aqueous solution
of an alkali metal silicate setting agent causes the silicate and
setting agent to react. This converts the mixture into a consolidated,
chemically and physically stable solid product that is substantially
insoluble in water and in which pollutants are entrapped in the solidi-
fied silicate so that the waste material is rendered nonpolluting and
fit for long term storage and disposal (Connor, 1974).
3.2.3 Storage Alternatives
3.2.3.1 Current Pract ices
At present, waste sludge from PVC production is being stored on
land in storage tanks and/or waste containers prior to being trans-
ported for ultimate disposal or treatment. Usage of these methods is
determined by volume of waste, type of waste, pumpability and cost.
Pumpable waste can be stored either in a tank or waste container, while
nonpumpable waste storage is limited to waste containers. Costs dic-
tate usage of waste containers for storing small volumes.
Steel drums and other waste containers used with or without plas-
tic liners provide some long-term containment and are the most conve-
nient storage and transportation mode for relatively small quantities
of potentially hazardous wastes. The most obvious problem with this
method is the eventual decay of the steel drum. Rate of decay infor-
mation for PVC sludge in drums has not been found. Unless disposed in
approved or secured landfills, future release of drum contents to the
environment is likely. Research performed to date has not identified
whether or not disposal in steel drums in a secure landfill will result
in releases to the environment. However, it is believed that by assuming
a slow release over a long period of time, a broad estimate can be
made.
Another problem associated with storage tanks and waste containers
is emission of toxic gases to the air. Air pollution incidents at waste
storage facilities have been cited in an EPA study. Problems can be
avoided by implementing good design and operational practices, which
are described in the following discussion.
3-30
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3.2.3.2 Best Available Technology
In many states, regulations governing the storage of hazardous
wastes are part of general hazardous material regulations. The guide-
lines applied to hazardous waste disposal are also applied to waste
storage facilities. In many states, waste storage is not specifically
mentioned in regulations. However, storage tanks or waste containers
and handling procedures are described at the time engineering plans
for a waste disposal facility are submitted for state review and approval.
The following items also should be considered in plans for handling and
storing hazardous wastes such as PVC wastewater treatment sludge:
•	Storage rooms for PCV waste storage containers should be dry,
well ventilated and fireproof
•	Signs should be placed on the storage building, a fence should
surround the site and doors should be kept locked
•	Fire fighting equipment and appropriate safety devices (respi-
rators, etc.) should be prominently placed. The fire depart-
ment should be aware of quantities and characteristics of
stored materials
•	Emergency instructions relevant to the materials stored should
be prominently displayed
•	Frequent inspection is desirable.
Storage cannot be used as an ultimate disposal method because of
deterioration of containers. Deteriorating containers must be replaced
promptly. A polyurethane foam method for plugging leaking containers
can be used on a temporary basis. This will assure safety while provid-
ing containment until permanent repair or replacement can be made. Con-
tainer materials which are commonly used and available include steel,
rubber-lined steel tanks, nonreactive plastic-lined steel drums and
plastic-lined concrete cases. Containers to be buried may be further
protected by additional inert casings.
Storage of waste with hazardous volatile components such as VCM
is a potential source of air pollution. Careful selection of original
storage container material and size, proper filling and sealing, regu-
lar inspections of the storage facility and prompt replacement of old,
deteriorating containers should permit safe, long term storage. In
3-31
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addition, those containers which require venting must be equipped with
a vapor recovery system.
Aqueous waste streams from PVC production are treated in various
ways at different PVC plants. Typical treatment practices employed are
chemical addition, followed by primary clarification and activated
sludge treatment. Primary clarification concentrates the solids content
of the waste, while wastewater is typically discharged to the municipal
waste treatment system or a surface stream. Chemical coagulants are
added prior to primary clarification and the precipitated materials are
physically removed by sedimentation and centrifugation. The final
waste material is a water-based sludge ranging from about 15 percent
solids from sedimentation to 40 percent solids from centrifugation.
Physical properties vary from water-like, thin slurries to thick pastes
approximately the consistency of a concrete premix.
EPA studies in the spring of 1974 at six PVC plants show concen-
trations of VCM in sludge ranging from less than 1 ppm to 3,520ppm in
wet sludge and from less than 1 ppm to 4,200 ppm in dry sludge. Most
of the samples contained greater than 10 ppm on either a wet or dry
basis. These fluctuations may reflect changing plant production schedules,
which affect production rates and product mixes (PVC homo-polymer types,
PVC copolymer types, ratio of homo-polymer to copolymer, etc.). Table
3.3 shows VCM concentrations found in PVC sludges in another EPA study
(EPa, 1976a). There are also insignificant amounts of various polymeri-
zation processing aids in the sludges. The chemical composition of the
sludge Includes 1 to 3,520 ppm VCM, 200 ppm PVC solids, 2 percent ash,
and very low concentrations of heavy metals (EPA, 1976a).
Vinyl chloride, which can volatilize from PVC wastewater treatment
sludge, is a colorless, flammable gas under normal temperature and pres-
sure. It has high volatility with a vapor pressure 2,660 mm Hg at 25°C,
boiling point 13.9°C. VCM polymerizes in light or in the presence of
catalyst. On combustion, it is degraded into hydrogen chloride, carbon
monoxide, carbon dioxide and traces of phosgene (Cleland and Kingsbury,
1977). Pure VCM is considered a severe fire and explosion hazard when
3-32
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vapors are exposed to heat and flame. At about 450°C, vinyl chloride
begins to decompose, forming small amounts of acetylene. Vinyl chlo-
ride is slightly soluble in water and soluble in alcohol and ether
(Kirk-Othmer, 1967).
l&uployees of PVC production plants must not be exposed to vinyl
chloride at concentrations greater than 1 ppm, averaged over an eight
hour period, according to the Occupational Safety and Health Adminis-
tration (OSHA). Also, no employee may be exposed to concentrations
greater than 5 ppm, averaged over 15 minutes or less. An estimated
20,000 workers, past and present, have been exposed to vinyl chloride
in manufacturing plants.
Toxic effects associated with vinyl chloride exposure include
narcosis from acute exposure and low grade liver and kidney damage
from chronic low exposures. Low exposure effects are similar to those
from exposure to other halogenated aliphatic hydrocarbons. In addition,
vinyl chloride disease, or anacroosteolysis, has been observed among
workers exposed to vinyl chloride. This disorder is characterized by
degeneration of bones in the fingers accompanied by Interference in
peripheral nerve response and diminished blood circulation. Anacrooste-
olysis has been associated primarily with physical contact with 7VC
and high levels of VCM (Dinman et al., 1971). This disorder has become
well documented in PVC epidemiological studies. Anacroosteolysis
appears to be a toxic effect unique to vinyl chloride compared to other
aliphatic chlorohydrocarbons. The multi-tumor response and appearance
of liver angiosarcoma in experimental animals at lower exposure levels
is similar to the cancer response reported in PVC/vinyl chloride workers
(EPA, 1978b).
When spilled on the skin, rapid evaporation of vinyl chloride can
cause local frostbite. At concentrations over 500 ppm, this chemical
has a slightly toxic action and irritates the eyes, and it is considered
to be a primary irritant for skin and mucous membranes. Acute vinyl
chloride toxicity in humans is rare since toxicity is not clearly per-
ceptible below 1,000 ppm. At 1,000 ppm, humans exhibit slight anesthesia,
drowsiness, slight visual disturbances, faltering gait, numbness and
tingling of the extremities (EPA, 1978b).
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Carcinogenic activity of VCM has been confirmed in several species
of rodents at 250 ppm and is associated with both sub-acute and chronic
low-level exposure when the experimental period was long enough to per-
mit tumors to appear. Tumors found in mice were primarily lung tumors,
mammary carcinomas and angiosarcomas (malignant haemangioendotheliomas)
of the liver. Angiosarcomas of the liver and other organs, zymbal gland
carcinomas and nephroblastomas occurred in exposed rats. Preliminary
studies have suggested that VCM also produces subcutaneous angiosarcomas
in the offspring of rats that have been exposed during pregnancy (Viola
et al., 1975).
In view of the extreme rarity of angiosarcoma of the liver in the
general human population, observation of the 16 cases in workers exposed
to VCM during the polymerization process is evidence of a casual rela-
tionship (Viola et al., 1971). The appearance of hepatic angiosarcoma
in experimental animals and the discovery of the rare lesion in PVC/
vinyl chloride workers underscores the predictive value of experimental
animal toxicology (Maltoni, 1974).
3.2.4 Disposal Alternatives
3.2.4.1 Current Practices
Burial operations and landfill are widely used in the plastics indus-
try for hazardous wastes which are not incinerated. These wastes are
essentially wastewater treatment sludges, such as those from PVC pro-
duction, and hazardous nonflammable solids. Burial and landfill locations
include both public and private landfills.
At the present time most, if not all, of these sludges are discarded
at municipal or privately owned landfills. Typically the sludges are
transported to the landfill or burial site in pressure-controlled tank
trucks or open-bed trucks and dumped into bulldozer-prepared pits or
trenches 0.6 to 3 or more meters deep. They are then covered with com-
pacted layers of trash and soil to a depth of 0.3 to 1 meter or more.
The problem with these disposal methods is that PVC sludges dis-
posed at landfills may still contain sufficient VCM to constitute a
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potential health hazard when the gaseous VCM escapes. An EPA study
reported that VCM air concentrations on the order of 1.0 ppm can occur
at normal breathing heights (1.5 meters) above ground level at these
landfills as long as 24 hours after PVC sludge deposits are covered and
VCM air concentrations as high as 0.37 ppm can occur in residential
or public access areas adjacent to these landfills. The study also
found that about 0.1 to 0.3 ppm of VCM present in air at landfills
where PVC sludges have been disposed for several years (EPA, 1976).
Monitoring of VCM concentrations in leachate or runoff water from land-
fill has not been conducted. However, it is possible that components
of PVC sludge, such as one or more of those listed in Section 3.2.2
may find their way into ground and surface waters.
3.2.4.2 Best Available Technology
At the present time, secured landfills are the best available land-
filling techniques considered adequate to prevent environmental damage
to air, and to ground and surface waters.
Secure landfilling would require the following:
1.	The composition and volume of each extremely hazardous waste
is known and approved for site disposal by a permitting agency.
2.	The site is geologically and hydrologically acceptable for
extremely hazardous wastes, Including the following criteria:
•	soil or soil liner permeation rate of less than 10 cm/sec
•	water table well below the lowest level of the landfill
•	adequate provision for diversion and control of surface water.
3.	Provision is made for monitoring wells, rain water diversion and
leachate control and treatment.
4.	Records are made of burial coordinates to avoid any chemical
interactions.
5.	Registration of the site is performed for permanent record of
its location once filled.
The typical landfill techniques presently practiced for disposal
of hazardous waste include surface adsorption, direct landfill, isola-
tion, burial and subsurface injection. Each of these techniques results
3-35
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in underground emplacement of wastes. The type of cover materials
vary with the disposal technique which, in turn, is determined by the
type of waste. Surface adsorption and direct landfill require only a
relatively shallow cover of impermeable material, whereas subsurface
adsoption and isolation burial need deeper underground placement of
waste materials. In isolation burial, the wastes are commonly sur-
rounded and covered by an impermeable layer of soil.
Relatively isolated impermeable soil conditions exist in many
areas of the country. If impermeable soil is not available, then
clay, special concrete, asphalt, plastic and other liners and covers
are available to accomplish similar containment and isolation of the
hazardous wastes.
Figure 3.6 shows a typical design for a secured landfill using
impervious liners (Lindsey, 1975). The impervious cover protects the
waste from rainfall and also prevents continuous escape of gases,
which may create other problems of pressure build-up and catastrophic
release. These problems can be corrected by installing gas venting
equipment at the landfill. Gas vents have been used successfully to
prevent underground migration and subsequent emission of pollutants
in areas adjacent to the disposal site (Pacey, 1975).
Either subsurface injection, surface adsorption, or consignment
burial may also be used as the disposal method. In the event that soil
covers or liners are not adequate to control emissions of toxic gases
from the VCM waste, waste pretreatment alternatives (encapsulation,
chemical fixation, neutralization, etc*) may be used.
The cost of secure landfill disposal varies with the burial tech-
niques employed. Isolation burial in a separate grid cell or subsurface
injection would cost about $9 to $12 per ton (1977) of wastes while
disposal of materials by surface adsorption costs about $3 to $8 per
ton (1977) (EPA, 1978b). Factors contributing to cost distinctions
from site to site include the available land and its value, geological
and meterological conditions, state design requirements for secure
3-36
-------
Iir.perviouj liner
Monitoring
well
Hazardous material
Cay
'l"> ' impervious
liner
¦WatBT Table
Figure 3.6 Secure Landfill Configuration (Lidsey, 1975)
3-37
-------
landfills, labor rate and equipment costs, the available market and
volume of waste processed, and types of cover materials used.
3.2.4.3 Methods Suggested by Related Technology
A category of ultimate disposal which is similar to, yet quite
different from deep well disposal, Is salt deposit disposal. This
technique may be applicable for the disposal of wastewater treatment
sludge from PVC production industries.
A process developed by D. A. Shock provides a method by which
predominantly organic waste materials of a highly toxic or noxious
nature, such as mustard gases, nerve gases, harmful biological agent6,
phenols and the like, may be permanently disposed In a safe manner.
Basically, and in its broadest aspect, the method involves mixing of
a toxic organic waste material with an oil-base fluid material which
is compatible with the waste material and forms a pumpable slurry.
Hie oil-based material contains appropriate jelling agents which
impart thixotropic properties to the slurry, or at least ensure that
the mixture will be in a solid state upon standing. The slurry may
be transported to, and allowed to solidify in, a location which is in-
accessible to human and animal life, and is isolated from contact with
useful mineral deposits. The physical and chemical properties of the
slurry are such that underground cavities may be utilized for permanent
disposition of the material if desired (Shock, 1965).
3.2.5 Engineering, Cost and Environmental Evaluation of Rotary Kiln
Incineration of PVC Sludge
The best available technology for treatment of PVC sludge, rotary
kiln incineration, has been used successfully for this waste stream.
The incinerator must be equipped with a secondary combustion chamber
align scrubber to meet air emission regulations. Waste streams from
wet scrubbers must be treated prior to recirculation or discharge.
Combustion residues include ash and burned out drums, which previously
contained nonpumpable sludge. These materials are not considered
3-38
-------
hazardous due to lw heavy-metal content and thus could be used as
landfill. Industry acceptance of this technique depends largely on the
added costs. This method does not recover salable materials or heat
from the waste stream, which would otherwise provide an added incentive
to the industry. Costs might be more acceptable if they were shared
among plants, using an off-site waste disposal contractor's rotary
kiln for this waste stream.
As an alternative, the Nittetu process is depigned to recover
heat and salable HC1, eliminating the waste stream from the wet scrub-
bing system of the rotary kiln. However, several mechanical problems
remain to be solved and tested with FVC sludge before this process can
be considered as the best available. For example, the interface between
the oxidation chamber and the acid tower will be subjected to continual
hot-cold temperature swings, which the refractory would be able to
withstand in an acid liquid environment. A special Interface has been
developed by Trane Thermal Company for this application. The acid
towers are constructed with acid-brick within a lined steel tower,
and the tower internals are usually made from inert materials such
as graphite or ceramic. Materials for the caustic scrubbing tower
must be able to withstand both acid and hypochlorite corrosion. If
caustic is used in the acid tower, the material selection must also
take this into consideration.
3.2.6 Recommended Treatment and Disposal Techniques
The most favorable treatment and disposal techniques for treat-
ment of wastewater treatment sludge from FVC production is the Nittetu
process. The rationale for selection of this process is that not only
can it control vinyl chloride emissions to meet existing pollution
codes, but also it can recover energy and by-product HC1. The process
developers also claim that it produces no by-product residues to be
collected and disposed. To date, it is estimated that about 30
installations using the Nittetu process have been designed and built
in the United States for chlorinated hydrocarbon waste disposal. Of
these, a few are installed for disposal of vinyl chloride sludge
3-39
-------
(Santoleri, personal communication, 1979). The problems associated
with the Nittetu process Include high costs of incineration equipment,
fuel, and operations and maintenance. Another drawback of this pro-
cess is that in the event of equipment breakdown, there is no back-up
system to assure adequate protection from exposure to vinyl chloride
emissions.
One major problem in the combustion of wastes is associated with
the introduction of waste materials into the combustion chamber. Major
problems with liquid injection are those presented by high viscosity
and solid particles in the sludge from the wastewater treatment plant.
To overcome these problems, an externally atomized nozzle developed
by Trane Thermal Company is utilized. This type of nozzle operates at
low pressure, minimizing the problems of pumping liquid wastes.
In the heat recovery process shown earlier in Figure 3.4, the
waste heat boiler uses hot gases being discharged from the oxidation
chamber to generate steam. Equipment downstream from the boiler can
be either an acid tower or a sub-X quench tank (Kaing, 1976). Because
of the acid and chlorine environment In the boiler, corrosion of the
boiler tubes is the major problem for this system (Hung, 1975). Cor-
rosion problems observed during startup and shutdown can be mitigated
by setting and following proper operational procedures.
Recovered HC1 has a quality comparable to commercial technical
grade HC1, and has a composition as follows: chlorine, 10 ppm; water,
60 ppm; and organics, 10 ppm. It was also claimed that by modifying
this system, recoveries of HC1 from 20 percent up to 100 percent could
be attained (Ezaki, 1971; and Naidel, 1976).
The process developer also claims that use of a vortex burner
permits operation at very near to stoichiometric levels with essen-
tially complete combustion, ensuring complete destruction of wastes
due to high heat release characteristics. Therefore, little residue
is produced in the combustion chamber, minimizing collection and
desposition problems.
3-40
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Rotary kiln incinerator capital and operating cost estimates were
reported for a system of the size tested at 3M Company and for a much
smaller system, more nearly matching the requirements of the average
individual PVC manufacturing facility. Results of these estimates
are shown below;
Ihe capital investment is based on March, 1976 dollars which is
represented by an Engineering News Record Construction Cost Index of
2,322 (EPA, 1977).
Capital investment includes equipment costs, site preparation,
engineering and contingency. Operating costs Include labor, overhead,
taxes and insurance as well as interest on equipment purchases.
Table 3.4 compares estimated vinyl chloride emissions for landfill
incineration and salt deposit disposal. Sue to potential air, ground
water and surface water pollution, direct land disposal of wastewater
treatment sludge from PVC production is not recommended. Rotary kiln
incineration of this waste stream can result in air emissions of
3
chlorinated organlcs at 0.02 mg/m of effluent stack gas, assuming
optimum operation of the incinerator. This can be compared to a
3
minimum acute toxicity effluent (MATE) for health of 2.55 mg/m for
vinyl chloride, which is conservative, since less toxic chlorinated
organics may be present in the stack gas emission (CIeland & Kingsbury,
The wastewater stream from the wet scrubber must undergo pH
adjustment and biological or physical/chemical treatment prior to
discharge. Although no data were available from the 3M facility, only
traces of organics are expected in the waste stream, and the MATE for
health of 38 mg/£ would be met easily.
3M System Smaller System
Incinerator Capacity (Metric Tons/yr)	6,696
Estimated Capital Investment ($)	7,780,000
Estimated Operating Costs ($/Metric Ton)	582
335
3,900,000
1,767
1977).
3-41
-------
Table 3.4 Vinyl Chloride in Wastewater Treatment Sludge
Estimated Emissions
Current Practice Best Available Transfer of Technology


Landfill
Incineration
with HCL
scrubbing
Salt deposit
disposal
Media
MATE VALUES



Air,
mg/m3
Health 2.55



Ecology
N.G.
1 part per million
0.02
<2.55
Water,
Health 38
High but probably
<38
Approaching
Zero

rog/1
Ecology
>100
<38
Land,
Health 76

<76
<76
ug/g
Ecology
200
>76
-------
Solid residue from incineration would be disposed as landfill and
would not contain organics, meeting the MATE of 76 Pg/g for land dis-
posal.
Information on emissions from salt deposit disposal was not avail-
able from the literature, but it is assumed that the waste would be
isolated so that MATEs for air, water and land would be easily met.
3-43
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3.3 TARS FROM ANILINE PRODUCTION
Anilines are used in dyes, as pharmaceuticals, photographic chem-
icals, rubber accelerators, antioxidants, herbicides and fungicides.
Aniline is also called aminobenzene, phenylamine, and aniline oil. The
industry code for anilines is found within SIC 2865.
3.3.1 Manufacturing Process and Waste Stream Characterization
Aniline is processed in two ways: the reduction of nitrobenzene
and the aminolysis of chlorobenzene (Ottinger et al., 1973). The
method utilizing nitrobenzene reduction is used for 95 percent of all
aniline production. Seven chemical companies manufacture anilines, and
three of these manufacture for captive use (Lowenheim and Moran, 1975) .
Captive use is estimated to consume between 47 and 60 percent of the
279,000 kkg of anilines manufactured annually (Ottinger et al., 1973).
This amount is expected to escalate because of increased production of
isocyanate which uses aniline in its synthesis. Figure 3.7 Illustrates
the mechanism for production of aniline by way of nitrobenzene reduction
(Lowenheim and Moran, 1975).
No by-products were found in the nitrobenzene reduction process.
Segregatable waste streams include the following (Lowenbach and
Schlesinger, 1978):
•	Waste from the separator which consists of aniline, carbon
monoxide, hydrogen, methane and nitrobenzene. No information
is available Indicating the percentage of each component
in the waste stream
•	Volatile components from the distillation column which contain
an unknown amount of cyclohexamine, volatile amines and water
•	Still bottoms from the distillation column, frequently referred
to as tars, which contain unknown amounts of aminophenol,
azepin, diphenylamine, nitrobenzene, phenylenediamine, and
nitrogen-containing high molecular weight polymers
¦ Extraction column residue containing aminophenol, aniline,
nitrobenzene, phenylenediamine and water-soluble amines.
The concentration of each component is not known.
3-44
-------
NitfefeCfttffftf

O
3:. J-Lii
m
°i1
J /Vi
h)**ogeA
U>
I
U*
NfOlO^fA
	Rft*cV	Afufarn
1	NtlroUnunc Kporuo.
Z	Rector with Buidurd cata)t|l bed
3	Ctrtliflf *ut<55.
4	(jla)i|it fillers.
5	P"-dud rond'iiitf
6	icCkV
<3
ArutiiH
•«t«r
1 3
X

a


. ui
10

imlifll
Purgt
WmI# *«1tf
1—=—1
Pwic
Ofrta, ft
fiecrcif
7	^nUirif-»«iiei vctiler and <3«canlCf.
8	Cnidc aniline snll
9	Rrt*nlci fui trod* anient tliU.
)0	Cor>i)cnMJ.
II	A.ni]ir>r firvvhing iiiU.
11 for anilirie lini«)iin£ »liU
CouftlfcT-curr^ni evtrftcclon coKan for inlllnt-vitef.
Figure 3.7. Catalytic Vapor-Phase Hydrogenation of Nitrobenzene
-------
Aside from equipment malfunctions, the aniline process appears to
produce little variability in the waste streams. However, the waste
streams from reduction of nitrobenzene differ greatly from the waste
stream from aminolysis of chlorobenzene. The nitrobenzene reduction
mechanism, since it is used for almost all of the aniline manufactured
in the United States, will be covered in detail.
Anilines are hazardous in that they are highly explosive and have
a flash point of 76°C (International Technical Information Institute,
1976). The aniline vapor forms an explosive mixture with air and it
can ignite in a violent reaction with HNO^. The TLV for aniline is
5 ppm and it is highly toxic when absorbed through the skin, inhaled
or swallowed. Nitrobenzene, which vaporizes easily, is also a very
toxic component of the waste stream.
3.3.2 Treatment Alternatives
Most commonly, aniline manufacturers use a combination of physical/
chemical and biological treatment for wastes. Host manufacturers also
combine all aniline processing wastes, including tars, for treatment.
The analysis of waste treatment practices is further complicated because
most aniline manufacturers also manufacture nitrobenzene and therefore
the wastes from both processes are combined. Figure 3.8 shows the
types of biological treatment used for aniline manufacturing wastes
(Lowenbach and Schlesinger, 1978).
Best available treatment for tar residues from aniline manufac-
ture is incineration. The hazardous nature of the waste stream has
caused biological treatment problems when combined with liquid wastes
from production facilities. These problems are associated with the
toxic materials in the waste stream killing the bacteria that comprise
the treatment process. Rotary kiln or multiple hearth incinerators are
effective for aniline distillation residue. Tests on the tar substance
show it to have a median heat value that would be well-suited to incin-
eration and other thermal destruction techniques. It is not known if
aniline wastes are incinerated directly; however, nitrobenzene wastes
are incinerated as are aniline wastes after they have been stripped.
3-45
-------
1
MAJOR U.S. fllTROftEMZENE/AHILIJit HAHUFALTUUJIS
U>
*-¦4

HAKE PLATE CAPACITY
HITTOSCNEBTC AHILIKI
KPDCS WO.
HEAHS or WASTEWATER
TBIATKENT'
HAM/TAtmnta
(Hillloo pounde/year)


First Mississippi Corporation
Pascagoule, Hieoieaippi
133 100
US
0001791
ffcutcslltatlon, equal-
Itatloo, stripping,
activated caibon adsorp-
tion .
AoaricaQ Cyaoanid'
Vlllov lalasd, Ueat Virginia
60 30
UV
0000787
Aerated lagoon, biologi-
cal contact, clarification,
sludge handling.
E»l. dufont de Nesouro 4 Co.
Beeumoat, Tases
310 230
T*
000*669
Equalisation, aereted
Isgoon, activated eludge
ecctoated carbon
edsorptlon.
C.I. duPont de Ncmuce 4 Co.
Clbbatovn, R«w Jersey
200 130
HJ
0004219
Organic evtrectlon,
(tripping, neutralisation,
equalltatlon, clarlfIcetloa.
Malllocltrodt, lac.
fcelelgh, Borth Carolina
4
KC
0003338
Equal1let Ion, et ablllts-
tlon pond, activated eludge,
clarification, cheslcal
treatnant (odor control),
stabilisation pond, land
application.
Hobay Chenlcsl Corporetioa
Hew Martlaevllle, U«et Virginia
133 100
W
0003169
Neutrallcstlon, clarifica-
tion, aqualltatlon, activated
aludgei activated cerboa
edaorptlon.
Rubicon Cbeiicslt toe.
Ceienar, Louisiana
73 60
Uk
0000892
Subsurface disposal.
^Cbcaical Mirkitlof Reporter, Jutury 7, 19H( Hay 24, 1971, August 30, 1976 «ad comunleitlonf with Industry;
«• cltid In Dlrtctotr of OteAleil Producer* - U.S.A.
'tact eoUuttd fro* tPA Organic* And FUitltl 308 Ruponta (1976), KPT Maitir file 11ii1q|. Note; This listing
repreeeots all unit treatoeot processes Is uee for *11 nltrobentens/anlllne saoufscturlog effluent*, however, It
ts ooC tb« loteotioo of this listing to oeceeearlly loplf ao ordering of unit processes. Furthermore, segregated
proceee «tie«u ere typletllf coabloed with other aanufacturlo| wastes at eech feclllty, asking e detailed descrip-
tion of weatewecer treatoeot facllfttlee from publicly eveileble Information iq>oailbl«.
'/iarlcio Cyanaald facility 1q Bound Brook, Rev Jexiey haa beta oo ate«d-by aloce 1974; oltrobeatene capacity:
85 elllloo poundo/yeer; aod mlliot cepaeityt WJ all I Ion pounda/yeer. This plaoc Is due to cobs on-1 toe to 1978.
^Production figures are tmsvaileble for this aniline oanufecturer Itote' Nitrobenzene la not produced at thie
facility-
Figure 3.8 Biological Treatments Used by Major U.S. Aniline Manufacturers
-------
Related technology in other industries suggests stream stripping as
a possible alternative for treatment of aniline tars (Lowenbach and
Schlesinger, 1978). An aqueous phase stripper can be used to separate
the waste. The product from the stripper contains 50 percent aniline by
weight which would be incinerated leaving a bottom product containing
0.2 percent aniline for biological treatment. The advantages to this
system are that it reduces the quantity of waste for incineration and
leaves the waste requiring biological treatment low in toxic aniline
concentration. A more detailed discussion of stream stripping is given
in Section 3.5.
Reference to the use of off-site contractors for treating tar
residues were not found; however, differences are not expected between
on-site and off-site practices.
3.3.3	Storage Alternatives
Storage techniques with particular application to aniline tar
residues were not found.
3.3.4	Disposal Alternatives
Presumably sludges from wastewater treatment are disposed either
on or off-site, although there is no literature on the subject.
Rubicon Chemical, Inc. of Louisiana currently practices off-site
deep well injection as a means of disposing of their nitrobenzene and
aniline wastes. Deep well injection is a proven hazardous waste dis-
posal alternative. However, few areas of the United States are underlain
with geological formations which permit environmentally safe deep well
injection. Therefore, their capacity to handle large volumes of wastes
may be more appropriately used for wastes for which no other reasonable
disposal alternatives exist.
Secure landfill may be a viable alternative for off-site disposal
of the waste stream, although no information was found on this practice.
3-48
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3.3.5 Recommended Techniques
Drawbacks for biological treatment of aniline tars include the
difficulty of acclimating biological organisms to the waste stream.
The stability of the treatment system varies with the waste loading,
and the treatment system must handle seasonal variations in loading.
Many of the organic compounds in aniline tars are volatile. If treated
in a lagoon or stabilization pond these compounds will vaporize and
be released ^nto the atmosphere. Many lagoons and stabilization ponds
are inadequately lined for hazardous wastes and can allow seepage of
these compounds into the ground water system. It is often difficult to
treat different waste streams in the same lagoon system and, as men-
tioned previously, they are not entirely effective in treating wastes
such as aniline tars.
Incineration, as discussed for other waste streams, has a number
of associated environmental burdens. An ordinary incinerator has the
burden of requiring much energy to burn most wastes efficiently, par-
ticularly those with low organic content. Also, disposal of the ash
residue and scrubber wastes from Incineration creates an additional
burden. This burden is lessened when anilines are Incinerated, because
this medium heat value allows recovery of energy in the form of steam
or hot water. With the use of air pollution control devices the air
pollution burden from incineration of aniline wastes is decreased ;
however, even with the use of flue gas scrubbers, some N0x emissions
will reach the atmosphere. Venturi scrubbers are the most common
gaseous air pollution control devices. The liquid scrubber effluent
will require biological treatment before disposal to the publicly
owned treatment works (POTW) or surface discharge.
Steam stripping presents a lower environmental burden than incin-
eration or biological treatment of tarry wastes. Biological treatment
and incineration are both used in steam stripping aniline tars. How-
ever, steam stripping cuts the burden on each of these systems, since
it halves the waste load handled by the biological treatment system,
thus increasing its effectiveness and incineration is only reauired for
half the amount of wastes, thus halving N0x emissions.
3-49
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Deep well injection is a burden predominantly to the ground water
environment due to the problems of seepage. Minimal amounts of volatile
components could be emitted to the atmosphere during the transportation
and injection process. Under Ideal conditions, contamination of ground
water can be prevented, but cracks in the geologic formation and any
minor faulting can lead to contamination of a ground water aquifer system.
Also there is an explosion hazard associated with injection of aniline
wastes, since they can explode under certain environmental conditions.
3.3.6 Engineering, Cost and Environmental Evaluation
The engineering and cost evaluation for incineration and steam
stripping is given in detail in Section 5.5. The evaluation is appli-
cable to aniline tars as well as nitrobenzene distillation residue.
Table 3.5 shows a comparison of estimated emissions of nitroben-
zene, a key component in aniline tars, with MATE values.
Biological treatment in a lagoon can cause many components of the
tar residue to be volatilized into the atmosphere. Lagoons and stabil-
ization ponds can often lead to ground and surface water contamination
because of seepage and leaching. However, many components of the waste
stream degrade readily into simpler, less harmful compounds when exposed
to air and light. Therefore, biological treatment is potentially more
effective for aniline waste than for other similar waste streams, pro-
vided aniline concentrations are not too high.
Incineration of aniline tars creates small impact on air pollu-
tion through the release of N0x to the atmosphere. There Is an impact
on water pollution due to the use of a wet scrubber to abate the air
pollution problem. The largest impact is that of energy usage to oper-
ate the incinerator. High energy demands of incineration play an impor-
tant role in evaluating the benefits of incineration. Energy demand can
be minimized with common heat recovery techniques. Another environ-
mental impact of incineration is from disposal of ash residue in secure
landfills after incineration. Although the waste stream has been
3-50
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Table 3.5. Nitrobenzene In Waste Tars
Estimated Emissions
Current Practice Best Available Transfer of Technology
Media
MATE VALUES
Land application
of sludges from
biological treat-
ment of combined
plant wastes
Rotary kiln
or multiple
hearth incin-
eration
Steam stripping
followed by incin-
eration of product.
Biological treatment
of bottoms
Air,
mg/m3
Health 5.0
Ecology
N.G
>5.0
<5.0
<5.0
Water,
mg/1
Health 75
Ecology
1.0
>1.0
<1.0
<1.0
Land,
"g/g
Health 150
Ecology
2.0
>2.0
<2.0
<2.0
-------
detoxified, Che ash must be properly disposed in a sanitary landfill
which is designed to abate ground and surface water problems.
The environmental Impact of steam stripping is the same for the
total impact of both biological treatment and incineration.
The environmental impact of deep well injection is on ground water.
The possibility of ground water contamination is always present with
this method of disposal.
In summary, steam stripping appears to be the best method for
disposing of aniline tars. The explosive hazard of the waste stream
makes it imperative that reliable procedures are used in the disposal
of this waste. Although, in our literature review, we found no recording
of damages due to explosions during aniline waste disposal.
3-52
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3.4 DISTILLATION RESIDUE FROM CHLOROBENZENE MANUFACTURE
Production of chlorobenzene, also called benzene monochloride, mono-
chlorobenzene and phenyl chloride, falls into SIC 2865. Chlorobenzenes
are used as solvents in lacquers, paints and waxes, and also as inter-
mediates for dyes (ITII, 1976).
3.4.1 Manufacturing Process and Waste Stream Characterization
More than 70 million gallons of chlorobenzene are produced annually
at 12 U.S. facilities (A.D. Little, 1973). The process of chlorobenzene
manufacture is shown in Figure 3.9. Chlorobenzene is manufactured by
reacting benzene in the presence of iron catalysts; gaseous chlorine is
bubbled into the reactor and the reaction is kept at 50°C to produce
crude chlorobenzene. Crude chlorobenzene 1s actualized, settled and
separated. Fractionation produces mono- and dichlorobenzene. It is
the residue from the fractionation towers which produce the hazardous
waste stream (PRI, 1977).
There are two by-products from chlorobenzene manufacture. One is
dichlorobenzene and the other is HC1 (PRI, 1977), Dichlorobenzene is
collected from the settling tanks and is recovered from the sludge.
HC1 is a product of the scrubbers from the reactors. HC1 is a by-
product insofar as it is emitted from the incinerator as a gas and
sent to a quench tank, where it is recovered In a gas scrubber.
There are six segregatable waste streams from chlorobenzene manu-
facture (PRI, 1977). They are:
•	hydrochloric acid from scrubber effluent
«	dichlorobenzene slwuige from settling tanks
•	benzene and water from fractionation towers
•	benzene and chlorobenzene from fractionation towers
•	chlorobenzene and dichlorobenzene from fractionation towers
•	polychlorinated aromatic resinous materials from fractionation
towers.
3-53
-------
u>
I
U1
¦t-
CHLOROOEHZENES HAHUfACTUP£
BASIS: 1 KG MONO CHLOROBENZENE
BENZE tE OR CHLOROGEtlZEliE
HYDROCHLORIC
ACID
BENZENE 3.9S
CHLORINE 0.875
CATAL*ST_0.0OT5
(IRON TURNINGS)
CIILORINATOR
O
HC1 SCRUBBER VEIfT
HCl 0.0014
AIR
WATER
CD
1 l i—— VENT
1		t I HCl 0. CfOI 35
"L
HTDROQILORIC
ACID Q.37
SCRUBBERS
SODIUM HYDROXIDE
{
HEUTRALIZER
DICHLOROOENZEIIE
SLUDGE TO RECOVERY
SETTLER
®
WASH STREAM Dl CHLOROBENZENE COLUMN
CHLOROBENZENE 0.00088
01 CHLOROBENZENE 0.0037
Water
BENZENE AND WATER 0.038
BENZENE ANO CHLOROBENZENE O.IS
CHLOROBENZENE 1.0
OtLOROOEKZEIIE «I0
DIOILOROBENZENE 0.18
©*©
POLYCHLORINATED AROMATIC
RESINOUS MATERIALS
ANO LOSS 0.044
PATCH FRACTIONATING TOWERS
©
ORTIIO-OICHLOROBENZEIIE COLUHI WASTE
CHLOROBENZENE 0.004
01 CHLOROBENZENE 0.0001
lAiid
Figure 3.9 Chlorobenzene Manufacturing Distillation Residues From Batch Fractionating Towers (PRI, 1977)
-------
For every kg of chlorobenzene manufactured, 0,372 kg of HC1 is
generated. Most of the HC1 is collected in water from the scrubber
used to collect waste material from the reactor. Less than 0.002 kg
of HC1 is vented to the atmosphere per kg of chlorobenzene. It is
not known whether the HC1 effluent is recovered for sale or reuse.
Cichlorobenzene sludge from the settling tank is collected and
recovered.
Benzene and water are components of one of four waste streams from
the fractionation tower with 0.038 kg of benzene and water waste
generated per kg of chlorobenzene produced.
Benzene and chlorobenzene from the fractionation tower are generated
at the rate of 0.15 kg per kg of chlorobenzene manufactured.
Chlorobenzene and dichlorobenzene from the fractionation tower are
generated at the rate of 0.18 kg for each kg of chlorobenzene manufac-
tured. The waste stream Is from both the dichlorobenzene and ortho-
dichlorobenzene column. The dichlorobenzene waste stream is deposited
with the water effluent from the plant. Ortho-dichlorobenzene waste
stream is deposited in landfills.
Polychlorinated aromatic resinous materials from the fractionation
towers are generated at the rate of 0.044 kg for each kg of chloroben-
zene produced. Ten percent of the waste stream is chlorobenzene, ap-
proximately 89 percent is composed of polychlorinated aromatic resinous
materials and less than one percent is dichlorobenzene (PRI, 1977).
No information is currently available which discusses the vari-
ability of the manufacturing process. Variation In production methods
used by the different chlorobenzene manufacturers would result in
variability in the waste streams. Variability would probably be ex-
pressed as variation in the orientation of the waste components rather
than variations in the components themselves.
Chlorobenzene distillation residue is considered a hazardous
waste because of the volatile nature of the polychlorinated aromatic
material in the residue (A. D. Little, 1973). Chlorobenzene, itself,
3-55
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is ignitable with a flash point of 28°C. In Dangerous Properties of
Industrial Materials. chlorobenzene is viewed by Sax as being mildly
toxic, with inhalation toxicity ratings of acute locaJ , 1; acute
systemic, 2; chronic local, 2; chronic systemic, 2.
3.A.2 Treatment Alternatives
3.^.2.1 Current Prac tices
Landfill disposal predominates in the industry. There is no
currently practiced treatment technology being used for chlorobenzene
distillation residues (Sax, 1975). There are isolated instances of
incineration of chlorobenzene wastes which are discussed as the best
available technology (Diamond Shamrock, Inc., personal communication,
1979) .
3.A.2.2 Best Available Technology
The best available treatment for chlorobenzene distillation
residue is incineration (Sax, 1975). Incineration can be practiced
both on-site and off-site. Incinerators used for distillation residue
are the rotary kiln type and can be equipped for hydrochloric acid and
energy recovery. Rotary kilns burning chlorinated hydrocarbons have
a specially constructed boiler and are not preheated because of poten-
tial corrosion problems. Controlled incineration of chlorinated hydro-
carbons converts all chlorine to HC1. Rotary kiln incinerators are
generally adapted with a wet gas scrubber system to control air emissions.
Incineration 'has the advantage of efficiently reducing the volume
of waste to be disposed and reduces the toxicity of waste by oxidation.
Depending on the employment of a EC1 recovery unit or energy recovery
process, the system has a high energy demand. (The controlled incin-
eration of chlorinated hydrocarbons is achieved by high temperature,
high water content and low oxygen, yielding a high concentration of
HC1.) (Eden, 1978). HC1 recovery is possible if the incinerator only
bums chlorinated wastes. However, rotary kilns operate most effectively
on a continuous feed system, and would have to handle more than the chlo-
rinated distillation residue from a typical manufacturing facility.
3-56
-------
A facility recovering HC1 from incinerating chlorobenzene dis-
tillation residue has not been found, although the method is practiced
in the plastics industry and appears applicable to this waste stream.
HC1 recovery is accomplished by controlled combustion, i.e., the gases
are caught in the scrubber and recovered from the scrubbing and quench
tower. Landfilling of ash residue can be performed either on- or off-site.
Energy can be recovered from the incinerator in the form of steam
or heat regardless of the type of waste incinerated. Energy from the
burning of chlorinated waste can be recovered by taking gases discharged
from the oxidation chamber to generate steam in a waste heat boiler.
3.4.2.3 Most Environmentally Sounu Technology
Chlorinolysis has been used for other similar waste streams as an
effective treatment for chlorinated pesticide wastes, such as DDT and
2,3,5,T (trichlorophynoxy acetate acid) (Landreth and Sogers, 1974).
Chlorinolysis has been used to convert chlorinated hydrocarbon wastes
to soluble products, mainly carbon tetrachloride (CCl^). Waste chlori-
nated hydrocarbons and chlorine are placed in a nickel-stainless steel
reactor and under controlled temperature and pressure are converted to
CCl^. By-products are formed depending on the chemical composition of
the waste stream. Reactor conditions are either high pressure and low
temperature, or high temperature and low pressure. Stoichiometrically,
four to eight chlorines are added for each carbon molecule. At 500°C and
200 atm of pressure in the presence of excess chlorine, the chlorine-
hydrocarbon bonds are broken and carbon is recombined with chlorine form-
ing CCl^ (A. D. Little, 1976). If hydrogen is present in the waste, as in
the case of chlprobenzene distillation residue, then HC1 is formed. If
oxygen is present in the waste, carbonyl chloride is formed as a by-
product .
The behavior of hexachlorobenzene, DDT and 2,4,5-T under chlori-
nolysis have been studied extensively. The reaction sequence for each
of these is listed below:
3-57
-------
Hexaehlorobenzene CI.
:i + ci
ci
Behavior of chlorobenzene in chlorinolysis is postulated below:
ci
Ql +ci2	> cci4 + HCl
Currently, there are several chlorinolysis facilities in operation.
Chlorinolysis is discussed as an on-site treatment, since many facilities
are operated by organic chemical manufacturers. Diamond Shamrock both
manufactureschlorobenzenes and operates a chlorinolysis facility. They
have, however, never tried to convert chlorobenzene distillation residue.
In the early 1970's, Diamond Shamrock conducted a pilot study on con-
verting hexaehlorobenzene distillation residue. They found that the
residue contained 80 percent hexachlorobutadiene and 20 percent hexa-
ehlorobenzene. Upon chlorinolysis, 95 percent of the hexachlorobuta-
diene was converted, but the hexaehlorobenzene fraction was not effi-
ciently converted. The kinetics of the hexaehlorobenzene reaction were
such that conversion was too slow to consider incorporation into that
plant process (Diamond Shamrock, personal communication, 1979).
It is not known whether these results indicate the possible
behavior of chlorobenzene distillation residue in chlorinolysis. The
polychlorinated resinous material of the distillation residue could
interfere with effective chlorinolysis.
A primary purpose of chlorinolysis has been to detoxify pesticide
wastes, but a major disadvantage to this method of treatment is that
sulfur in concentrations of 20 ppm or greater will poison catalysts in
the reaction system. For this reason, wastes cannot contain sulfur
compounds.
3-58
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Success of chlorinolysis as a waste treatment method is critically
dependent on the salability of CCl^. Currently, CCl^ appears to be
marketable, making chlorinolysis a cost-effective treatment alternative.
Eighty-five percent of the CCl^ manufactured is used for the manufacture
of Freon. There are several operating chlorinolysis facilities: Diamond
Shamrock has a 5 ton/day reactor; Hoechst-Uhde has a 10 kg/hr reactor
and is planning a 50,000 ton/year facility. Diamond Shamrock focuses on
the chlorinolysis of aromatics while Hoechst-Uhde works mainly with ali-
phatic compounds and operates at 400°C lower temperature than the Diamond
facility.
All of the treatment alternatives discussed in this section apply to
on-site as well as off-site treatment, although no reference was found
for a facility using off-site treatment.
3.A.3 Storage Alternatives
No reference was found for storage of chlorobenzene distillation
sludge.
3.4.4	Disposal Alternatives
landfills are the current method used for handling polychlorinated
resinous material from chlorobenzene distillation towers. Landfills are
the prevalent method for disposal of distillation sludge. There is no
evidence to suggest that any special handling of the waste at the land-
fill is used (Diamond Shamrock, personal communication, 1979).
3.4.5	Other Environmental Pollution Control Problems
TVo major environmental burdens are associated with the incineration
of chlorobenzene distillation residue: air pollution problems and
the disposal of Incinerator residues. To meet both federal and state
environmental regulations, air pollution control devices must be used
with incineration. Rotary kilns most commonly use gas and wet scrub-
bers to control air emissions. Incineration of chlorobenzenes causes
some problems in that the HCl formed is highly corrosive to a rotary
3-59
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kiln and attention must be focused on the design and strength of the
equipment. Ash residue disposal causes a second environmental burden.
Ash residue from all the wastes incinerated are generally sent to a
landfill for disposal.
Chlorinolysis has not been used on this waste stream, therefore
any environmental problems associated with chlorinolysis treatment of
polychlorinated resinous material wastes have not been documented.
3.4.6 Engineering. Cost and Environmental Evaluation of Incineration
Techniques and Chlorinolysis as Applied to Chlorobenzene Dis-
tillation Sludge
The following equipment is required for incineration of chloro-
benzene distillation residue.
•	auto-cycle feeding system:
-	feed chopper
-	pneumatic feeder
-	slide grates
•	rotating cylinder
•	ash burner
•	auto burner
•	scrubber system
•	exhaust fan
•	stack
•	fly ash sludge collector
•	after burner chamber
•	pre-cooler
Incineration of chlorobenzene distillation is a feasible treat-
ment technique. Industry is currently using this method of treatment
and it is, therefore, judged to be acceptable to them.
Recovery of HC1 in conjunction with incineration would require the
use of the following additional equipment:
•	quench tank
•	wet scrubber to remove effluent
3-60
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Recovery of HC1 is a feasible, veil-demonstrated process. It is
not known if HC1 recovery has been tried during incineration of chloro-
benzene distillation residue nor whether industry would accept this
additional control. If the incinerator is used only to burn chlorinated
waste, it appears likely that HC1 recovery would be widely accepted.
Lack of detailed Information makes an engineering evaluation of
chlorinolysis speculative.
The cost of landfilling chlorobenzene distillation residue at a
sanitary landfill $17.00/kkg, while the cost for using a chemical
landfill is $77.Q0/kkg (Diamond Shamrock, personal communication, 1979).
Cost evaluation for incineration of chlorobenzene distillation
residues is based on 1977 data for a 1,400 kkg waste stream of residue
per year. The incinerator has a 195 kg/hr capacity:
This capital annual cost works out to $0.97 per kkg of waste
(Diamond Shamrock, personal communication, 1979).
Costs for incineration with HC1 recovery would be the same as those
cited above excepted for additional costs for the quench tank.
No cost information was found for chlorinolysis.
Table 3.6 compares estimated emissions of chlorobenzene in dis-
tillation residue with MATE values. Environmental release factors for
incineration of chlorobenzene distillation residue are given for
emissions to air, water and land. Emissions from the incinerator to
the atmosphere are expected, even though scrubbers used with the rotary
kiln meet current air pollution standards. Emissions are mostly parti-
culates and HC1. Emissions to air were estimated based on 99.9 percent
$205,000
$ 49,200
$ 5,000
$ 8,200
$ 73,000
Installed capital cost
Depreciation value/year
Utility cost/year
Maintenance/year
Labor/year
$135,400
Total annual cost
3-61
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Table 3.6 Chlorobenzene In Distillation Residue
Estimated Emissions
Current Practice Best Available Transfer of Technology


Landfill
Incineration
with HCL
recovery, land
disposal of
residue
Chlorinolysis
Media
MATE VALUES



Air,
mg/m'
Health 350
Medium


Ecology
N.G.
(<350)
0.001
Not Known
Viater,
Health 5.300
>100
<5,300


rag/1
Ecology
100
<100
Practically Zero
Land,
Health 11.000



"b/b
Ecology
0.2
>11,000
<0.2
Practically Zero
-------
combustion efficiency, 99.8 percent scrubber efficiency and 40 percent
excess air.
As residue is the only other environmental problem associated with
incineration, and the ash material is disposed in landfills. There
would be relatively little hazard associated with the ash from incin-
eration of polychlorinated resinous material, and it does not represent
a great danger to surface and ground water. Scrubber effluent is sent
for neutralization prior to disposal in the POTW. With pretreatment
the environmental burden is lessened. Baissions to air from landfill
are based on a vapor pressure of 10 ran Hg at 22°C for chlorobenzene.
Emissions to water and land were based primarily on solubility of
chlorobenzene, which is 49 mg/100 ml of water at 20°C. References for
environmental releases of hazardous substances to the environment due
to chlorinolysis were not found. Such releases are expected to be
quite small.
In stannary, the currently practiced method for disposal of poly-
chlorinated resinous material, landfill, may not be environmentally
acceptable due to such things as toxicity, solubility and mobility in
a landfill environment. Incineration, with or without HC1 recovery,
is a recommended means of disposing of this waste stream. Recovery
of HC1 or energy coupled with incineration helps offset costs making
the technique more acceptable to industry. Chlorinolysis converts
the waste stream to a salable product, increasing its acceptability.
Chlorinolysis has not been tested for polychlorinated resinous material,
as most of the studies have been for toxic substances such as DDT,
Agent Orange and other materials that are difficult to dispose. Since
chlorinolysis facilities are currently in use, we recommend that
chlorinolysis be examined as a means for treating chlorobenzene dis-
tillation residue.
3-63
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3.5 HEAVY END WASTES FROM NITROBENZENE COLUMN BOTTOMS
The SIC code for nitrobenzene is found in 2865 (SIC, 1972).
3.5.1 Manufacturing and Waste Stream Characterization
Nitrobenzene is an organic intermediate from aniline. Annual pro-
duction, by seven manufacturers, amounts to 140,000 metric tons (1978).
Nitrobenzene is manufactured by introducing benzene into a reaction ves-
sel, followed by mixed acid. Mixed acid is approximately 55 percent
sulfuric acid (H^SO^,), 35 percent nitric acid (HNO^) and about 10 per-
cent water. Reaction occurs at a temperature of 45° to 95°C. The mix-
ture is separated into an upper phase (nitrobenzene) and lower phase
(spent acid) in a liquid contacting vessel. Nitrobenzene is then
purified by distillation. Figure 3.10 diagrams the manufacture of nitro-
benzene (PRI, 1977).
There are no by-products in the manufacture of nitrobenzene. Segre-
gatable waste streams include the following:
•	spent acid
•	washer wastes
•	column wastes
Spent acid from the reactor is captured from the liquid-liquid
separator and sent to a sulfuric acid concentrator for recovery. Re-
covered acid is reused in the manufacturing process. From the flow
diagram, we have assumed that all of the nitric acid is used in the
reaction and none is discharged in the waste stream.
Washer wastes from the washing step preceding the column wastes
consist of approximately 0.00004 kg of nitrobenzene for each kg of
nitrobenzene manufactured and 0.025 kg of sodium sulfate/carbonate
350 tons total (Na2S0A/H2C03) (PRI, 1977). This effluent is dis-
charged with other aquatic effluents for primary treatment and disposal
in POTW.
3-64
-------
BASIS: I KG NITROBEHKHE
SULFURIC AC
O.OIS "
NITRIC ACID
O.S1
WATER
0.109
SPENT ACID
TO RECOVERY
0.706
SULFURIC ACID
AaSORBM
REACTOR	SULFURIC ACID LiqUIOAIQUlD
CONCENTRATOR SEPARATOR
Figure 3*10 Nitrobenzene Manufacture (EPA, 1977b)
OIIUTE SOOIUH
CARBONATE 0.010
HASHER WASTES
MTR08ENIENE
X"
Y.
0
CO.UMI HASTES
©
ABSORBER VENT
BENZENE 0.008)
110	0.00009
UllROBEilZEHE .'III
\
AIR
©
ACID CONCENTRATOR-VENT
HO* O.UOOIS
\
AIR
©
HASHED WASTES
HITROBE.IUNE 0.0000*
N<2S04/H2C0, 0.02S
~
WATER
©
COllMI HASTES
HEAVY EIIOS O.OOZS
I
IANB
HASHERS
NITROBENZENE
COIUHI
-------
Column wastes consist of still bottom or heavy ends from the
purification process. Exact composition of these heavy ends Is un-
known, but 0.0025 kg of heavy ends is generated for each kg of nitro-
benzene.
The manufacture of nitrobenzene appears to be a very controlled
process with little room for chemical variability within the process.
No variability is expected In the composition of heavy ends.
Chemical composition of heavy ends from the purification column
is not known, although it can be hypothesized that nitrobenzene, benzene
and various forms of sulfate and nltroso compounds would be present.
Nitrobenzene is a volatile and toxic chemical sith Sax toxicity
ratings of: acute local, u; acute systemic, 3; chronic local, u;
and chronic systemic, 3 (Sax, 1972). On the basis of the chemical
constitutents of the waste stream, this waste stream is categorized
as volatile. The waste is considered highly toxic due to the nitro-
substltuted aromatics expected to be in the heavy ends.
3.5.2 Treatment Alternatives
Treatment of nitrobenzene heavy ends is not currently practiced
either on-site or off-site.
The best available treatment for heavy ends is incineration. In-
cineration, either performed by itself or in association with heat
recovery, is most commonly carried out in rotary kiln Incinerators with
scrubbers to capture the NO^ emissions. Because of large amounts of
nitrogen in the waste stream, there is a large potential for heat re-
covery. For every kg of nitrobenzene heavy ends incinerated, 5,990
kcal of energy can be recovered (PR1, 1977). At a facility producing
20,000 kkg of nitrobenzene, 200 million kcal of heat can be recovered
(PRI, 1977). At a facility producing 20,000 kkg of nitrobenzene, 200
million k>cal of heat can be recovered annually. Heat, or energy, can
be recovered as steam for reuse.
3-66
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A three step procedure involving steam distillation and alkali
hydrolysis, followed by catalytic reduction, has been suggested as a
means of treating nitrobenzene heavy ends. This stripping procedure
is outlined in Figure 3.11 (PRI, 1977). Steam distillation of the
heavy ends will strip off any nitrobenzene present. Nitrobenzene stripped
off in the distillation step will reenter the processing line. Column
bottoms are presumed to contain m-, o-, and p-dinitrobenzene. The
m-dinitrobenzene is separated from the other isomers by adding a 5 to 10
percent caustic solution at 90-100°C. Ortho and para isomers are con-
verted to the corresponding nitrophenols and removed as soluble salts.
These alkali salts and the alkaline solution are disposed in a landfill,
in lined drums. m-Dinitrobenzene is a salable product and can be sold
at this point or reduced in a catalytic reactor to produce m-nitro-
aniline or m-phenylenediamine. Aqueous phenylenediamine can be used
in this form for dye preparation or can be further purified by distilla-
tion.
No Indication was found of the percentage of treatment practiced
on-site versus off-site for this waste stream.
3.5.3	Storage Alternatives
No alternatives were found for storage of nitrobenzene purification
column heavy ends. It can be assumed that storage in steel drums is
used for low volume wastes until a truck load is accumulated. This
storage procedure is adequate for short-term storage, but not for long-
term.
3.5.4	Current Disposal
The current method for disposal of nitrobenzene heavy ends is to
bury them in a secured landfill in sealed steel drums (PRI, 1977).
Three hundred fifty tons of heavy ends are disposed in this manner
annually. Landfill sites can be located either on-or off-site, although
no indication of an actual split was found.
3-67
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u>
I
00
NITROBENZENE
RECYCLE TO NITROBENZENE PRODUCTION
SKKg/TR
NITROBENZENE
COLUMN WASTE
101
CAUSTIC
SOL'N
4KKg
n«oh/tr
50	—
10.3 KKg/YR
0, P-NITR0P1IEN0LS
STEAM
TO LANDFILL
45 KKg/YR
HAINLT M-1I1NTR0BEHZENE
SOME O-DINITROBENZENB 	
AND TRACE TRINITROBENZENE
| FB/IICL
AO KKg/TR H-DINITROBENZENE
ALTERNATE
	I
40 lUCg/YR
H-DINITROBENZENE
TREATMENT
I H-PHENYLENEDIAHIHE
FLAKES TO DRUMS
(FOR SALE)
FLAKER
CONDENSER
NEUTRAL-
IZATION
Figure 3.11 Nitrobenzene Stripping of Heavy Ends from Purification Column in Nitrobenzene Manufacture
-------
3.5.5 Other Environmental Pollution Controls
There are three environmental burdens associated with use of incin-
eration as a treatment alternative: air emissions, scrubber effluent
and landfill of ash residue. Air emissions from the Incineration of
nitro-aromatic compounds are high in NO^. To reduce these emissions,
wet scrubbers are used to collect the NO^. The second problem is dis-
posing of the scrubber effluent which, commonly, goes through pretreat-
ment at the site and is then disposed with other aquatic effluents into
the POTW. Ash residue from incineration is disposed in landfills located
either orror off-site. Energy recovery is not thought to be widespread
among facilities incinerating nitrobenzene column bottoms.
The only environmental burden from nitrobenzene stripping is the
disposal of the nitrophenols in a landfill. Approximately 73.5 kkg of
nitrophenols would have to be landfilled annually if nitrobenzene strip-
ping was universally practiced in industry, and a primary concern is
potential leakage of nitrophenols from drums. Nitrobenzene stripping
was the most environmentally sound treatment technology found for
nitrobenzene column bottoms. Phenols provide a special hazard to
ground water because of the difficulty in removal by treatment and their
low waste threshold.
3.5.6 Engineering, Cost and Environmental Evaluation of Acceptable
Alternatives for Nitrobenzene Column Bottoms
Equipment required and costs for incineration of nitrobenzene
column bottoms are the same as those for chlorobenzene distillation
residues given in Section 3.4.6. The amount of waste is too small
to consider separate incineration equipment for nitrobenzene heavy
ends.
Equipment requirements for nitrobenzene stripping are as follows:
•	holding tank
•	holding tank pump
•	steam stripper
•	stripper condenser
3-69
-------
•	decanter
•	caustic treat tank
•	decanter/condenser pump
•	stripper bottoms pump
•	treat tank waste pump
•	flaker.
Nitrobenzene stripping is a fairly simple chemical system. It is
not known how readily industry would accept this treatment alternative,
and the costs might diminish their interest. Nitrobenzene heavy ends do
not represent a high volume waste stream. Costs associated with nitro-
benzene stripping are given in Table 3.7.
Incineration of nitrobenzene heavy ends would have some environmental
impact. Although air pollution control devices are used, there are still
some NO^ emissions to the atmosphere from heavy ends incineration.
Effluent water from the scrubber is sometimes discharged to a holding
pond prior to pretreatment. In ponds, toxic substances can be leached
to both surface water and ground water. Table 3.8 compares estimated
emissions of nitrobenzene in column bottoms with their MATE values.
For nitrobenzene stripping, landfill of the alkaline nitrophenol
solution represents the only significant impact on the environment.
Landfill in steel drums is regarded as a relatively safe method for
disposal of hazardous waste. Use of lined drums or encapsulation
in more durable containers would be preferred. Environmentally,
nitrobenzene stripping is a more acceptable treatment, highlighted by
recovery of a valuable waste stream component and the volume reduc-
tion of the waste stream prior to disposal.
In summary, Incineration is more acceptable treatment at the
present time because of existing facilities and industrial acceptance.
Nitrobenzene stripping may ibe a more environmentally acceptable treat-
ment alternative but will require further testing and investigation
before it can be fully evaluated and successfully implemented.
3-70
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Table 3.7 Costs Associated with Stripping of Nitrobenzene Wastes
1. Estimated Installed Capital Cost
Basis: 0.167 kkg/day of nitrobenzene column
Equipment Item
Hold Tank, 760 L
Hold Tank Pump, 8 LIm
Steam Stripper, 50 cm dia x 4.5 mH
Stripper Condenser, 160 -£/m
Decanter, 560 t
Caustic Treat Tank, 760 L
Treat Tank Pump, 40 t/m
Decanter/Condenser Pump, 20 1/m
Stripper Btms Pump, 40 LIm
Treat Tank Waste Pump, 40 £/m
Flaker
Subtotal
Engineering at 10 percent
Contingency including freight at 20 percent
Total Estimated Installed Capital Cost
waste
Estimated Cost
$38,750
3,200
44,100
7,400
7,300
38,750
3,360
3,210
3,360
3,360
8,760
$161,600
16,200
32,400
$210,200
3-71
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Table 3.7 Costs Associated with Stripping of Nitrobenzene Wastes
(Continued)
2.	Annual Fixed Charges
Depreciation $210,200 @ 10%/year	$21,000
Interest $210,200 @ 10%/year	21,000
Insurance
and Taxes $210,200 @ 4%/year	8,400
Total Annual Fixed Charges	$50,400
3.	Direct Operating Cost
Raw Material -
50% NaOH 4 kkg @ $160 =	$640
Utilities	1,800
Maintenance - 0.04 x $210,200 =	8,400
Direct Labor -
4,200 MH x $9.00 x 1.5 -	56,700
Annual Direct Operating Cost	$67,540
Annual Disposal Cost	2,500
Total Annual Cost	$120,440
Recovered Materials -
m-Dinitrobenzene 40 kkg @ $790 x 0.7 »	$22,120
Nitrobenzene 5 kkg @ $510 x 0.7 ¦	1,780
-23,900
Net Total Annual Cost	$96,540
4.	Cost Per kkg Product - $96,540 + 20,000 °	$4.83
5.	Cost Per kkg Waste - $96,540 ¦* 50 =	$1,930
6.	Impact on Product Cost
(Market value of 1 kkg product a $510)
Cost/kkg •? Market Value = $4.83 -t $510	0.95%
3-72
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Table 3,8 Nitrobenzenes in Column Bottoms
Estimated Emissions
Current Practice Bnst Available Transfer of Technology
Media
MATE VALUES
Disposal in sealed
steel drums in
secure landfill.
Rotary kiln
incineration
with NO con-
trol ancf heat
recovery.
Land disposal
of residue.
Steam distillation,
alkali hydrolysis
followed by catalytic
reduction. Disposal
of nitrophenols in
landfill.
Air,
mg/m^
Health 5.0
<5.0
<5.0
<5.0
Ecology
N.G.
Water,
Health 75

> 1.0
<75
<1.0
tng/1
Ecology
1.0
<1.0
Land,
Health 150

<2.0
<2.0
ug/g
Ecology
2.0
<2.0
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3.6 DAT FLOAT FROM PETROLEUM REFINING INDUSTRY
As defined by the Standard Industrial Classification (SIC 2911),
a petroleum refinery is a complex combination of interdependent opera-
tions engaged in converting crude oil into more than 2500 products
including liquefied petroleum gas (LPG), gasoline, kerosene, aviation
fuel, diesel fuel, a variety of fuel oils, lubricating oils, asphalts
and cokes, and feedstocks for the petrochemical industry.
3.6.1 Industry Description
Crude oil is the major raw material processed in a refinery. The
chemical composition of crude oil varies widely depending on its source.
It is largely a mixture of paraffinic, naphthenic, and aromatic hydro-
carbons containing varying amounts of sulfur, nitrogen, oxygen and
inorganic ash. However, over 3,000 different chemical compounds may also
be present. The chemical composition of the crude oil being processed
will partially determine the product slate from a particular refinery.
For example, a paraffinic crude oil will tend to produce better lube oil
stocks than a naphthenic crude oil and is thus the favored feedstock for
that product.
As of 1 January 1979, the processing capacity of the United States
petroleum refining industry was 2.73 million cubic meters (17,169,909
barrels) per day. According to the Oil and Gas Journal, (1979) the
petroleum refining industry has been expanding at the rate of about four
percent a year. Table 3.9 presents historical data on the growth of
the U.S. petroleum refining industry. Future growth rates may depend
largely on the Federal government policy on importing crude oil versus
importing refined products.
One trend in this industry is increasing dependence on imported
crude oils. In 1971 only about 270,000 cubic meters (1.7 million barrels)
per day of imported crude were consumed (Dickerman et al., 1977) while in
1978 over 1,290,000 cubic meters per day (8.1 million barrels per day)
were used (Geotimes, 1979). Foreign crude accounts for nearly half of
all oil refined in the U.S.
As of 1 January 1979, 153 companies comprised the U.S. petroleum
refining industry. These companies operated 289 refineries in 41 states
3-74
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Table 3.9 Crude Oil Processing Capacity of U.S. Refineries
Capacity Per Calendar Day
Year*
1967
1968
1969
1970
1971
1972
1973
1974
1975
1976
1977
1978
1979
hnf
1.662
1.771
1.832
1.932
2.016
2.081
2.128
2.260
2.360
2.397
N.G.
2.678
2.730
Thousands
of Barrels
10452
11142
11523
12155
12681
13087
13383
14216
14845
15075
N.G.
16846
17170
Growth Over
the previous
year
(Percent)
6.6
3.4
5.5
4.3
3.2
2.3
6.2
4.4
1.5
N.G.
N.G.
1.9
*As of January 1 of the year indicated
N.G. = Not Given
Source: Oil and Gas Journal, Annual Refining Issues
3-75
-------
with most of the refining capacity found near the coasts. There is
considerable variation in the size of refineries, and their production
rates range from 500 cubic meters per day to more than 64,000 cubic
meters per day (Oil and Gas Journal. 1979). Approximately one third of
U.S. refineries capacities of less than 1,600 cubic meters per day
(10,000 bb/day). These refineries represent only 2.5 percent of total
industry capacity. Refineries capacities greater than 24,000 cubic
meters per day (151,000 bb/day) represent about 9 percent of U.S. refin-
eries and account for 43 percent of total industry capacity. Total
annual employment of the industry in 1974 numbered approximately 140,000,
and total industry-wide sales were $28.9 million (Statistical Abstracts,
1979). Texas has the greatest concentration of refineries, with a total
of 54 facilities representing 18.7 percent of the national total. Calif-
ornia has 39 refineries and Louisiana, Illinois, Kansas, Oklahoma, Penn-
sylvania and Wyoming each have- 10 or more (according to the Oil and Gas
Journal 1979). Refining capacity of individual states roughly parallels
the number of facilities. Sixty-four percent of all U.S. refineries, or
a total of 158 refineries, were constructed between the years 1944 and
1970 (Rosenberg et al., 1976).
3.6.2 Manufacturing Processes
Processes involved in the manufacture of refined petroleum products
involve distillation, absorption, extraction, thermal and catalytic crack-
ing, isomerization and polymerization. Figure 3.12 is a flow diagram il-
lustrating the sequence in which these processes interact to produce re-
fined products. Few refineries, if any, employ all of these processes,
and some processes are designed for a particular crude oil. Larger refiner-
ies use most of the processes shown. American refineries usually use
more processes than foreign refineries, since they concentrate on gaso-
line production, while European refineries generally concentrate on
production of heating fuels which are more easily produced than gasoline.
Complex American refineries generally produce a minimum of residual oil.
Fuel oil for the U.S. East Coast comes predominantly from Caribbean
refineries with minimum facilities for gasoline production.
Approximately 2,500 products are produced wholly or in part from
3-76
-------
wit it* niHuwm tmii in mwinr
U3
I
•""J
I -rnt-zW
m few ritnw.ii

i.m w/*•!
| «¦"" ¦¦¦ IW
' MCUIIU «¦!
» t o>l*y
II I >*/<«|
I mill1 tuife*
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IU bui*r
Mnj-
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UCrl IM .
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a k«f4«f
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«.«»« •*#*»!

ULtlk
1,111 »Vl4l
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urvtl
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uai» «i
UM 0M • III IN
mcu* « l» >V*'i
8 W B'/*f
cetd • llt.M
Figure 3.12 Representative Flow Diagram for a U.S. Refinery (Bombaugh et al.,1976)
-------
petroleum. Most of these products are blends of several refinery
streams. Table 3.10 lists the major petroleum products and their pro-
duction in 1974.
Refinery products vary widely with location, climate, and season.
In winter, there is higher demand for heating fuel oils. Winter gasoline
also must contain a higher percentage of volatile products to enhance
cold weather starts. Summer weather requires reduction in volatile
components to decrease chances of carburetor vapor lock and to minimize
evaporation losses.
The petroleum refining industry also provides raw materials for
the petrochemical industry. Petrochemical feedstocks supplied by re-
fineries include olefins, LPG» and aromatic compounds. In addition,
naphtha is cracked in .a thermal cracking process to produce ethylene.
Ethylene production is performed in both refineries and petrochemical
plants. Petrochemical feedstocks accounted for only about two percent
of the refining industry's production in 1973 (Dickerson et al., 1977).
As the size of a refinery increases, so does the number of products
produced, and the processing operation becomes more flexible. The pro-
duction rate of each product can be varied significantly with relatively
minor changes in refinery processing conditions. Hydrocarbon fractions
can be shifted from one product to another to meet product demands.
Many refineries have crude capacities of less than 800 cubic meters
(5,000 barrels) per day. Economic operation of these small refineries
is possible only through production of specialty items, lube oils, or
asphalts.
The major trend in the industry is the increase in production of
gasolines, especially non-leaded, high-octane gasolines. Expansion of
processing units that produce high-octane blending stocks, such as
catalytic reforming units, can also be anticipated to meet this growing
demand.
3.6.3 Petroleum Refining Waste Stream Characterization
The petroleum refining industry produces gaseous, solid, and liquid
wastes. Air emissions make up by far the largest potential source of
3-78
-------
Table 3.10 Major Petroleum Products Produced By U.S. Refineries in 1974
(Bombaugh et al., 1976)
Product
Gasoline
Kerosene
Jet Fuel,
Naphtha type
Kerosene type
Distillate Fuel Oil
Asphalt
Residual Fuel Oil
Marketable Coke
LPG
Petrochemical Feedstocks
Other (Fuels, misc.)
Volume Percent of Total
Refinery Products*
49.0
1.2
1.5
4.9
20.4
3.4
8.2
1.3
2.4
2.8
4.9
*Based on total U.S. production
-------
contamination from the industry. The major gaseous wastes emitted are
particulates, hydrocarbons, carbon monoxide, sulfur oxides, and nitro-
gen oxides.
The major liquid effluents are oil and grease in condensed steam
from various processes, cooling water from various processes, tank
cleaning wastes, spent chemicals, waste caustics containing cresylic
acids and sulfides from gas treating, oil spills and lead waste.
Solid wastes include fines from cracking units, coke fines,
iron sulfide, clay filtering media, and sludges from tank cleaning
operations, oil-water separators, and biological processes. Spent
catalysts not worth processing for recovery of valuable components are
an intermittent solid waste stream. Typical components of waste cata-
lyst streams are aluminum, cobalt, nickel and titanium compounds.
3.6.A Treatment Alternatives
Treatment and disposal methods used by the industry are contingent
upon the nature, concentration, and quantities of waste generated. They
are further affected by geographic conditions, transportation distances,
disposal site hydrogeologic characteristics, and regulatory agency re-
quirements.
One of the primary references consulted for this section was a
study conducted for the EPA Office of Solid Waste in 1974 titled
"Assessment of Hazardous Waste Practices in the Petroleum Refining
Industry" (Rosenberg et al., 1976). The study included a survey of
16 refineries representing 18 percent of U.S. crude capacity. The
survey included visits to refineries and sampling and analyses of
wastes.
Another major reference is a study conducted for the American
Petroleum Institute titled "The 1976 API Refinery Solid Waste Survey"
(API, 1978). This was a survey of 78 refineries representing 57 per-
cent of the U.S. crude refining capacity. Information was received on
28 air flotation units in the industry while analytical data on 18 units
were tabulated. Some comparisons of the API study and the EPA study
3-80
-------
show higher amounts of oil and solids in air flotation units, and
varying metals content as shown in the following in metric tons per
year:

API Study
EPA Study
Oil
12,000
9,000
Solids
28,000
11,000
Oil & Solids
40,000
20,000
Arsenic
0.001
0.1
Cadmium
0.02
0.0003
Chromium
5.32
8.4
Copper
0.43
0.4
Lead
0.23
0.5
Mercury
0.003
0.03
Nickel
0.17
0.001
Selenium
0.003
0.1
Vanadium
0.13
0.003
Zinc
5.88
6.3
Total Metals
12.2
15.8
Same of the differences are explained as follows:
• Many refineries added air flotation systems in the
period 1974-1976 adding oil and solids to the
waste stream,
e Different data bases were used to derive this
information.
The differences in the two studies are not great enough to sub-
stantially change this discussion of DAT float. If the API study were
used as a major reference, an even greater emphasis would be placed on
petroleum rerefining as best available technology, due to the increase
in oil content of the waste and the increase in crude oil prices since
the study was written.
3-81
-------
3 .6.4.1 Current Practices
The technology of treating refinery wastewater streams is well
established. Basic water cleanup processes commonly found in refineries
are oil/water separation, sour water stripping, suspended solid sedimen-
tation, acid base neutralization and biological oxidation. Although
many compounds are present in the liquid effluent from refinery pro-
cesses , they are generally eliminated or reduced to an acceptable level
before the water is discharged from the refinery.
Solid wastes from petroleum refineries are generally landfilled or
incinerated. Spent catalysts are usually disposed in landfills.
In 1973, 51 percent of petroleum refinery wastes were disposed in
landfills, 40 percent by lagooning, 7 percent by land spreading and
1 percent by incineration. Approximately 44 percent of refinery wastes
were managed on-site, and 56 percent were hauled by private contractors
to off-site disposal locations. Of refinery wastes handled on-site,
38 percent were disposed of by landfilling, 41 percent by lagooning,
and the remainder by landspreading and incineration (Rosenberg et al.,
1976). Table 3.11 compares waste disposal methods used in 1973 with
those projected for 1983. This table illustrates two trends expected
for the industry	a move to more on-site disposal and much greater
emphasis on landspreading at the expense of lagooning. Table 3.12
shows generation rates and distribution of 17 categories of solid and
liquid wastes produced by the industry in 1974. Many of these waste
streams are especially hazardous because ignitable, volatile, and reac-
tive chemical mixtures have been concentrated in them.
Figure 3.13 shows a relatively complex system for handling waste-
water streams. Unit operations involved vary from refinery to refinery
depending on local requirements. All refineries can be expected to
have an API separator to separate oil and soluble solids from effluent.
Dissolved air flocculators (DATs) are more compact than API separators
and are becoming commonplace. Many newly designed DAT units have been
installed in the past few years. Biological oxidation units are less .
common and there are only one or two activated carbon bio-oxidation
3-82
-------
Table 3.11 Comparison of Refinery Waste Disposal Methodologies Used in 1973 With Those Projected for 1983
(Rosenberg et al., 1976)
Disposal Procedure
Landfilling
Lagoonlng
/
Incineration
Landspreading
Total
Onslte
(%)
16.8
18.3
0.8
8.4
44.3
1973
Of fsite
(%)
34.3
21.4
0
_0	
55.7
Total
<%>
51.1
39.7
0.8
8.4
100.0
Onsite
<%>
24
12
3
34
1983
Offsite
(%)
20
7
0
0
73
27
Total
(%)
44
19
3
34	
100.0
Net
Change
(%)
-7
-21
+2
+26
Net Change
+29
-29
-------
Table 3.12 Generation Rates and Volume Distribution of 17 Waste Streams
From the Petroleum Refining Industry
Waste Stress
Generation Bate
(Uee Weight)
Met Tons/Year/
1000 BPSL *
Percent
Of Total
Waste
Generation
Generation Bate
(Dry Weight)
Met Tons/Y
-------
ntcovtoto
OIL.
bTOf-Att-e.
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-------
units presently in service. The maximum rate through these wastewater
systems is limited by the capacity of the biological oxidation and air
flotation units.
DAF skimmings present a special problem to the industry because
they contain a number of highly volatile, ignitable, and reactive chemi-
cals or mixtures in varying quantities. A discussion of the hazards
associated with this wastestream follows.
3.6.5 Special Problems Associated with DAF Systems
In a DAF system, air is first dissolved in the wastewater under
2
pressure (2.1 to A.9 kg/cm ). Air bubbles are then released from the
liquid by reducing the pressure to atmospheric level. For smaller
systems the entire flow can be pressurized. For larger systems only a
portion of the effluent is pressurized, and this portion is then mixed
with the unpressurized main stream just prior to entering the flotation
tank.
As air bubbles rise through the wastewater in the system, oils and
insoluble particles are carried upward to the water surface where they
form a dark, oily froth. This float is skimmed off on a continuing
basis and either disposed or returned to the API separator for oil
recovery. Heavier tars and particles settle to form a sludge which is
usually discarded. Wastewater from the DAF system either is sent to
tertiary treatment systems (e.g., carbon a'dsorption) or is discharged
into streams or municipal sewers. Figure 3.14 is a schematic drawing
of a typical DAF system.
Petroleum refineries generate about 66.15 metric tons of DAF
float annually for every thousand barrels of oil refined each day
(Tarnay and Krishnan, 1978). For a typical 32,000 cubic meter (200,000
barrels) per day refinery this amounts to 13,230 metric tons per year.
Assuming that refineries process an average of 14.4 million barrels of
crude oil a day (85 percent of their total capacity as of 1 April 1979),
952,560 metric tons of DAF float will be produced in the United States
this.year.
3-86
-------
Motor & goaf
U)
I
00
Skimmingi hopper
- . . v
-V
Clean-wMJf
dischvg«
CZZN-
Comornied sir
Rotating skimmer blade
r
i
Fiecyctd water
°<4oO°0°0
b o^)
¦ p o
w / Rd00
„«,d.»< ¦-—
pump
Aeration
tanic
Dilrujer
coru /
W\°
° \
Skimmed-oil ¦ P
discharge-
Aerotsd recycle water
Ruing-alr
bubble* with
attochsd oil
I ' " -'"j.	*->"¦ •% «.* *»,
Q-* Flash vatv» (release* bubbles V-
Water
K		
Oo^X) °00°-XD°0U -5}
a
lily-watar IpMueot
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CZK
Figure 3.14 Typical Dissolved Air Flotation System (Ford and Elton, 1977)
-------
The quantity and composition of float produced at each refinery
depends primarily on two factors: the nature of the influent waste-
stream and the operation of the system. Generally, float volume is
0.2 percent to 2.5 percent of the influent volume (American Petroleum
Institute, 1969). DAF system influents usually come directly from API
separators. Table 3.13 summarizes water quality estimates on a typical
API separator effluent. As the concentration of oils and solids in the
DAF system influent wastestream increases, so will the quantity of
float. This observation is supported by Table 3.14. The composition
of the float depends on the waste stream mix of the refinery and thus
on the types of crude, the processes, and the product mix used. These
factors also influence the nature of API separator influents. Conse-
quently, both the quantity and composition of DAF system influents and
effluents are highly variable.
Operating conditions also affect froth generation. Principal
operation variables are:
•	residence time
•	air-to-solids ratio
•	depth of scraping
•	use of chemicals
Residence time in the DAF system for wastewater is generally 10 to
40 minutes. As the residence time increases, more froth is generated per
unit of influent.
The air-to-solids ratio in the system is .generally 0.01 to 0.03.
As the air-to-solids ratio increases so does the amount of solids in
the float, producing a thicker, more dense float. The thickness of the
scum layer will be approximately inversely proportional to the square
root of the air-to-solids ratio (Bratby, 1977).
The depth of scraping is usually 5 mm to 200 mm, but will depend
on the thickness of the scum layer and the adjustability of the DAF
unit. The greater the depth of scraping, the greater both the proportion
of water in the skimmings and the amount of float collected.
3-88
-------
Table 3.1i Water Quality Estimates of Typical Effluents Sent to DAF Systems
From API Separators (Bombaugh, 1976)
EXPECTED CONCENTRATIONS (ppra)
Minimum
Maximum
Average
BOD
COD
Solids
Suspended
Dissolved
Alkalinity
PH
Oil
Phenols
Sulfide
Phosphorus
nh3(n)
1
69
83
14
6.8
3
0.5
0.2
0.5
21
1,180
3 ,080
1,950
15,180
2,620
9.5
870
335
240
6
1,000
413
1,170
480
2,630
600
8.2
140
76
30
3
480
Water is greater than 98 volume percent of the total flow.
*As8umes 85Z efficiency of the API separator which may be a high estimate.
-------
Table 3.
14 Oil Concentrations
and Removal
Efficiencies For 14
DAF Systems





Oil *



Influent
Effluent

Removed
Calculated
Configuration
Chemicals
oil mg/£
oil mifl
% removal
m&/l
of oil in f
Circular
No
170
52
70
118
7
Circular
Yes
125
30
71
95
6
Circular
Tes
100
10
90
90
6
Circular
Yes
133
15
89
118
7
Circular
Yes
94
13
86
81
5
Circular
Yes
1,930
128
93
1,802
t
Circular
Yes
580
68
88
512
32
Rectangular
Yes
105
26
78
79
5
Rectangular
Yes
68
15
75
53
3
Rectangular
Yes
638
60
91
578
36
Rectangular
Yes
153
25
83
128
8
Rectangular
Yes
75
13
82
62
4
Rectangular
Yes
61
15
75
46
3
Rectangular
Yes
360
45
87
315
20
AVERAGE

328
37
83
29 L
11
MINIMUM

61
10
70
46
3
MAXIMUM

1,930
128
93
1,802
t
RANGE

1,869
118
23
1,756
t
**
Source: Ford and Elton, 1977, except as noted
^Calculated by subtracting the oil concentration of the effluent from the oil
concentration of the Influent.
**Calculated from "oil removed" by assuming a float generation rate of 1.5 Z of
float per 100 L of influent and a float density of 1.077.
tValue calculated was over 100 percent which indicates that the float generation
assumption cannot be valid for this case.
3-90
-------
Coagulents such as lime, alum, ferric salts, and polyelectrolytes
are commonly used to improve floe formation. They will increase both
the density and the quantity of float produced.
Depending on these factors, oil and solids removal efficiencies
for DAF systems can range from about 70 to 90 percent. Table 3.14 is a
list of removal efficiencies for 14 DAF systems. Although this data is
insufficient for purposes of statistical inference, it appears that
addition of chemicals does significantly improve removal efficiency.
The system's configuration has little effect.
As research on DAF system operation and chemical flocculants pro-
gresses, the average oil removal efficiency should improve. With this
improvement will come higher scum generation rates. In addition, more
refineries are turning to DAF systems as a means of treating oily waste-
water. These trends clearly point to increasingly larger amounts of
waste DAF float in the future.
3.6.5.1 DAF Float Composition
Table 3.15 gives measured percentages of oil, water, and solids
for eight samples of DAF float. The percentage of oil in this table
supports values calculated for Table 3.14. For the sake of consistency,
values given by Rosenberg et al. and Tamay and Krishnan will be used in
all subsequent calculations requiring float composition estimates.
These values are:
•	82 percent water
•	12.5 percent oil
•	5.5 percent solids
Given these approximations of float composition, the specific gravity
can also be estimated. This is shown in Table 3.16.
Little or no information is available on the composition of the
oil or the concentrations of organic chemicals in DAF float. Concentra-
tions of inorganic constituents, primarily metals, are described in
Section 3.6.5.2.
3-91
-------
3.6.5.2 Potential Hazards of DAT Float
Two components of DAF float that present a significant hazard to
the environment are oils and trace constituents. Based on a DAF float
generation rate of 66.15 metric tons per year per 1,000 barrels refined
per stream day (BPSD), of which 12.5 percent is oil, approximately 8.27
metric tons of DAF scum oil is produced annually for every 1,000 barrels
of oil refined. With a refinery capacity of 17 million BPSD (as of
1 April 1979), the industry could generate up to 40,600 metric tons of
oil this year. Assuming a weight of 7.11 barrels per metric ton (based
on a specific gravity of .8871 for the oil) this amounts to 1 million
barrels per year. By comparison, the 1976 Argo Merchant spill was
178,600 barrels. Admittedly, the industry does not produce at 100 per-
cent of their capacity, but even at the more reasonable estimate of
85 percent capacity, 850,000 barrels would be generated annually. A
typical 200,000 BPSD refinery would have to dispose of 10,000 barrels
of waste oil from their DAF system alone.
It is difficult to judge how hazardous the oils in DAF float are
because of the lack of data on their composition and variability. It
can be assumed that DAF scum is a mixture of light and heavy fractions.
Certainly, some of the oils are volatile and ignitable, and some may
be carcinogenic (see Table 3.2). Little else is known for certain.
Additional studies are needed to focus on this problem, especially in
light of the large quantities indicated.
Substances present in DAF float in trace amounts can present po-
tential hazards despite low concentrations because of ignitable, vola-
tile, and toxic properties. Trace substances include inorganic metallic
compounds as well as solvents and organic compounds.
There is considerably more data on concentrations of metals in DAF
scum than there is on organic compounds. Table 3.17 gives concentrations
of 28 elements found in DAF scum. Using a solids generation rate of
3.64 metric tons per year per 1,000 BPSD, calculations of annual produc-
tion nationwide and at a "typical" (200,000 BPSD) refinery were made.
These values as well as the Minimum Acute Toxicity Effluent (MATE) are
also shown in Table 3.17. Table 3.18 compares generation rates with
3-92
-------
Table 3.13 Percentages of Oil, Water, and Solids In DAF Float
Oil
12.5
16.9
14.4
5.9
2.4
6.1
11.25
10
to
22
Solids
*
*
*
*
*
1.2
2.5
3
to
3.6
Water
*
*
*
*
*
92.7
86.25
75
to
85
Reference
4
4
4
4
4
9
9

9

Refinery
C4
B4
A2
A4
C2
A
B

C

Identification
Code
*Rosenberg et al. do not list specific percentages of solids or water for
the five samples it presents, but average values of 82 percent for water
(range 30 percent to 99 percent) were obtained. An average content value
of 5.5 percent for solids was found by subtraction.
-------
Table 3.16 Calculation of Specific Gravity of DAF Float
Assumptions
OJ
i
VO
•O-
Component
Water
Oil
Solids
Percent of
Composition
82
12.5
5.5
Assumed
Specific
Gravity
1.0000
.8871
2.65
Basis for Assumption
This value ignores dissolved solids.
Consequently, it is a minimum value.
This is the average specific gravity for
crude oil. The true specific gravity for
DAF float oil is probably lower, since
the heavier oil would tend to sink.
This is the average specific gravity for
quartz. This value was assumed in the
absence of additional information because
most of the solids are fine sands and
silts which are commonly quartz.
Component
Water
Oil
Solids
Composition
.82
.125
.055
Calculations
Specific Gravity	Subtotal
1,0000	.8200
.8871	.1109
2.65	.1458
1.077
-------
Table 3.17 Concentrations, Generation Rates, and Minimum Toxicity Levels
of 28 Elements Found in DAF Scum
Annual Quantity

Concentration
Total
Annual
at a typical
32,000 cu.m./day
(200,000 BPSD)

Minimum Acute Toxicity Effluents (MATEs)
Health Ecologv
Constituent
in DAP Float
(ms/kit)
Quantity
flut/vr)*
Refinery
{ttt/vear)
Air
(ms/a
Hater
) (me/Li
Land
(tus/eI
Air
(mg/a )
Water
(mg/L)
Land
(mg/g)
Aluminum
13*
800
9,490
5.2
80.
.16

1.
.002
Arsenic
2.0
120
1,460
.002
.25
.ooos
—
.05
.0001
Barium
31
1,900
22,630
.5
5.
.01
—
2.5
.005
Beryllium
.003
.2
1.8
.002
.03
.00006
—
.055
.00011
Boron
2*
120
1,460
3.1
47.
.093
—
25.
.05
Cadmium
.005
.3
3.6
.01
.05
.0001
—
.0001
.000002
Calcium
246*
15,200
179,580
—
—
—
—
—
	
Chlorine
7*
430
5,110
—
—
—
—
—
	
Chromium
140
8,700
102,200
.001
,25
.0005
—
.25
.0005
Cobalt
2.0
120
1,460
.05
.75
.0015
—
.25
.0005
Copper
7.0
430
5,110
.2
5.
.01
—
.05
.0001
Fluorine
15*
930
10,950
—
—
—
—
—
	
Gallium
2*
120
1,460
4.95
74.
.15
—
—
	
Iron
29*
1,800
21,170
—
—
—
—
—
	
Lead
7.5
460
5,470
.15
.25
.0005
—
.05
.0001
Magnesium
340*
21,000
248,200
6.
90 i
.IB
—
B7.
.174
Manganese
2*
120
1,460
5.
.25
.0005
—
.1
1.0002
Mercury
.27
17
197
.05
.01
.00002
.01
.25
.0005
Molybdenum
.05
3
36
5.
75.
.15
—
7.
.014
Nickel
.025
2
18
.015
.225
.00045
—
.01
.00002
Phosphorus
18*
1,100
13,140
1.
15.
.03
—
.0005
.000002
Potassium
76*
4,700
55.4B0
2.
30.
—
—
23.
—
Selenium
2.0
120
1,460
.2
.05
.0001
—
.025
.00005
Silver
.25
15
182
.01
.25
.0005
—
.005
.00001
Strontium
45*
2,800
32.B50
3.06
46.
.092
—
—
—
Sulfur
3370.
208 , 000
2,460,100
—
—
—
—
—
—
Vanadium
.05
3
36
.5
2.5
.005
.001
.15
.0003
Zinc
85.
5,200
62,050
4.
25.
.05
—
.1
.0002
1)	Values taken from Rosenburg, et al., except for those marked with an asterisk, which were calculated from
Tamay and Krishnan, using a specific gravity for DAF skimmings of 1.-077.
2)	Calculated from the concentration based on a dry weight generation rate of 3.64 metric tons/year/1000 BPSD
and a total capacity of 17,000,000 BPSD (1 April 1979).
3)	Source: Cleland and Kingsbury, 1977.
3-95
-------
MATEs for these elements. Daily generation rates were calculated by
dividing annual production at a typical refinery (Table 3.17) by 365
days per year. The amount of land needed daily to meet MATEs were cal-
culated by dividing the daily generation rate by the appropriate MATE.
This calculation assumes all these elements will be disposed on land,
either by landfilling, landspreading, or lagooning. The data indicate
that lead, chromium, selenium, zinc, and phosphorous would appear to
be the most troublesome metals. A typical refinery could need up to
20 metric tons (about 10 cubic yards) of soil per day, or 7,300 metric
tons (about 2 acre feet) per year, to dispose of its DAF scum while
meeting MATE levels. Although these calculations are inexact and tend
to be liberal, the numbers are high enough to warrant added concern
about safe disposal of DAF float.
The presence of solvents and organic chemicals is also of interest
in assessing the hazardousness of trace materials in DAF skimmings.
While many compounds have been identified in this waste stream, few have
been measured precisely. Table 3.19 lists 27 chemicals that have been
identified in DAF influents and some of their physical and chemical
properties. It is not known which compounds are in DAF float. Their
concentrations are also unknown. However, insoluble, and some slightly
soluble chemicals with a low specific gravity (less than 1.077) probably
do rise in the system and mix with the float. Chemicals having a higher
specific gravity (e.g., tetraethyl lead) or aqueous solubility (e.g.,
pyridine) may also be present in the scum layer if they are dissolved in
the scum oil. Some of these chemicals are highly volatile and ignitable.
Hydrogen sulfide, hydrogen cyanide, benzene, cyclohexane, hexene, metha-
nethiol., and methyl-2-butene all have high vapor pressures and low
flash points. In sufficient concentrations, they appear to present a
significant potential for explosion.
Table 3.20 measures the hazardousness of these 27 chemicals. Some
are highly toxic (e.g., tetraethyl lead, hydrogen cyanide, and cresol)
and some tend to become magnified in the food chain (e.g., anthracene
and biphenyl). Many of these compounds pose a threat to health and
environment even in miniscule amounts (e.g., hydrogen cyanide, cresol,
phenol, ammonia, tetraethyl lead, and naphthalene). It is impossible
3-96
-------
Table 3.18 Comparison of Daily Generation Rates for 28 Elements in DAF
Float with Their MATE Values
Daily generation race	Amount of soil needed daily to
at a typical 200,000 BPSD	meet MATEs for land in leg
Constituent
refinery in mg/day
Health
Ecology
Aluminum
26.
.2
13.
Arsenic
4.
8.
40.
Barium
62.
6.
12.
Beryllium
.005
.08
.04
Boron
4,
.04
.08
flarim-fnm
.01
.1
5.
Calcium
492.
—
_
Chlorine
14.
—
—
Chromium
280.
560.
560.
Cobalt
4.
3.
8.
Copper
14.
1.
140.
Fluorine
30.
—
—
Call ilia
4.
.03
—
Iron
58.
—
—
Lead
15.
30,
150.
Magnesium
680.
4,
4.
Manganese
4.
8.
20.
Mercury
.5
25.
1.
Molybdenum
.1
.7
7.
Hickel
.05
.1
2.
Phosphorus
36.
1.
18,000.
Potassium
152.
—
—
Selenium
4.
40.
80.
Silver
.5
1.
50,
Strontium
90.
1.
—
Sulfur
6,740.
—

Vanadium
.1
.02
- ,3
Zinc
170.
3.
850.
Totals
8,842.3 mg/day
692.3 kg/
day
19,942.4 1
3-97
-------
Table 3.19 The Hazards of 27 Chemicals Found in DAF Influents
Id
R«Cbyi*2*6ucti
Cyclofc*a*ne
CalOilaTID
IIQaCOW-
UUTICN
FaCTOi
100
47
h r fa indices
HEALTH
runu<
hinihu* kcsnt Toxicm cmuom (hatu)
»*wd on torn Haalib Mild oa Uolotlol I»ten
Uat«r Laod
• ¦"¦>"1	• u ¦ . •«i«i ian«	. Mtn mm
ntm* TIVITr («/¦') (m/1) («/«) (¦»/¦) (¦»/!) (¦/»)
iMpCOpfl >HIBI
(CUMM)
110
0
2
0






I7I1H
56
2
)
0
433
6,500
13
-
I
.002
liplMByl
546
-
-
-
1
IS
.03
-
-
-
Toluafi*
32

3
0
373
3.600
11
-
1
.002
ltbylb«aa«M
64

3
0
433
6,500
13
-
I
.002
Oacalls









—
NspCbaltM
13*
2
2
0
50
730
1.5
—
.1
.00002
Aatbccca&a
3,447
-
-
-
36
640
1.60
-
-
—
TatrMCbyl l«4d
—


3
0.1
l.J
.003
—
<.1
.00002
'i.4tlw 5olbM«










tcbaaocbiwl
5
-
-
-
1
15
.03
-
-
-
HachtMCblsl
3
-
-
-
I
13
.03
-
-
-
Waiim
16


0
3
43
.09
-
1
.002
WurnH Acid
(Capro Lc Acid)
6









Craael
3


0
22
.003
.00001
-
.3
.001
bcaioie Add
13
-
-
-
140
2,100
4.2
-
-
-
ttfdrogn Swlflda
7


0
13,000
23
—
—
.01
—
So Lib la










Hydrago Cyaalda
-
4
4
2
U
.3
.001
34
.025
•00000!
linn la
.04
3

0
11
2.3
.003
.35
.03
.00001
rocvaidabyd*
0.3
2
2
0
1.6
24
.046
.3
1
.002
FyrldlM
-
2

0
130
223
.43
-
10
.ozo
Vpdrocbiouc Acid
0.3
3
0
0
-
-
-
-
-
-
acatlc acU
-
2
2
1
23
300
.76
-
1
.002
IbMOl
2.3
3

0
19
.003
.00001
-
.5
.001
VoAlC Acid
—
3

0
9
140
.21
-
-
-
1)	Calculated fr» ttu lomilt blo«ccuaul*tloa iactor • 10* vt»r« « • 3.41 •
0.108 log (aquMttd Mlublllcy Uuulu par litir). (Chiou •( *1., 1977)
2)	Sourroi Clala&d tod cuogibury, 1977
1) lUtlOMl Plro Procoeiloo Aitoelatloa Unlets, 1969. (ft«« ouc p«t>.)
4) Sowrcoi BFFA, 1969
3-98
-------
Table 3.20 National Fire Protection Association Indices for Hazards of 27 Chemicals Found
In UAF Influents
ill M III
U - Materials which on very short
exposure could cause death or
major residual injury even
though prompt medical treatment
were given
3 - Materials which on short ex-
posure could cause serious temp-
orary or residual injury even
though prompt medical treat-
ment were given.
2 • Materials which on Intense or
continued exposure could cause
temporary Incapacitation or
possible residual Injury unless
prompt medical treatment is
given
1 - Materials which on exposure would
cause Irritation but only minor
residual injury even if no treat-
ment Is given.
U ¦ Materials which on exposure under
fire conditions would offer no
hazard beyond that of ordinary
combustible material.
H AMHAP1UTY
4 • Materials which will rapidly or com-
pletely vaporize at atmospheric pressure
and normal ambient temperature, or
which are readily dispersed In air and
which will burn readily.
3 - Liquids and solids that can be ig-
nited under almost all ambient temp-
erature condltIons.
2 - Haterlals that must be moderately heated
or exposed to relatively high ambient
temperatures before ignition can occur.
1 ¦ Materials that must be preheated before
ignition can occur.
0 • Haterlals that will not burn.
RbACl ivnv
4 ¦ Materials which In themselves are
readily capable of detonation or of
explosive decomposition or reaction ut
normal temperatures and pressures.
3 • Materials which in themselves ar£ cap-
able of detonation or explosive reac-
tion but require a strong initiating
source or which oust be heated under
confinement before initiation or
which react explosively with water.
2 " Haterlals which In themselves are
normally unstable and readily undergo
violent chemical change but do not
detonate. Also materials which may
react violently with water or which
may form potentially explosive mix-
tures with water.
I ¦ Haterlals which in themselves are nor-
mally stable, but which can become un-
stable at elevated temperatures and
pressures which mny react with water
with some release of energy but not
violently.
0 - Materials which In themselves are
normally stable, even under fire ex-
posure conditions, and which are not
reactive with water.
-------
to determine how much of a hazard these compounds present without data
on their levels in DAF skimmings. Research in this area would be quite
beneficial.
One trace substance that merits special attention in assessing
the hazardousness of DAF float is benzo(a)pyrene. This compound is
closely associated with oil and is a known carcinogen. It is insoluble
in water but soluble in oil and has been measured in DAP scum at an
average level of .002 mg/kg (Rosenberg et al., 1976). Based on the float
generation rate and industry capacity assumptions mentioned previously,
124,000 mg benzo(a)pyrene will be produced in the United States this year.
A typical 200,000 BPSD refinery could generate as much as 1,460 mg per
year, or about 4 mg per day. Because M&TEs based on human health for
'benzo(a)pyrene are so low (.020 mg/m for air, .300 mg/£ for water, and
6 ug/g for land) special care is needed to ensure that the public's
health will not be endangered at DAF float disposal sites.
Based on these considerations, DAF float has significant potential
for causing damage to man and the environment because of the toxicity,
volatility, and ignitability of the waste stream, and because it is
generated in relatively large quantities.
3.6.5.3 Current DAF Waste Treatment Storage and Disposal Practices
Petroleum refineries currently use a variety of methods to treat,
store, and dispose of DAF skimmings. Table 3.21 outlines the treat-
ment and disposal strategies of eight refineries. These refineries are
typical of the industry in that most use some type of treatment to de-
water the scum before disposal and most use a land-based disposal tech-
nique .
(a) Treatment alternatives
DAF float is approximately 82 percent water, and dewatering results
in a significant reduction in waste volume. Refineries use four methods
to dewater DAF wastes: gravitational separation; filtration; heat treat-
ment ; and chemical treatment.
3-100
-------
Table 3.21 Treatment/Disposal Strategies for DAF Float at Eight Petroleum Refineries
(Rosenberg et al., 1976)
Refinery Source of Influent
Code	to DAP System
Processes Applied
to OAF Float
Before Disposal
Disposal Method
Comments
Lo
I
• Two-stage API
separator
A-2	« API separator
A-3	o APT separator
Centrlfuglng
Oil recovery
Centrlfuglng
Vacuum filtering
or
Incineration
Centrlfuglng
Unspecified off-
site method
Filtered material
Is landspread
Incinerated residues
are landfilled on-
site
Centrifuge cops are
returned to the API
separator; centri-
fuge bottoms are land-
filled on-site
Plost la mixed vlth DAF
sludge and wastes froo
slop oil recovery system
before being centrlfuged
Float Is mixed vlth API
separator sludge and
waste blcsludge before
centrlfuglng and with
tank bottoms afterwards
Float Is mixed with API
separator sludge before
centrlfuglng
A-4	o API separator
a Vacuum filtering
• Landfilled off-site
Float is mixed with wastes
from emulsion-breaking
treatment of slop oils
and with waste blosludge
before filtering
B-4
o API separator
o Hone
Unspecified on-site
nethod
C-l
API separator and
blo-oxldatlon
system
Dewatered In a
cone-shaped tank
« Landfilled off-site
Nixed with thickened
API separator sludge
and waste blo-oxldatlon
sludge before dewaterlng
C-2	o API separator	o None
C-*	o ATI separator and	• None
bio-treatment system
e Lagooned
0 iflnriflUed off-site
-------
Gravitational separation is based on differences in the specific
gravities of the three components of scum: water, oil, and solids.
The simplest method of physical separation is to let the scum stand,
allowing water and solids to settle out. The remaining float is then
decanted. Up to 15 percent by volume of the waste stream can be elimi-
nated in this manner, most of it as water (American Petroleum Institute,
1969). In some cases, the three components are tightly bound together
and settling is not very efficient. Several refineries are experimenting
with centrifuging their DAF float. Industrial centrifuges provide a
fast, efficient, but costly method for dewatering this waste. This
physical separation technique is limited to small volumes of scum and
has not alwdys proved successful where oil and solids are bound together.
Furthermore, erosion from gritty solids may cause significant maintenance
problems.
Scum filtration is usually done with a precoat filter. Processing
with these filters is done in three stages. A slurry of diatomaceous
earth and recirculated water is pumped through the filter unit until a
thin protective precoating layer of the earth is deposited on the filter
elements. Then wastewater is fed into the filter with a small ratio of
the slurry in a continuous operation. The filter is considered fully
operable when effluent water is sufficiently clear to be sent to the
next treatment process or discharged into sewers. Slurry is added con-
tinuously to the feed to maintain the porosity of the filter cake on the
filter elements. When the pressure differential increases, indicating
that the filter cake is plugged, the wastewater feed is cut off and the
filter system is back-washed to a sump. This removes the spent filter
cake. The complete cycle is restarted. As oil/water emulsions pass
through interstices of the filter cake and precoat material, globules
break up and stabilizing solids are removed. The resulting effluent
is then more amenable to gravitational separation.
Precoat filters usually require less space than other solid/liquid
separation equipment and can filter out even some clay-sized solids.
They are also capable of adjusting to variations in the conditions of a
wastestream. Although operating costs are usually high, and the diato-
mite slurry makes an additional solids disposal problem, many petroleum
3-102
-------
refineries use precoat filters to treat DAF scum before routing the oils
back to the process area.
Heating DAF scum to break up oil/water emulsions is a simple and
economical technique which is nearly always advantageous. Heat markedly
reduces the viscosity of the oil phase, melts interfacial waxy films,
and occasionally reduces the efficiency of emulsifying agents. Heat is
frequently used in conjunction with centrifuging, filtering, and chemi-
cal treating. The cost-to-benefit ratio can be reduced dramatically if
waste heat can be used for treating DAF scum, or if waste heat from
scum treatment can be used elsewhere in the refinery.
An extreme form of heat treatment is distillation. In this pro-
cess, oils are removed from the scum in a much purer form than in other
treatment processes. However, distillation is very energy intensive
and costly. No refineries use distillation to treat scum on a full-
time basis.
The primary purpose of chemical treatment of DAF scum is to break
oil/water emulsions. Certain chemicals balance or reverse interfacial
surface tension on each side of an interfacial film, neutralize stabili-
zing electrical charges or precipitate emulsifying agents, thus enabling
+ | I I
oil and water to separate. Reactive cations such as H , A1 ' and
| j |
Fe will break oil/water emulsions.
While nearly all refineries use chemicals to aid in the DAF pro-
cess itself, some also use them on the resulting sludges and skimmings
in order to extract more usable oil. It is frequently difficult to
predict how efficient a given chemical will be in treating DAF scum
because of the chemical and physical variability of the waste stream.
Selection of a treatment scenario for a refinery's DAF float
depends to a great extent on how much oil can be recovered from the
waste. Most refineries use gravitational separation to treat their
DAF scum when they are attempting to recover oil or reduce the waste
quantity. Chemical treatment is used primarily during, and not after,
the air flotation process. When heat treating is used it is usually
in conjunction with another form of treatment. More elaborate schemes,
such as the combination of heating with filtering and/or centrifuging,
3-103
-------
are common only where oil recovery on a large scale is a goal. Other-
wise, if any treatment is used at all, it is a simpler and less costly
treatment such as gravitational settling.
(b)	Storage
Petroleum refineries have not generally been concerned about the
storage of DAF float. Most commonly, the scum is collected in open
troughs until hauled away for disposal. This procedure permits volatile
components to contaminate the air surrounding the DAF unit and the
collection troughs. The industry's lack of concern may be due to lack
of any data on air contamination from DAF operations. At this time,
it is unknown whether DAF scum storage represents a serious problem or
not.
(c)	Disposal Alternatives
Land disposal is the most frequent means of disposing of DAF wastes.
Landfilling is now used at a majority of U.S. refineries. Land treatment
and lagooning are less common. However, land treatment is on the rise
and landfilling and lagooning of DAF scum are declining. OiL recovery
is also increasing as the price of crude oil escalates. Most refineries
already have in-plant schemes for oil recovery from process wastes al-
though DAF wastes are not always included. Incineration is used pri-
marily where oily wastes are not recoverable and where other methods
are not cost-effective for reasons such as the cost of suitable land
for landspreading.
Table 3.22 gives estimates of the current and projected use of
these five waste management methods.
1. Landfilling and lagooning
Landfilling and lagooning are, theoretically, the simplest
methods for disposal of DAF float. They are also the most commonly
used. However, lagooning frequently leads to air and ground water con-
tamination, and cases exist where a lagoon's berms fail, resulting in
a massive release of wastes to soils and surface waters. There is
pressure on industry from environmental groups to phase out this dis-
posal method.
3-104
-------
Table 3.22 Current and Projected Percent Use of Several Methods
For Managing DAT Scum
Method
Lagooning
Current Projected
n	2.3
Use	Use
20%
0%
Rationale for Projected Use
Lagooning will be phased out
as a disposal method because
it does not adequately protect
the environment. It may still
be used for temporary storage,
however.
Landfilling
70%
50%	Landfilling will continue to
be popular because the tech-
nology is so well established.
However, the shift to land
treatment will cause a decline
in landfill use.
Land treatment 20%
50%	The use of land treatment will
increase dramatically as more
research is done on solving
the problems of protecting the
environment.
Incineration	10%
10%	The high cost of land in some
areas will continue to make
incineration of non-recoverable
oils cost effective despite
rising fuel costs.
Oil Recovery
20%
80%	Attempting to recover oils
from DAF scum will increase
as the price of crude oil
increases. Some DAF waste
streams, however, will prob-
ably not be recoverable.
1)	Based on Table 3 . 2J.
2)	The estimates sum to more than 100 percent because some refineries
use more than one method.
3)	Based on current trends in technological development, the economy,
and environmental protection.
4)	The value of oil recovery from any refinery waste stream is much
higher	probably over 75 percent. Refer to Table 3.13 for estimates
of the percent of use of disposal methods for all refinery wastes.
3-105
-------
Landfills tend to be somewhat safer than lagoons. However, since
oil does not degrade very rapidly under the anaerobic conditions found
in fills, they are, in a sense, permanent storage facilities. There
are three basic types of landfills: open dumps, sanitary landfills,
and secure landfills. Open dumps are pits where wastes are dumped and
left uncovered until the pit is filled. Like lagoons, open dumps are
being phased out of use.
Sanitary landfills are similar in design to open dumps but their
operation is quite a bit different. In a sanitary landfill, wastes are
covered at frequent intervals, usually daily or after each disposal
operation. This method of landfilling is rapidly becoming the most com-
mon because it frequently provides adequate protection for the environ-
ment, and is always less expensive than a secure landfill.
In 1976, a well managed sanitary landfill for oil wastes (at
least 3.5 percent oil by weight) cost about $5.39 per wet ton of
wastes disposed, or about $28.23 per dry ton. By comparison a secure
landfill costs about $16.54 per wet ton or about $86.61 per dry ton
(Tarnay and Krishnan, 1978).
Secure landfills are more expensive because advantageous geo-
hydrologic conditions and leachate containment structures such as
liners must provide extra protection from leachate migration. Favorable
geohydrologic conditions require thick, impermeable earth materials
under a site, and very deep water tables. Not all liners are chemically
compatible with oily wastes such as DAF float. Only oil-resistant PVC,
polyethylene, polypropylene, soil cement, soil bentonite, and compacted
clay liners are acceptable from a chemical resistance point of view
(Stewart, 1978). Besides liners, containment structures include cement
structures and metal drums (Ghassemi and Quinlivan, 1975). However,
acceptability may change with the issuance of Final EPA regulations
under RCRA.
2. Land Treatment
Land treatment is becoming increasingly important as a method for
disposing of oily wastes. The strategy behind this technique is to
3-106
-------
leave the waste on or near the land's surface where it can degrade.
Degradation is mainly by oxidation, solution, and emulsification. Most
of the degradation results fxom oxidation. However, evaporation plays
a major role in decreasing the volume of wastes disposed on the surface.
Oxidation, including photo-oxidation, auto-oxidation, and especially
bio-oxidation accounts for most of the degradation occurring at land
treatment facilities for oily wastes.
Bio-oxidation agents are known to include species from 28 genera
of bacteria, 30 genera of filamentous fungi, and 12 genera of yeasts
(Zobell, 1973). The rate at which oils are degraded depends primarily
on these factors:
•	availability of free oxygen
•	temperature
•	concentration and dispersion of the oil
•	organic content of the soil
•	abundance of bio-oxidizing organisms
•	availability of nutrients, such as nitrogen and
phosphorous.
The overall rate of decomposition is usually in the range of 5 to
60 pounds of oil per cubic foot of soil per month. Besides carbon diox-
ide and water, the principal products of the breakdown of oil by micro-
organisms includes various hydroperoxides, alcohols, phenols, carbonyls,
aldehydes, ketones and esters. These products probably do not accumu-
late in sufficient concentrations to be injurious to the environment
(Zobell, 1973).
Selection of a site that will not release contaminants to ground-
water or surface water, and control of air emissions, are probably the
two most basic problems associated with landspreading. Equations have
been derived to calculate the maximum areal migration of pollutants from
landspreading sites (Ministry of Interior, Federal Republic of Germany,
1970). Cold weather is also a problem although some oil degradation
goes on even under Arctic conditions (Loynachan, 1978). Some hydro-
carbons appear to be fairly persistent, such as paraffin waxes and the
3-107
-------
high molecular weight, polyaromatic material typically found in cata-
lytically-cracked, slurry oil. However, even these are eventually
consumed (Zobell, 1973). The problem that receives the most attention
from researchers, however, concerns the buildup of heavy metals in the
soil, and their transmission to other environmental media, especially
vegetation, where they can enter the food chain.
In 1977, Parr et al. listed the most important factors affecting
metal uptake and accumulation in plants:
•	Soil pH: Toxic metals are more available to plants
below pH 6.5
•	Organic matter: Organic matter can chelate and complex
heavy metals so they are less available to plants
•	Soil phosphorus: Phosphorus interacts with certain
metal cations to reduce their availability to plants
•	Cation exchange capacity (CEC): Important in binding
of metal cations; soils with a high CEC are safer for
disposal of sludges
•	Moisture, temperature, and aeration: These can affect
plant growth and therefore the uptake of metals
® Plant species and varieties: Vegetable crops are more
sensitive to heavy metals than grasses
•	Organs of the plant: Grain and fruit accumulate lower
amounts of heavy metals than leafy tissues
•	Plant age and seasonal effects: Older leaves of plants
will contain higher amounts of metals
e Time: With time, metals may revert to unavailable
forms in soil
« Amount and type of metals: Zinc, copper, nickel and
other metals differ in their relative toxicities to
plants and in their reactivity in soils.
Under certain conditions, high enough concentrations of heavy metals
can accumulate in plants to be toxic to animals using the plants as a
food source. Research results are often conflicting however. One
3-108
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study done on an API separator sludge landspreading site in southeastern
Texas, showed significant increases in sodium, zinc, and lead concentra-
tions in both soil and vegetation (Phung et al., 1977). The data from
this study are summarized in Table 3.23. However, a second study found
the main problem arising from applications of large amounts of spent
motor oil to soil was immobilization of nutrients, primarily nitrogen.
Furthermore, this second study seemed to show no problem from plant up-
take of metals (Gliddens, 1976). The differences may be simply due to
differences in chemical constituents between API separator sludge and
waste oil.
Land treatment of oils continues to increase despite the potential
for environmental problems, because of its relatively low cost. In 1972,
one land treatment operation in California cost less than $11 per dry
ton, making it comparable with landfilling (Gliddens, 1976).
Land treatment has definite advantages over landfilling, but there
are still unanswered questions regarding its environmental safety.
Careful operation and monitoring is needed to ensure that these sites
do not become a major source of contamination of soils.
3. Incineration
In areas where the price of land suitable for disposal of oily
wastes is too high to be cost-effective, DAF float can be destroyed by
burning and incineration. Successful burning requires that the waste
have a high enough heat content to sustain combustion. No special
equipment is used to control either combustion or air contamination.
Consequently, burning waste oil without removing contaminants can re-
sult in significant emissions to air of lead and other heavy metals,
and volatile organic chemicals. DAF scum must be extensively dewatered
to sustain combustion, therefore open burning is not an important method
of disposal for this waste stream.
Incineration, on the other hand, is a	common disposal method for
DAF float. Equipment is specially designed	to control both combustion
and air emissions, and fuel can be added to	sustain combustion. DAF
scum must usually be dewatered and filtered	to a certain extent before
3-109
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Table 3.23 Summary of the Data From a Study of the Effects of Land
Treatment API Separator Sludges
(Phung, Ross, Landreth study)
Background Information on tlx Bite:
Area of Sice
Vaste Type
Uaste Volume
Application Race
Fercilizacion/Liaing
Soli Characteristics
Depth of Soll/Uaste Mixture
Site Age
Vegetative Types
8.2 ha (20 ac)
API oil/vater separator sludges
Periodic disposal, 29,600 m^/yr (185,000 bbl/yr)
1.27 * 103m3/ha (3.22 x 103 bbl/ac)
None
Clay, poorly-drained, alkaline
15 to 30 an (6 to 12 in)
5 Years
Weeds and shrubs along the disposal area perimeter
Chemical Characteristics of the Surface Soils froa Control and Oil-Treated Plots on the Site:
pH
EC, nahos/co
Oil, I
TKN, X
Org. C, 2
P
Na
B
Mn
N1
Zn
Se
>to
Cd
Pb
Control
7.41
2.21
0.080
2.10
Treated
7.40
3.91
2.06
0.134
5.10
	ppm	
17.5
185
0.2
65
4.8
53.5
0.01
0.6
0.06
212
17.5
375
0.22
71.6
5.3
71.5
0.028
0.55
0.06
242
Change
-0.01
+1.70
+2.06
+0.054
+3.00
0
+190
+0.02
+6.6
+0.5
+18.0
+0.018
-0.05
0
+30
3-110
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Table 3.23 Summary of Che Data From a Study of the Effects of Land
Treatment API Separator Sludges (Continued)
Analysis of Vegetation Sampled from the Control and Treated Plots at the Site;
Nutgrass Leaves			CocVIeburr Seeds
Element
Control
Treated
Change
Control
Treated
Change







N
1.44
1.42
-0.02
3.05
1.07
-1.98
P
0.17
O.U
-0.06
0.29
0.16
-0.13
fla
2,062
6,187
		ppm
+4,125
1,000
6,870
+5,870
B
7
IS
+8
28
14
+14
tta
63.6
48.7
-14.9
18.8
19.1
+0.3
N1
1.9
6.3
+4.4
3.6
3.1
-0.5
Zn
93.8
131.9
+38.1
43.8
53.1
+9.3
Se
0.23
0.23
0
0.04
0.04
0
No
7.1
9.5
+2.4
4.2
8.7
+¦4.5
Cd
0.41
0.41
0
0.15
0.15
0
Pb
61.5
90.5
+29.0
11.2
23.2
+12.0
API separator sludge will have sore oil bnd solids and less water than DAF scum. The sludge
averages 22.61 oil, 24.AX solids, and 53Z water (before dewaterlng). Scum averages 12.51 oil,
S.SZ solids, and 822 water (NFPA, 1969).
3-111
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it can be incinerated because the water and solids in the waste are not
combustible. If there is a substantial total volume of waste (above 50
gallons per hour), then removal of water by either chemical or mechanical
separation is usually advisable because the oily layer probably will
sustain combustion by itself (Mann, et al., 1970). However, if the
oily waste is miscible and in small quantity, then it is not economical
to separate the water prior to incineration.
DAP scum that contains emulsions may require chemical treatment
prior to incineration. Emulsions pose special problems for incineration
systems because they contain inconsistent mixtures of oil and water re-
sulting in erratic combustion. This requires greater use of auxiliary
fuel. There is no rule-of-thumb concerning the selection of direct in-
cineration of an emulsion versus prior breaking of the emulsion because
costs of auxiliary fuel vary too widely throughout the country. Each
case must be evaluated separately.
Combustible liquid mixtures normally have calorific values above
8,000 BTUs/lb (Mann, et al., 1970). Grease and scum will have a heating
value about 16,700 BTUs/lb (EPA, 1974a),but they represent only a small
portion of the DAP waste stream. Auxiliary fuel is usually needed. Most
organic waste materials require temperatures between 650°C and 980°C
(1200°F and 1800°F) for complete combustion (Mann, et al., 1970).
Incinerator design for a partially combustible liquid waste oil
may take a variety of forms, depending on concentration of the organic
material in the waste, viscosity, specific gravity, and a number of
other factors. Most incinerators used for oily wastes are cylindrical
and refractory-lined. They may be either vertical or horizontal.
Three types of incinerators have been used for DAF float: Rotary
kiln; multiple hearth; and fluidized bed. However, studies suggest
that fluidized bed incineration is the optimum choice for refinery
wastes (Tarnay and Krishan, 1978).
A fluidized bed is essentially a vessel containing inert granular
particles, such as sand. Blower-driven air enters at the bottom of the
bed and rises vertically, agitating the particle mass and causing it to
behave like a dense liquid. Wastes are injected into the bed by pumping,
3-112
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by air pressure, or by gravity, where rapid and relatively uniform mixing
of wastes and bed material occurs. Wastes must usually be predried in
order for adequate combustion to take place.
In the combustion process, heat transfer occurs between bed mater-
ials and the injected waste materials. Typical bed temperatures are in
the range of 760° to 870°C (1400° to 1600°F). Due to the high heat
capacity of the bed material, the heat content of the fluidized bed is
3	3
approximately 142,000 kg-cal/m (16,000 BTUs/ft ), about three orders of
magnitude greater than the heat capacity of flue gases in typical incin-
erators operating in the same temperature range ( Tarnay and Krishnam,
1978). Heat from the combustion process is transferred back to the bed
material. Solid materials remain in the bed until they have become
small and light enough to be carried off with the flue gas as a particu-
late. As with most other incineration techniques, fluidized bed com-
bustion generates both particulates and gases which require air pollution
controls prior to release. Wet scrubbers are effective in reducing par-
ticulate emissions. The method used to control gaseous pollutants de-
pends on the particular combustion products. Normally, no odors and
little nitrogen oxide is produced from fluidized bed combustion, due
to relatively low gas temperatures and low excess air requirements.
The cost of incinerating the majority of a typical refinery's oily
wastes using a fluidized bed is about $29.77 per dry metric ton or
about $5.50 per wet metric ton in 1976 dollars ( Tamay and Krishnaa,
1978). By comparison, the cost of incinerating a similar amount of
waste using a multiple hearth would be about $25 per dry metric ton
(EPA, 1974 b). These costs are comparable to disposal in a sanitary
landfill.
Incineration does have disadvantages. The process has a high
capital cost as well as high annual operation and maintenance costs.
Stricter air pollution regulations may require extremely expensive
and complicated air pollution control devices at some future date,
thus reducing the cost-effectiveness of the process. Finally, as
much oil as possible is now extracted from all refinery waste streams.
As a result, the thermal value of the various sludges has decreased to
3-113
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such a point that combustion is no longer self-sustaining or is only
marginally so. Continued operation of incinerators thus requires
additional thermal energy. Therefore, incineration should not be
considered a panacea for the disposal of DAF float, especially in light
of the high demand for an uncertain supply of oil in this country.
4. Resource Recovery
As the price of oil increases, resource recovery becomes more
attractive. Resource recovery involves three different strategies for
managing oil in refinery waste streams: direct reuse, product reclama-
tion, and oil terefining. Because the oil in DAF float comes from so
many different processes and is so variable, product reclamation is not
applicable. Reuse and rerefining are applicable, however.
The extent to which oils can be reused is determined, in part, by
their composition and condition. Thus, reuse potential must be evalu-
ated on a case-by-case basis. DAF waste oils may be useful as form
release oils for concrete pouring operations and as raw materials for
asphalt production. They have also been used successfully in several
areas to control dust and weeds and to provide considerable surface
consolidation to unpaved roads. However, road oiling can result in
substantial environmental contamination, since 70 percent to 90 percent
of untreated waste oil applied is transported to the atmosphere on dust
particles or to surface water via runoff (Fennelly et al., 1977). This
reuse may constitute disposal under RCRA Section 3007 regulations.
In some cases, rerefining waste oil is more cost effective than
finding an environmentally safe use. Waste oil very low in solids can
be returned directly to the slop oil recovery system in the refinery.
Otherwise, it must be pretreated. The American Petroleum Institute has
outlined nine basic processes for handling recovered oils from oil-
water separators, slop emulsions, and other refinery sources (API
Manual on Disposal of Refinery Wastes: Liquid Wastes). The cost and
suitability of each process for recovering DAF oils would vary widely
between refineries and must be evaluated on an individual basis. Never-
theless, rerefining has proved to be technically and economically success-
ful both In the petroleum refining industry and in other industries.
3-114
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A western Pennsylvania steel mill refines an average of 50,000 gal-
lons of used hydraulic oil a year. The oil is collected and settled in
a large storage tank. Then it is processed in a package rerefining unit
that filters the oil and vacuum distills the filtrate. This process
produces a distillate and a reusable hydraulic oil. The cost of the
operation is 14c per gallon, for a savings of 16c per gallon or $8,000
per year (Mann et al., 1970).
Jacobs Engineering Co. (JEC) has designed an oil recovery system
that can be used to process all oily wastes from a typical refinery. Fig-
ure 3.15 is a process flow diagram of this system. This approach is
notable because it considers all refinery wastestreams and not just ones
with very high oil contents. JEC estimates treatment costs with this
system to be $6.90 per wet metric ton or $36.13 per dry metric ton,
making it only slightly more costly than either incineration or land
disposal (Tarnay and Krishnan, 1978). These costs are based on a value
of recovered oil of $8 per barrel. As the price of virgin crude rises
on the world market, so too will the price of recovered oil. Consequent-
ly the unit cost of recovering oil will decrease somewhat, making the re-
refining of oily wastes in the industry more attractive.
The trend to more recovery of oil is most apparent with regards
to waste oils. In Massachusetts in 1975, 23 percent of the waste oils
generated in the state was reclaimed; 13 percent was used for dust con-
trol; and 4 percent was used in making asphalt. Almost 52 percent was
used as fuel, either in industrial burners or in incinerators. Only
4 percent was landfilled and most of that was spilled oil contained on
absorbing media (Fennelly et al., 1977).
In summary, the basic technology for recovering oil from wastes
presently exists. However, the cost-to-benefit ratio is not always
favorable. As the price of crude oil continues to increase, this situ-
ation will change, making oil recovery more economical.
3.6.5.4 Methods Suggested by Related Technology
* v
Two recent innovations in landfill design for other kinds of in-
dustrial wastes may be applicable to oily wastes. The first involves
3-115
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Rvco*vr«4 SoWcnt
Roary
Drt«r
MftM*
Solution r*«4 Pump
D*t«< SoU6» to L^AtfUI
Sel*n( Caui Swja T«m
Ixinct TmmA Poap
S*apl« Palct
(1)
(Z)
(3)
(«>
- f3>
Stapl* DviciipOot
Waal* Slurt
r «*4
Aectos* Solv*at^
Oriad Solid*
W»atv«»»t«r
A»«l*Jne4
OU
CcaywfBti -





Ae«(M«
k|«/hc
lb./h*

7,647
(16,013)
0.1
(0.2)


an*
hp/bt
lb*/hr
•OT
(l.TTS)

U
PD

793
(1.745)
Witif
kp/hf
lbt/br
1.600
O.S20

16
(35)
1.584
(3. 4*5)

Solid*
k|«/br
lb«/br
568
n.uo)

561
(l.UOl


TCTAij
kf»/br
lbo/hr
2, 975
(6.543)
7,647
(L6.8Z3)
598.1
(1.316)
1,504
(3.485)
793
(I. 745)
(I) • kii« V«h«i vtUk fiarry CMO^«tlU«a*
Figure 3.15 Process Flow Diagram of a General Oil Recovery System
for Refining Wastes (Tarnay and Kirshnan, 1978)
3-116
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2.	DAF Operations
•	Are volatile components emitted in harmful quantities
during the operation of the DAF unit or during storage
of the scum?
•	If there are harmful air emissions, what can be done
to reduce them?
3.	Oily-waste Landfills
•	Is the concept of using an "absorption barrier" in
landfills that receive oily wastes worth pursuing?
•	If it is, what is the best absorptive media in terms
of capacity, long-term stability, and cost-effectiveness?
4.	Rerefinability
•	Are all DAF scum oils technically and economically re-
refinable?
•	What unusable wastes will be produced from rerefining?
And how can these wastes be safely disposed of?
a Is the phase separation system developed by Jacobs
Engineering Co. practical?
Because the composition and generation rate of DAF float is so
variable, environmentally-safe, cost-effective, treatment/storage/dis-
posal processes for each refinery must be developed on an individual
basis. This is especially true for the treatment and storage options.
Furthermore, greater emphasis should be placed on ensuring that the
operation of DAF units and the temporary storage of DAF float does not
contribute to air contamination.
Unlike treatment and storage procedures, disposal methods can be
evaluated in more general terms because they are not so dependent on
the composition of the waste. Table 3.24 lists the primary advantages
and disadvantages of the disposal methods now used for DAF scum.
Table 3.25 rates the potential for air, land, and water contamination
from each method. Table 3.26 gives estimates of the costs of the
methods. Based on these tables, sanitary landfilling appears to be a
3-117
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use of gravel "drainage blankets" between layers of sludge in conjunc-
tion with a leachate collection/treatment system to manage waste from
the pulp and paper industry (Ledbetter, 1976). The second relies on a
"neutralization barrier" of limestone particles to stabilize sludges
from the electroplating industry that contain heavy metals (Crumpler,
1977). In place of the gravel and limestone used in these designs,
perhaps some oil-absorbent medium could be used. Straw, perlite,
chalk, diatomaceous earth, talc, polyurethane foam, pine bark, sawdust,
peat, composted refuse (Vaux, et al., 1971), silt, and paper processing
sludge (Jones, 1975), are all useful for absorbing oil. Use of an oil
absorption barrier in a sanitary landfill might provide increased en-
vironmental safety at only a moderate increase in cost. However, none
of these media have been used for this purpose in a landfill, and their
long-term effectiveness is unknown.
3.6.6 Re commendat ions
Although quite a bit of information concerning treatment, storage,
and disposal of DAF float has been presented, there are gaps in the
data. JRB has defined four areas of inquiry: the waste stream, DAP
operations, oily waste landfills, and rerefinability. Within each area,
we have also developed a set of questions to help direct future research
activities. The areas of inquiry and research questions are as follows:
1. Waste stream
« What are the physical and chemical characteristics
(and variability) of the oils in DAF float?
e What are the concentrations (and variabilities) of
the trace substances listed in Tables 3.18 and 3.19
in the oil, water, and solid fractions?
• What are the physical characteristics (e.g., density,
degree of emulsification, volatility, ignitability)
of the waste?
3-118
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simple, cheap method of disposal that has a relatively high potential
for polluting the environment. Secure landfilling is a bit more com-
plex and much safer environmentally, but it is very expensive. Incin-
eration can be pollution-free if residues are managed properly, and
comparable to sanitary landfilling in cost. Reuse can be the most cost-
effective, method also yielding the most pollution. Rerefining is
safe, but slightly more expensive, and not applicable in all cases.
Any of these techniques can be suitable for disposing of DAF float
if implemented correctly. However, rerefining provides both safe dis-
posal and an environmentally-optimum method. Where practical, JRB
recommends that refineries recycle DAF skimmings and all other oily
wastes as well.
3-119
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Table 3.24 Summary of Environmental Effects of Disposal Methods for DAF Float
Hcthod
Sanitary landfllllng
and 1agoanlng
Advantages
•	Technology la well established
•	Operation la simple
•	Existing sites are very available throughout
the country
Plaodvantagea
Potential for environmental contamination
la high
Hay becone a long-tern liability
Not aultable (or all hacardou* waatea
Public'opposition nay be high
Secure landfllllng
•	Technology Is fairly well established
« Potential for environmental contamination
Is low
•	Suitable for most haeardoua waatea
o Successful Implementation of tha method
can be difficult
•	Existing sites are relatively acarce
•	Finding aultable altea can be very difficult
t Site volumes are generally Halted
•	Perpetual care Is needed because of the
haeardoua nature of the wastes
•	Public opposition nay be high
Landspreadlng
o Technology Is fslrly well established
•	Operation Is fairly simple
•	Site nay be able to be returned to another
use
•	Finding aultable sites nay ba difficult 1
e Not aultable for all haeardoua wastes
e Site volunes limited by waste decomposition
ratea
9 Potential for environmental contamination
can ba high
•	Public opposition nay bd high
Incineration	• Technology Is veil established
•	Operation Is relatively staple
•	Existing sites ore fairly available
throughout the country
•	Decreased total volume of vaBte9 for
disposal
•	Suitable for nany hazardous waates
s Potential for environmental contamination
la low with adequate controls
e Hay require aupplemental fuels
s Public opposition nay ba high
final • Residues must be disposed
• Potential for mechanical failure can be
relatively high
Resource recovery
•	Technology Is fairly well established
•	Potential for environmental contamination
la lower because chere Is less waste
•	Public opposition would ba low
•	Could help to reduce somewhat the U.S.'*
dependence on Imported oil
s Successful operation nay be complex
e Not aultabl* for many haiardous wastaa
s Residuals still oust be disposed of
s Recovered oil may caua* problems In some
refinery processes
-------
Tahle 3.25 Summary of Potential Emission Levels from Disposal Methods
for DAF Float
Potential For Release To
Method
Air
Land
Water
Sanitary	Low (landfllling) to High
landfllling (lagooning)—depends on the
and	thickness and permeability
lagooning of the cover material used
(for landfills), on the
quality of vaste management,*
and on the volatility of
the wastes
Moderate—some release of
contaminants is likely
depending on soil perme-
ability
Moderate—(same as for
land)
OJ
H-•
to
Secure	Low—depends on the speed
landfllling and success of waste-cell
construction
Low—assuming that the
liner or geologic control
remains intact and that
water Is kept out of the
site
Low—(same as for land)
Land	High—direct release of
treatment	contaminants to the air;
volatile components may
reach high concentrations
High—direct release of
contaminants to the soil
Moderate—depends on
the site's geologic and
hydrologic conditions;
could be very low at
well selected, well
managed sites
Incineration Low—assumes proper resi-
dence and temperature for
the Incinerator. Adequate
measures taken for con-
trolling air pollution
Low—assumes adequate
disposal method used for
solid residues
Low— assumes adequate
treatment and disposal
of scrubber waste-
waters
Resource	Low—assumes adequate con-
recovery	trols used during reuse
of recovery
Very high^-lf used as a
dust control measure.
Low—If rereflned
Low—with rereflnlng
-------
Table 3.26 Summary of Costs of Disposal Methods for DAF Float
Cost per metric ton in
second quarter 1979 dollars
Method
Wet basis Dry basis References
Sanitary
landfilling
6.60	34.54	Tarnay and Krishnan, 1978
45.42 237.84	Rosenberg et al., 1976
Secure
landfilling
20.24 105.98_	Tarnay and Krishnan
77.05 403.48	Rosenberg et al.
Landspreading
9.98	52.282	Bratby, 1977
19.90 104.20	Rosenberg et al.
Incineration
4	4
6.73	36.43	Tarnay and Krishnan
Resource recovery	8.44	44.21
Tarnay and Krishnan
1.	All costs were derived from 1976 dollars, multiplying by 1.2237
(except as noted).
2.	Calculated for DAF float only; the other costs in this table assume
that most refinery wastes would use the same disposal system.
These values were inflated from 1973 dollars to 1979 dollars,
multiplying by 1.5463.
3.	Average of six values first converted from $/ton to $/metric ton
and then inflated from 1972 dollars to 1979 dollars, multiplying
by 1.6379.
4.	These costs do not include the cost of waste disposal from inciner-
ation and air pollution control.
3-122
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3.7 WASTEWATER TREATMENT SLUDGE FROM THE ELECTROPLATING INDUSTRY
In 1976, there were a total of 2,254 electroplating and metal
finishing industry job shops in the United States. An EPA study indi-
cated that 89 percent of the job shops are small and medium-size plants
with 1 to 50 employees (EPA, 1976a).
3.7.1 Manufacturing Process and Waste Stream Characterization
Most electroplating or metal finishing operations involve a series
of unit operations that includes prefinishing, finishing and post-
finishing. There are a total of 12 electroplating and finishing proces-
ses, with most of the operations being electroplating. An average of
four different metals or alloys are deposited per job shop (EPA, 1976a).
Prefinishing operations prepare the piece for plating by removing
all foreign matter, such as oil, grease, dirt and oxide, that could re-
tard or prevent the plate from adhering to the workpiece surface. This
operation includes deburring, degreasing, acid pickling, and alkaline
cleaning. Finishing operations include application of one or more elec-
troplates, such as copper, chromium, nickel, zinc, or anodizing, and
electroless plating. Postfinishing operations include bright-dipping,
passivating, chromating, phosphating, buffing and polishing.
The services offered by this industry, listed under SIC 3471, vary
from a single operation to multiple-step processing. A simple electro-
plating process generally includes sequential operations of cleaning-
rinsing-plating-rinsing-drying. Very complex operations require a
number of cleaning steps with additional steps of acid dipping, striking,
activation, multiple rinses and deposition of more than one metal.
Figure 3.16 is a flow chart for a typical electroplating facility (EPA,
1978a). Cleaning prepares the piece for plating by removing all foreign
matter. Abrading, pickling, and other preliminary treatment is often
necessary, followed by rinsing to remove pretreatment solutions. Rins-
ing enhances surface adhesion and prevents contamination of plating
3-123
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V.OHX FLOW
RINSE
SLUDGE
TREATED WATER
RINSE
ACID
COPPER
PLATE
RINSE AMD
DRY
ACID
DIP
CYANIDE
COPPER STRIKE
CHROMIUM
PLATE
RINSE
NICKEL PLATE
ACID
DIP
RINSE
RINSE
PRECIPITATE
CHROMIUM
PRECIPITATE
COPPER
PRECIPITATE
NICKEL AND COPPER
NEUTRALIZE AND
PRECIPITATE
OXIDIZE
CYANIDE
SETTLE
REDUCE
CHROMIUM
Figure 116 Process Flow For a Typical Electroplating Facility
3-124
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solutions. At the end of the plating process, all workpieces are
rinsed before being allowed to dry, to avoid spotting.
The primary source of pollutants in the electroplating industry
is the process solution drag out from workpieces as they are moved from
tank to tank in plating operations. Drag out appears in rinse waters,
spent process solutions, and in spills and leaks from the process tanks.
Rinse waters, representing 90 percent of water usage in electroplating
processes, become polluted with drag out from various process tanks and
are discharged (EPA, 1978a),
Toxic substances accumulating in the rinse water, or used in the
plating solutions, often find their way into plant wastewaters through
accidental spillage or tank leaks, Intentional tank dumpings, drag out
from one tank to another, periodic cleaning and replacing of filters
and vapor sprays or mist collection systems.
Closer supervision of the electroplating process will reduce acci-
dental spillage and leaks, toxic vapors, and losses from the cleaning
of filters. Drag out is a more difficult and continuous problem result-
ing from the transfer of racks or barrels from one solution to another
and is the major source of pollution. Intermediate rinsing solutions
become contaminated with solutions from previous tanks, necessitating
periodic dumpings. However, the volume of plating and the type of pro-
cess used are important elements in determining the amount of pollution.
The estimated quantities of potentially hazardous water pollution
control sludge generated from the electroplating and metal finishing
industry for 1975, and projected for 1977 and 1983, are given in
Table 3 .27 (EPA, 1976 b), The 56,399 metric tons (dry weight) represents
nearly three times the sludge quantity in 1975. Only an estimated
35 percent of the total electroplating and metal finishing plants pro-
duced water pollution control sludge in 1975. Regulations which have
taken effect since 1975 require wastewater treatment, resulting in
production of more of these sludges.
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Table 3.2 7 Production of Water Pollution Control Sludge From the
Electroplating and Metal Finishing Industry (Job Shops)
Sludge (Dry Weight)
Year	Metric Ton (ton) Per Year
1975	19,740	(21,764)
Projected 1977	56,399	(62,182)
Projected 1983	73,882	(81,458)
Water pollution control sludges are the single largest waste
streamsdestined for land disposal in the electroplating and metal
finishing industry. The sludge contains solids levels ranging from
less than 5 to more than 20 percent, depending on water pollution con-
trol technology and degree of sludge dewatering employed. The liquid
portion includes rinse waters from each plating step and process solu-
tions such as alkaline cleaners, acid dips and pickles, and conversion
coating solutions, and may contain significant concentrations of cyanides.
Solids in the sludge are precipitated metal hydroxides. Metal hydroxides
found in this wastewater sludge, and their comparative values, are shown
in Table 3 .28.
Table 3.28 Metal Hydroxide Wastes in Water Pollution Control Sludges
From the Electroplating Industry (1975)
Metal Hydroxide	Percent*
Iron	12.36
Copper	8.88
Zinc	12.72
Nickel	17.90
Aluminum	10.65
Chromium	33.37
Cadmium	1.73
Tin	0.14
Lead	1.98
Manganese	0.03
*Calculated from the total quantity of hazardous metal hydroxide wastes
generated in the water pollution control sludges from the electroplating
and metal finishing industry (job shops); metric tons; dry weight; 1975
(EPA, 1976b), It does not reflect waste production from any one plant.
Although destruction of cyanides through chlorination is prac-
ticed in the industry, certain cyanide complexes require longer reaction
times and large amounts of oxidizing chemicals to insure removal from
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wastewater streams. Thus, it is likely that significant concentrations
of cyanides are disposed with the wastewater treatment sludge. Simple
compounds such as sodium or zinc cyanide are more easily broken down by
chlorination than silver, gold, nickel and cobalt salts. Iron cyanides
are not amenable to treatment by chlorination, but they are not as toxic
as most cyanides (National Commission on Water Quality, 1975).
There is no indication of changes in the unit operations and
technology of the electroplating and metal finishing industry, and no
sudden changes are expected in the foreseeable future. Therefore,
characteristics of the water pollution control sludge are not expected
to change to any significant degree in the near future. Indiscriminate
mixing of spent process solutions from pre- and postplating operations
can make waste streams extremely variable, however, and this might
overload and upset wastewater treatment system performance and
efficiency.
The quantity of sludge generated in an electroplating and metal
finishing plant is not uniform for any given process because drag out
and spillage vary from plant to plant. Wastewater and sludge volumes
depend on the total production of the electroplating and metal
finishing industries.
There is no by-product other than sludge generated from the waste-
water treatment plant in the electroplating and metal finishing industry.
Water pollution control sludge in the electroplating and metal
finishing industry is suspected to be reactive and volatile because it
contains various heavy metal hydroxides and may contain cyanide
compounds. An EPA report indicates that chromium metal ions, which
are present in many electroplating sludges, are hazardous to man in
various valence states. It can produce lung tumors when inhaled and
induces skin sensitizations. Large doses of chromates also have corrosive
effects on the intestinal tract and can cause inflammation of the kidneys
(EPA, 1974a). Chromium (VI) is a known carcinogen.
Specific data on toxic effects of sludge waste from the electro-
plating and metal finishing industry which is destined for land disposal
are very sparse, and little is known about possible synergistic effects.
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The most widely accepted basis for defining many of these materials as
potentially hazardous is the relatively low acceptable levels of the
various metals in drinking water. Criteria for public water supplies
issued by the U.S. Environmental Protection Agency are shown in Table 3.29.
Water containing any of these metals in concentrations equal to, or more
than, that listed is considered hazardous to health. On this basis, all
known wastes from electroplating and metal finishing operations have the
potential to contaminate ground water to hazardous levels.
Bioconcentration is the selective concentration, or storing, of a
specific chemical species by an organism. Studies show that several
substances in wastes from the plating industry can be retained and
stored by organisms at harmful levels. These include cadmium, lead,
and mercury (EPA, 1977c).
Mutagenic or teratogenic materials are not widespread in electroplating
industry wastes. Other than chromium (VI), a few other suspected
carcinogens may be present, although trichloroethylene is the only
suspected carcinogenic agent in common use in this industry. Mutagens
cause changes within the genes. The literature indicates that nitrates
are probably the only suspected mutagens which may be present in the
wastes of these industries. A teratogenic effect is one creating
abnormalities during gestation. According to the National Academy
of Sciences, teratogenic effects are usually seen only at doses well
above likely exposure levels for environmental chemicals such as solvents,
and some compounds of mercury, lead, cadmium, and other metals (NAS, 1975).
Table 3.30 summarizes treatment, storage, and disposal technology
which is, or may be, applicable to the water pollution control sludge
waste stream from the electroplating and metal finishing industry. The
current practice is solids concentration through the use of lagoon and
holding tank settling to produce a 1 to 5 percent solids sludge for
disposal in a handfill. Approximately 60 to 70 percent of the plants
use off-site disposal for their sludge (EPA, 1976b). Although a few
plants may use advanced treatment techniques such as chemical fixation,
solidification, etc., common practice is to utilize the simplest, least
expensive disposal techniques acceptable to pertinent regulatory
3-128
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Table 3.29 Criteria for Public Water Supplies
Waste
Constituents
Permissible
Concentrations, ppm
Arsenic
0.05
Beryllium
0.2
Cadmium
0.01
Chromium (hexavalent)
0.05
Copper
1.0
Cyanide
0.01
Gold
0.4
Iron (filterable)
0.3
Lead
0.05
Manganese (filterable)
0.05
Mercury
0.004
Nickel
0.8
Oil and Grease
7
Palladium
7
Phosphates
545
Selenium
10.01
Silver
0.05
Sulfates
250
Tin
1.2
Zinc
5.0
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Table 3.30 Summary of Treatment, Storage, and Disposal Technology for
Water Pollution Control Sludge From the Electroplating and
Metal Finishing Industry
Practices
Treatment
Current or Broad
	Average	
Concentration to
1-5 percent solids
through the use of
lagoon, holding
tank or clarifier
settling
Best Available
Technology
Sludge is con-
centrated to
*20 percent
solids through
the use of cen-
trifugation of
filtration
Suggested By
Related Technology
Chemical fixation/
solidification
Storage
Holding lagoon
Steel drums
Encapsulation
Disposal
Lagoon or landfill
Approved land-
fill
Secured landfill
or reclamation
-------
agencies. This generalization applies to both the industry and to waste
disposal contractors. Discussions of levels of treatment, and storage
and disposal technology applicable to the water pollution control
sludge are included in the following sections.
3 .7.2 Treatment Alternatives
3.7.2.1 Current Practice
The usual practice employed to separate treated wastewater is
to concentrate solids through the use of simple settling using lagoons,
holding tanks or clarifiers to create a 1 to 5 percent solids sludge
for disposal. Table 3.31 shows the treatment methods used by the 30
job shops in a survey reported in a 1976 EPA study. Thirteen of the
50 plants (26 percent) used holding tanks to separate the sludge from
the treated wastewater.
Table 3.31 Treatment Methods Used by Fifty Job Shops to Separate
Solids From Treated Wastewater (EPA, 1976b)

Treatment Method
No. of Plants
Percent
Lagoon
8
16
Holding Tanks
13
26
Tank and Clarifier
4
• 8
Clarifier and Dewatering
2
4
Direct Dewatering
10
20
Unknown
13
26
Total Plants
50*

*The number of shops reporting disposal was 50; more than one treatment
is used in some shops.
Lagoons may be natural water bodies or man-made water bodies con-
structed either by digging out a depression in the earth or by erecting
dikes. Most lagoons used in waste disposal operations are man-made on
specific selected sites. The lagoon may be unlined, or it may be lined
3-131
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with clay or plastic sheets overlaid with about 1 foot of gravel. La-
300ns are used for clarification of both chemical plant process waters
and wastewaters, and can concentrate solids to 1 to 5 percent. Settling
or thickening lagoons are used when conventional units are overloaded
or, sometimes, as substitutes for conventional processes.
As the basins fill, they are cleaned and the sludges removed and
discarded, or the sludges are left to dry in the basin and new basins
are constructed. If the liquid portion of the waste can contaminate
groundwater, the lagoon bottom must be sealed to prevent leakage.
Instead of settling wastewater in a lagoon over a period of months
or years, some plants dewater their slurries to sludge immediately.
This treatment is used when: land is not available or is too expensive
for lagooning; states prohibit lagooning of these wastes; or lagoons
may overflow, leak or break. In many instances, dewatering is the
only treatment available. The degree of dewatering depends on the
local situation, particularly on the distance between the plant and
disposal site.
The least complex treatment method is.a holding tank in which
solids may be concentrated to about 1 to 2 percent. A thickener or
clarifier may be used to treat overflow from the tank to increase den-
sity of slurries. This operation can increase the solids content to
about 2 to 3 percent. These thickening slurries may be sent directly to
a lagoon or landfill, or may be further treated by filtration or cen-
trification. Slurries may also bypass tank settling and/or thickening
and be processed by direct dewatering.
1.7.2.2 Best Available Technology
The best treatment technology for electroplating water pollution control
cludge involves concentration of solids and dewatering to levels of 20 percent
or more. The dewatering operation utilizes filtration or centrifuga-
tion to produce a high solids, lower volume sludge cake for ultimate
disposal. Rotary vacuum filters can concentrate sludge containing 4 to
8 percent solids to 20 to 25 percent solids (EPA, 1976^). Because the
effluent concentration of solids is usually less than 4 percent, a
3-132
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thickener tank is often employed between the clarifier and the filter.
The filtrate often contains excessive suspended solids and is recircu-
lated to the clarifier.
Centrifuges can also thicken sludges to 20 to 25 percent consis-
tency, and have the advantage of using less floor space. The effluent
contains suspended solids in excess of 20 mg/£ and needs to be recir-
culated to the clarifier.
The same solids content can also be attained with pressure filters.
This filtrate contains less than 3 mgIt of suspended solids so return to
the clarifier is not needed. Semicontinuous tank filters may further
increase solids content to as high as 35 percent. Plate and frame
presses can produce filter cake of 40 to 50 percent solids, while auto-
mated tank type pressure filters will produce the highest solids content
waste ol about 60 percent (EPA, 1976b).
An estimated 24 percent of the plants employ centrifugation and
filtration to dewater their sludge prior to land disposal (EPA, 1976).
The choice of dewatering technique is highly dependent on economics,
available space, or environmental limitations imposed on the ultimate
disposal site.
An EPA study estimated capital investment costs in centrifuge
system and operating costs for waste handling and disposal at three
model electroplating and metal finishing plants of different sizes
(EPA, 1976). These costs are shown in Table 3 .32. Model plant opera-
tions were based on 250 working days per year, and costs are in December
1973 dollars. The centrifuge systems were designed to dewater the
sludge to 20 percent solids. Capital and operating costs for filter
units which thicken sludge to the above range of consistency would be
comparable to those for centrifuges.
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Table 3.32 Estimated Centrifuge System Capital and Operating Costs
For Three Different Size Electroplating and Metal Finish-
ing Model Plants
Amount of WPC Installed Cost of Handling
Sludge 20%	Centrifuge and Disposal of
Solids Metric System	Wastes*/Metric Ton
Model Plant Size Ton/Year	 Cost
Small (16-man)
Medium (38-man)
Large (87-man)
76.25
176.00
353.00
$ 7,150
19,500
48,700
$129.57
122.22
115.96
*This represents the total cost for collecting, hauling, handling and
landfill disposal for the wastes.
3 .7.2.3 Methods Suggested by Related Technology
Chemical fixation utilizes a physical chemical matrix structure
to tie up hazardous liquids and solids for disposal. Sludge may be
solidified by addition of chemical fixing agents which insolubilize
the metal hydroxides, and thus prevent or retard leaching of the
waste in the environment. Approximately 2 percent of all plating
sludges are treated on-site by the chemical fixation and solidification
treatment techniques (EPA, 1976b).
Chemical fixation/solidification is a process that involves mixing
cementing agents such as Portland cement, lime-pozzolin cements, lime-
based mortars, certain mixed organic polymers or inorganic compounds to
produce a friable, solid-like material which may be acceptable for land-
fill. After mixing the cementing agent with the semi-solid lagoon sludge,
the mixture is pumped out on land for solidification. It is then dis-
posed as landfill. A number of firms offer chemical fixation/solidifi-
cation commercially. Some processors have portable equipment for on-
site treatment at a client's plant (Fields and Lindary, 1974). Units
are also sold for permanent installation at sites requiring continuing
processing of wastes.
Costs for fixation and solidification of industrial wastes vary
widely, depending on such factors as the process used, type of waste,
transportation costs, equipment renting, and landfilling costs.
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A typical price range given by several waste processors for
treating an industrial waste is from $8.00 to $20.00 per metric ton of
waste (Crurapler, 1977).
The advantages for using this method for plating wastes are:
•	commercial availability and applicability to both
large and small sludge generators
•	low cost of fixation
•	decreased leachate production
•	stabilization of wastes so that metal ions do not migrate
•	ease of disposal
•	reduced disposal cost, since fixed solidified material
may be acceptable for general landfill.
3.7.3 Storage Alternatives
3.7.3.1 Current Practice
The most prevalent storage practice in the electroplating and
metal finishing industry is lagoon storage. The wastes stored in the
lagoons include both liquids and sludges, including water pollution
control sludge. The lagoons are usually located on company owned lands.
It is estimated that more than 30 percent of the plants store waste
sludge in lagoons on a short-term basis (EPA, 1976b). This technique
provides a simple and economic approach to on-site waste disposal,
where applicable. However, there are significant drawbacks.
•	The lagoons must provide protection from both surface
and groundwater contamination. In almost all areas
this means a lined pond. Liners include clay, plastic,
concrete and epoxy, all relatively expensive.
•	Lagoons are prone to be "flushed out" with massive
rainfall. It is difficult and expensive to provide
flood protection.
•	Except in very dry climates, lagoons that do not
normally discharge will overflow after	rainfall.
3-135
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3.7.3.2 Best Available Technology
Containerization of water pollution control sludge In steel
drums prior to disposal is considered the best storage technique for
the electroplating and metal finishing industry. Both plastic lined
and unlined drums and barrels are used. A 1976 EPA study estimated
less than 4 percent of the plants in this industry employ this storage
method.
Steel drums provide some long-term containment and are the most
convenient storage and transportation mode for relatively small quan-
tities of potentially hazardous wastes. Drum burial procedure usually
entails filling the drum with the waste, sealing the drum, transporting
drums to the disposal site and, finally, land storage or land burial.
The obvious problem with this method is eventual decay of the steel
drums. Unless disposed of iti an approved ot secured landfill, future
release of drum contents to the environment is likely.
3 .7.3.3 Methods Suggested by Related Technology
Encapsulation and cementation of potentially hazardous waste are
special disposal safeguards currently employed for only the most hazard-
ous wastes, such as nerve gas, biological warfare agents, radioactive
wastes, etc. If permanent storage is required, these techniques could
be used to transform waste pollution control sludge for ultimate dis-
posal. At present, there is no indication that these techniques are
employed for the water pollution control sludge in the industry. EPA
found that one waste disposal contractor actually uses concrete encap-
sulation for disposal of small quantities of plating wastes so that the
waste is isolated from the environment. It is assumed that less than
1 percent of the total quantity of the plating waste is disposed utili-
zing this technology (EPA, 1976b). A detailed discussion of encapsulation
and cementation techniques is presented in Section 3 .2.3.3. The cost
of encapsulation is estimated to be approximately $40 to $85 per ton of
dry waste (Buck, et al., 1974). This cost is based on 1973 dollars.
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3.7.4 Disposal Alternatives
3.7.4.1	Current Practice
The usual disposal practice for water pollution control sludge
after solids concentration treatment is simple land disposal, including
surface and deep burial, open dumps, lagoon and municipal landfills.
EPA estimates that 59 percent of the plants employed this simple land
disposal method both on-site and off-site. Sixty-six percent of the
plants employ off-site disposal (EPA, 1976).
This disposal technique is considered inadequate for health and
environmental protection, because of potential contamination of ground-
water or surface water supplies. The waste sludge is mainly an aqueous
slurry of metal hydroxides, and when exposed to an acid environment,
metals re-enter solution. The metal ions can then migrate to groundwater,
by way of rain water percolating through the land disposal site.
A summary of contractor hauling, treatment, and disposal charges
'for electroplating and metal finishing sludges for a simple or municipal
landfill is presented in Table 3.33.
3.7.4.2	Best Available Technology
The best available disposal technology for water pollution control
sludge is an approved sanitary landfill. An EPA study reported that
about 4 percent of the plants employed this method for off-site disposal
(EPA, 1976b). These landfills meet the criteria under Section 4004 of
RCRA as well as Section 3004 criteria as given in the Federal Register
of Thursday, September 13, 1979, while Section 3004 criteria were under
development as of August, 1980.
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Disposal of water pollution control sludges in an approved sanitary
landfill is considered adequate for short-term disposal. Long-term pro-
tection cannot be assured since surface run-off and rain water can perco-
late through the disposal area, leading to leachate formation (EPA, 1976b).
Estimated costs for contractor disposal at an approved landfill is
shown in Table 3.33.
3.7.4.3 Methods Suggested by Related Technology
The disposal technologies considered environmentally adequate for
water pollution control sludge include use of secured landfill and mat-
erials reclamation. A secured landfill employs basic site selection and
leachate control procedures described for an approval landfill, with
additional safeguards discussed in the previous section. Estimated cost
for disposal in a secured landfill by a contractor is shown in Table 3.33.
Sludges and liquids from electroplating and metal finishing wastes
contain valuable metals and other materials which, theoretically, may be
recovered by chemical treatment. By reclaiming the dissolved plating
metals in the wastewater during the plating operations, sludge formation
would be circumvented altogether. At present, no viable techniques for
the reclamation of these materials from sludges have been demonstrated
on a commercial scale. However, many techniques for metals recovery
are currently practiced and techniques for concentrating aqueous liquids,
such as reverse osmosis and evaporation, have been demonstrated success-
fully (EPA, 1976b). Other recovery methods are being tested on bench-
scale but have not yet reached commercial scale. These are electrodialy-
sis, freezing, carbon adsorption, ion-flotation techniques, and liquid-
liquid extraction (Crumpler, 1977). Other such operations include chemi-
cal precipitation and crystallization from solution.
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Table 3.33 Summary of Estimated Contractor Hauling, Treatment, and Disposal Charges for Electroplating
and Metal Finishing Waste Destined for Land Disposal (EPA, 1976b)

Hauling
Charge*8'
Contractor Charge
For Combined
Hauling, Treatment
and DiBDOsal^b^
Contractor
Charge for
Treatment and
Disposal'0^
Total Contractor
Charge to the
Electroplater
Treatment
Technology
C per
liter
C per
gal
C per
liter
C per
gal
C per c per
liter gal
C per
liter
C per
gal
Simple or municipal
landfill
1.32
5.0
3.6
13.6

3.6
13.6
Approved landfill
1.32
5.0
5.0
19.0
-
5.0
19.0
Secured landfill	1.32 5.0	-	-	6.9 26.0 8.2	31.0
(a)	This Is the charge made by the contractor for collecting and hauling the waste to the disposal
site.
(b)	This represents the charge made by the contractor to the electroplater for confined hauling,
treatment (if any), and disposal in a landfill. The charge includes landfill fees.
(c)	This is the charge for treatment and disposal of the waste after delivery to the disposal
site.
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The practicability of reclamation schemes is determined by such
factors as recovery costs versus virgin materials costs, energy require-
ments, the availability of energy, and the cost of environmental pro-
tection (EPA, 1976 b).
3.7.5 Recommended Treatment and Disposal Techniques
The most appropriate treatment and disposal methods for the water
pollution control sludge in the electroplating and metal finishing in-
dustry would be chemical fixation and solidification treatment followed
by disposal in an approved landfill.
The advantages of chemical fixation are:
•	Wastes may be stabilized so that metal ions are not
readily available to the environment.
•	Costs of -fixation are reasonable ($8 to $20 per
metric ton of waste).
•	The process is commercially available and applicable
to both large and small plants.
The advantages of approved landfill are:
•	Hazardous heavy metal sludge may be disposed of in
a controlled and environmentally safe fashion.
9 Selection of landfill sites and disposal technology
for environmental suitability still leaves a great
~umber of available landfill sites.
•	Disposal costs for transporting sludge to treatment
site and landfilling site are at levels close to
those for general purpose sites and much lower than
for secured landfill.
The disadvantage of the above treatment and disposal techniques
is that no resource recovery is practiced. However, it appears that resource
recovery may become a viable option in the future. T.ono-terw storage of these
sludges may be a feasible alternative to allow subsequent resource recovery
of a large volume of wastes.
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3.7.6 Environmental Impact
Table 3.34 shows a comparison of emissions of alkali cyanides in
wastewater treatment sludge with associated MATE values. The basis for
the values is the properties of cyanide which create problems for treat-
ment and disposal. These include a generally low vapor pressure and
high solubility in water, and release of hydrogen cyanide from contact
with acid.
Table 3.35 compares emissions of chromium from wastewater
treatment sludge with its associated MATE values. Properties of
chromium include low vapor pressure and low solubility.
These tables are used to show very rough estimates of releases.
Although disposal of this waste in steel drums may not appear to
provide long-term protection, it was determined to be the best
method in practice at this time.
A means of comparing disposal methods for metallic constituents
in plating sludge with criteria offered by the State of Illinois is
offered in Table 3.36. The Illinois criteria describing methods of
disposal for Alternatives I, II and III follows. Assuming a high
degree of leachability of the sludge components, the characteristics
of an acceptable disposal site may be determined from this comparison.
It appears that an Alternative II disposal site would probably
have to be used to dispose of plating sludge in the State of Illinois.
Actual laboratory testing of sludge samples, including leachability,
would be necessary to verify this.
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Table 3.34 Cyanides In Wastewater Treatment Sludge
Estimated Emissions
Current Practice Best Available Transfer of Technology


Landfill
Sludge de-
watering ,
disposal in
steel drums
in approved
landfill.
Sludge dewatering,
encapsulation,
disposal in
secure landfill.
Media
MATE VALUES



Air,
mg/m-*
Health 5'°
<5.0
<5.0
<5.0
Ecology
Water,
Health 0.5
>0.5
<0.5
<0.025
mg/1
Ecology
0.025
Land,
Health 1*0
>1.0
<0.025
<0.05
"g/g
Ecology
0.05
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Table 3
35 Chromium
In Wastewater Treatment. Sludge
Estimated Emissions



Current Practice
Best Available
Transfer of Technology


Landfill
Sludge de-
watering,
disposal in
steel drums in
approved land-
fill.
Sludge dewatering
encapsulation,
disposal in
secure landfill.
Media
MATE VALUES



Air,
mg/m3
Health 0.001



Ecology
Low
<0.001
<0.001
Water,
Health 0-25
>0.25
<0.25 .
<0.25
mg/1
Ecology
0.25
Land,
Health 0.5


<0.5
ug/g
Ecology
0.5
>0.5
<0.5
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Table 3.36 Comparison of Plating Sludge Metallic Constituents With
State of Illinois Criteria
Concentration
in Dry Sludge
mg/kg
Criteria for
Alternative
I
Criteria for
Alternative
II
Criteria for
Alternative
III
Iron
Copper
Zinc
Nickel
Aluminum
Chromium
Cadmium
Tin
Lead
Manganese
6,180
4,440
6,360
8,950
5,325
16,685
865
700
990
15
500
250
200
500
150
275
2,000
750
600
2,000
450
825
6,000
2,250
1,800
6,000
1,350
2,475
Assumptions: (1) 5% solids in sludge.
(2)	Constituent concentrations in plating sludges
calculated from information in the discussion
of chemical composition of sludge.
(3)	Illinois criteria stipulates that allowable
concentrations may double if waste contains
greater than 2.5 percent excess lime alkalinity
and quadruple if 5 percent.
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The following offers additional explanation of. Table
3.36 and was taken from Illinois Pollution Control Board Rules
and Regulations, Chapter 9 Special Waste Handling Regulations,
Supplemental Permit System, and was promulgated on March 15,
1979. (Illinois, 1979):
"Waste components are examined to determine the major
contaminants, their environmental pollution potential,
and the suitability of the proposed disposal method and
site. Waste containing higher leachable heavy metals
(as determined by Agency leach test procedures) or
significant toxic chemicals concentrations are required
to utilize more conservative disposal methods and sites
with better geology to minimize potential environmental
harm.
Criteria applied to wastes containing significant
leachable heavy metals (up to those values in Alterna-
tive I) allows for co-disposal with municipal waste,
above grade, at a site with at least ten feet of under-
lying soils with a permeability of 1 x 10"? cm/sec or
less. Wastes containing leachable heavy metals up to
those values in Alternative II, may be co-disposed
with municipal waste below grade in a site with ten
feet of underlying soils with a permeability of 1 x 10"^
cm/sec or less. Wastes with leachable heavy metals up
to those in Alternative III may be disposed of in a
trench accepting only like materials in a site with at
least ten feet on bottom and sides of 5 x 10 cm/sec
or better soil. Wastes with leachable heavy metals
greater than those in Table III must be disposed of in
a trench accepting only like materials in a site with
at least ten feet on bottom and sides of 1 x 10~® cm/sec
or better soil.
Since no specific criteria relating toxicity to
disposal method of organic wastes has been devised, best
engineering judgment is applied to all supplemental
permit applications. The more toxic the waste, the
better the geology, and disposal method required, e.g.,
a chlorinated organic such as hexachlorocyclopentadiene
in any significant concentrations would be required to
be containerized, utilize best available geology, and
be disposed of in a trench containing only compatible
or similar materials. A less toxic and less persistent
organic in concentrations which presented no bulk hand-
ling problem could be permitted to be disposed of along
with municipal waste at a special waste sanitary land-
fill having underlying soils with the permeability of
1 x 10"^ cm/sec."
3-145
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3.8 WASTEWATER TREATMENT SLUDGES FROM WOVEN FABRIC DYEING AND FINISHING
IN THE TEXTILE INDUSTRY
3.8.1 Manufacturing Process and Waste Stream Characterization
Of the 5366 textile plants in the United States (SIC 2261, 2262)
EPA has identified 651 as plants that perform woven fabric dyeing and
finishing operations. The typical product is a polyester-cotton blend
fabric, although some plants only process 100 percent cotton fabric or
only process 100 percent synthetic fabric. The total estimated annual
production was about 1,801,000 kkg/year, based on the 1972 Census of
Manufacturers (EPA, 1976c). An estimated 56 percent of plants performing
woven fabric dyeing and finishing operations have wastewater treatment
systems (EPA, 1976c and EPA, 1977d). Therefore, sludges are generated
only in facilities having their own wastewater treatment systems. The
total estimated quantities of wastewater treatment sludges from woven
fabric dyeing and finishing operations in 1977 were 13,661 metric tons
(dry weight). This amount is expected to increase to 48,481 metric tons
(dry weight) by 1983 (EPA, 1976c).
A typical woven fabric dyeing and
includes the following operations:
•
singe
•
desize
•
scour
•
mercerize
•
bleach and wash
•
dye and/or print
•
applied finish
s
mechanical finish.
finishing process in textile plants
A mass balance flow diagram of the typical woven fabric dyeing and fin-
ishing process is shown in Figure 3.17. The waste streams generated
from the dyeing and finishing process are listed in Table 3.37.
3-146
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Table 3.3 7 Waste Streams Generated by Typical Woven Fabric Dyeing and
Finishing Plant (EPA, 1976;c)
Waste
Cloth
Cloth
Cloth
Cloth
Flock
Dye
containers
Chemical
containers
Fiber
Wasted sludge
Retained
sludge*
Source
Singe and desize
Mercerize
Bleach and wash
Mechanical finish
Mechanical finish
Dye and/or print
Dye and/or print,
applied finish
Wastewater treatment
screening
Wastewater treatment
Wastewater treatment
Quantity (kg of waste/
kkg of product)	
0.2
0.1
0.2
6
4
0.5
0.8
0.8 (dry) 2.8 (wet)
20 (dry) 2,300 (wet)
67 (dry) 7,300 kg (wet)
*The retained sludge quantity is an accumulation over the life of
the pond.
Note: The typical plant produces 5,600 metric tons of product per year.
3-147
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CMCMtCAL COMTAINCASO J
ore coMTAiNins oi
ovt cwmovMrufH »
*OVKN
CACtOt
coooi .
i cni
^ OI1IZC	tCOUA I 	1	 ¦	1	1	—j
L—LA4M
•— MIQPCal7| I — BtCACH I — OVI AHOJ I
I HASH
f
biik ie
-fs
00
WAS 1
IVi
Lf» - LIQUIDWASTI
^ - PAOCfSt WASTC TO LAMQ
caustic
CLOTH
POTENTIALLY
HAZARDOUS
CONSTITUENTS*
RESIOUAL
CHEMICAL! OD*
FINISHED
» WOVEN
fabric \jjoo
CLOTH I
HOCK «
o
-	VVA1ER POLLUTION
ABATEMENT WASTE
TO LAND
-	POUMTIALLV
MA2AROOCS IVASTS
STREAM TO LAND
-	see table 3 m for
trceipic METALS
WIHimiY HA2ANOOUI
CONSTITUENT*
residual oyestuf# ooon
RETAINED SLUOQI*
SEE NOTE
PRE TREATMENT

NAtrmATCfl



TREATMENT

iioute
(MIUKNY
(MOT INCLUDf O IN
MASSBALAMCS)
N0H AM AVtnA0(O*«7 KO CDRYI. IJOOKOfHlT)
IIUOGC II RtTAlNEOCONTAWINQ 0-fl3 KO TOTAL
HEAVY METALS." UalQ-* KQ TOTAL CHLO*INAT«0
OROANlCI ANO )4KQ QYCSTUFF (MOT MCUSOIO W
MASS BALANCEI
POTENTIALLY HAZARDOUS
CONSTITUENTS
TOTAL HEAVY METALS'* 0 10	.
TOTAL CHLORINATEOOROANlCSttOa 10"
ovt injpf ta
Figure 3.17 Typical Woven Fabric Dyeing and Finishing Process (EPA, 1976c)
-------
Sludges in the wastewater system contain hazardous constituents
such as the heavy metals chromium, copper, and zinc and chlorinated
organics, and dyestuffs which are considered potentially hazardous.
No by-products are generated from the process. All wastes from
woven fabric dyeing and finishing operations are routed to the wastewater
treatment system where sludges are produced.
Wastewater treatment sludge has solid concentrations ranging from
less than 1 percent to more than 20 percent, depending on the wastewater
pollution control technology and degree of sludge dewatering techniques
employed (EPA, 1976c). The sludge wastes include some of the many chemi-
cals used in dyeing and finishing operations, such as acids, alkalies,
bleaches, adhesives and polymers, cross-linking agents, conditioners,
catalysts, detergents, dye carriers, chemical finishes (including flame
retardants) and solvents. Solvents commonly used in the operations
include acetone, methanol, naphtha, trichloroethane, dioxane, butyl carbi-
tal, and butyl cellosolve. Dye carriers are organic compounds that also
appear in the sludge. They include biphenyl, orthophenylphenol, butyl
benzoate, methyl salicylate, trichlorobenzene, perchloroethylene, and
other chlorinated aromatics (EPA, 1976c). The sludge contains an estima-
ted 75 percent (by weight) of non-hazardous materials such as common salt
and sodium sulfate. The hazardous chemical composition of the sludge is
shown in Table 3.35. Iron accounted for 52 percent by weight of the
total heavy metal content, and zinc accounted for 25 percent of the total
heavy metal content according to these measurements. Additional analysis
for total chlorinated organics showed 98.8 percent by weight of the total
content (15.2 ppm) was found in the solid phase of the sludge, with the
remainder in the liquid phase (EPA, 1976c).
Because products in the woven fabric dyeing and finishing operations
are ultimately used for apparel, furnishings, and other consumer products,
waste projections are closely related to population growth. This is
about 3 percent per year (EPA, 1976c). Little or no change is anticipa-
ted in the near future in wastewater treatment technology or dyeing and
finishing operations for woven fabrics. Therefore, the broad characteris-
tics of the waste stream are not expected to change to any significant
3-149
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Table 3. 38 Woven Fabric Dyeing and Finishing Sludge Chemical Composition
iag/kg of dry sludge* mg/kg of wet sludge*
Arsenic
1
0.01
Barium
39
0.56
Cadmium
4.4
0.07
Chromium
1,196
20.43
Cobalt
26
0.26
Copper
652
8.46
Iron
4,910
77.23
Lead
36
0.57
Manganese
128
1.90
Mercury
0.35
0.004
Molybdenum
17
0.2
Nickel
32
0.51
Zinc
2,370
39.92
Total Heavy Metals
9,412

Aluminum
4,640
72.74
Magnesium
2,820
29.59
Potassium
3,580
38.44
Sodium
51,300
525
Strontium
16
0.23
Total Chlorinated Organic
15.2

Suspended Solids
0.88

Total Solids
1.26

~Average of 20 measurements
from five points

3-150
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degree in the near future. However, sludge constitutents may vary due
to process startingt process shut down, or changing products. When
textiles are dyed, a sufficient amount of dyestuff is used to make the
shade. Various other chemicals may be used to help deposit the dye, or
to develop the color. Dye loading varies widely, depending on the
weight of fabrics being treated and the depth of color desired. The
range of chemicals employed in dyeing varies widely from plant to plant
and process to process, and depends substantially upon the dictates of
the marketplace.
Wastewater treatment sludge from woven fabric dyeing and finishing
operations is the most complex waste stream generated from the textile
industry. It Includes such hazardous components as heavy metals, resi-
duals and absorbed dyestuffs, organic solvents and chlorinated organics.
Because it contains toxic compounds (heavy metals, chlorinated organics),
and ignitable compounds (flammable hydrocarbon solvents), this waste
stream is considered potentially hazardous. Although believed to be
present, it is not known to what degree flammable hydrocarbon solvents
may be contained in the sludge, since this analysis was not shown in the
literature.
Cadmium, lead and mercury bioaccumulate in the environment because
very low levels of these pollutants can be retained or stored by organ-
isms until harmful quantities are accumulated (E?A, 1977c). Carcinogens,
mutagens or teratogens are not widespread in textile industry wastes.
However, a few suspected carcinogens may be present depending on use of
solvents, dye carriers and finishing agents such as trichlorobenzene,
polyvinyl chloride, perchloroethylene and others. A teratogenic effect
is one creating abnormalities during gestation. According to the National
Academy of Sciences, teratogenic effects are generally seen only at doses
well above likely exposure levels from disposed solvents and compounds of
mercury, lead, cadmium, and other metals used in textiles manufacturing
(EPA,"1977c).
3-151
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Table 3.39 Drinking Water Limit for Metals and Chlorinated Organics
Parameter
Arsenic
Barium
Cadmium
Chromium
Copper
Iron
Lead
Manganese
Magnesium
Zinc
Total Chlorinated Organics
Limit (ppm)
0.05
1.00
0.01
0.05
1.00
0.30
0.05
0.05
60.00
5.00
0.70
U. S. Public Health Service, Drinking Water Standards, 1962.
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3.8.2 Treatment Alternatives
Treatment, storage and disposal methods usable for wastewater treat-
ment sludge from woven fabric dyeing and finishing operations in the tex-
tile industry are summarized in Table 3.40. The most prevalent method
currently used for the wastewater treatment sludge are lagoon disposal or
storage, open dumping, landfill, and landspreading. Most of the sludges
are stored (disposed) in unlined lagoons. Land disposal (open dumping,
landfill, landspreading), both on and off-site are commonly practiced
by the majority of plants. Advanced technology such as use of special
landfilling techniques, chemical fixation, incineration, etc., is seldom
employed by the industry or off-site waste disposal contractors. Dis-
cussions of treatment, storage, and disposal technology which are, or
may be, applicable to wastewater treatment sludge are discussed in the
following sections.
3.8.2.1	Current Practices
For wastewater pollution control sludges, universal practice in
the textile industries would be lagoon for pond settling.
This technique produces a sludge with a solids content from 1 to 10 per-
cent. Some of the ponds are used for aeration or activated sludge treat-
ment. The excess sludge is periodically removed and disposed. About 208
plants or 32 percent of those having their own treatment facilities are
not using pond settling (EPA, 1976c). Because some 46 percent of the
treatment ponds are unlined thus permitting percolation to groundwater,
this treatment practice is considered to be environmentally inadequate
(EPA, 1976c). Discussion of lagoon or pond settling was presented earlier
in Section 3.7.3.1.
3.8.2.2	Best Available Technology
The best treatment technology for wastewater treatment sludge is
solids concentration and dewatering to at least 20 percent solids by
means of centrifugation and filtration. Presently, the sludge from woven
fabric dyeing and finishing is not treated by these techniques. Further
3-153
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Table 3. 40 Summary of Treatment, Storage, and Disposal Technology for Wastewater Treatment Sludge from
Woven Fabric Dyeing and Finishing Operations
Practices	Current or Broad Average	Best Available	Technology Suggested by Related Technology
Treatment	Sludge concentrated to
1-5 percent solids
through the use of
lagoon or pond settling
Sludge concen-
trated to 20
percent solids
through use of
centrifugation
or filtration
Incineration
Storage	Unllned lagoons
Disposal	Land disposal (open
dump, landfill, land-
spreading, or lagoon)
Lined lagoons
Approved land-
fill
Encapsulat ion
Secured landfill
-------
discussions of centrifugation and filtration treatments are presented
in Section 3.7.2.2.
3.8.2.3 Methods Suggested by Related Technology
Incineration is another potential treatment alternative applicable
to wastewater treatment sludge. The two areas of concern related to
sludge incineration are incinerator air emissions, and contaminated ash
containing dye and chemical carrier residue and leachable heavy metals
(EPA, 1976c). The air emissions probably do not differ greatly from
those from incineration of municipal trash or activated sludge, since
dyes and chemicals usually constitute a minor portion of the wastes.
Therefore air pollution abatement facilities of normal capabilities will
be required. The major concern is the incineration end-product, ash,
which contains a significant quantity of heavy metal contaminants and is
considered a potentially hazardous material. Disposal of the ash in an
approved or secured landfill is environmentally adequate (EPA, 1976c).
At present,' most of the textile plants do not incinerate wastewater
treatment sludges because of high costs of environmentally adequate
incineration equipment and the high cost of fuel. Detailed discussions
of the incineration process are presented in Section 3.2.2.2 and 3.2.2.3.
It is estimated that on-site incineration of wastewater treatment sludge
from textile industries will cost approximately $100 to $300 per metric
ton of dye solids, in 1975 dollars, based on charges cited by a con-
tractor (EPA, 1976c).
3.8.3 Storage Alternatives
3.8.3.1 Current Practices
Wastewater treatment sludges from woven fabric dyeing and finishing
operations are currently stored or retained in wastewater treatment sys-
tems, either in disposal ponds or in the bottom of ponds or lagoons used
for aeration and activated sludge treatment. The sludge will eventually
reach the capacity of the pond or lagoon and other storage will become
3-155
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necessary. These storage ponds are usually unlined, which may result in
percolation to groundwater supplies (EPA, 1976c). Therefore, present
storage technology is considered not environmentally adequate.
3.8.3.2	Best Available Technology
As mentioned previously, storage ponds in the woven fabric dyeing
and finishing operations are usually unlined. Lining the ponds would
be the best method of preventing leachate from reaching groundwater.
This technology is widely used in this and other industries. Lining
materials employed can be plastic sheeting, clay or concrete. The dis-
advantages of this method include possible chemical attack or the inad-
vertent cracking of pond liner, and costs of lining ponds will be high.
Table 3.41 gives estimates of installed costs for various types of pond
liners (EPA, 1976c).
A typical pond size used in the woven fabric dyeing and finishing
operations is 0.38 hectare (0.9 acres). Estimated costs for cleaning
and preparing the typical pond prior to installation of liners are:
Pond Size
0.38 ha. (0.9 acre)
Cleaning of existing pond	$18,750
($10 per m^ of removed sludge)
Earthwork on existing pond	$ 1,250
($1 per m of earth moving)		
Total Cost	$20,000
The estimated costs are based on 1975 dollars (EPA, 1976c)
3.8.3.3	Methods Suggested by Related Technology
Encapsulation is used primarily for those hazardous wastes not
amenable to other pretreatment methods. Candidate wastes include
sludges containing toxic compounds, and arsenic waste compounds. Encap-
sulation of a waste usually involves packaging and containment of a
specific quantity of a hazardous waste to prevent leaching. This is
3-156
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Table 3.41 Estimated Installed Costs for Various Types of Pond Liners
(EPA, 1976c)
Liner Material	Installed Cost $/sguare meter*
Thin Clay liner (2 inch)
2.50
Sprayed asphalt
2.50
20 millimeter PVC
3.70
30 millimeter Hypalon
7.40
Concrete
10.00
Thick Clay liner (2 feet)
10.00
^Estimated costs are based on 1975 dollars.
-------
achieved by forming a watertight jacket around the waste. Materials used
to form this capsule include concrete, polyethylene or polyurethane
polymers, asphalt and tars. Prior to actual covering, the wastes are
usually agglomerated with a binder. Materials that have been used as
binders include cement, asphalt, polybutadiene, and other polymers (Wiles
and Lubowitz, 1976). Further discussion of the encapsulation technique
is presented in Section 3.2.3.3.
This encapsulation technique could be applied for storage of waste-
water treatment sludge generated by the woven fabric dyeing and finishing
operations. Presently there is no indication that this technique is prac-
ticed by the textile industries. Encapsulating a waste could cost an
estimated $40 to $85 per ton of dry waste (Buck and Lobowitz, 1974). The
estimated cost is based on 1973 dollars.
3.8.4 Disposal Alternatives
3.8.4.1 Current Practices
A 1976 EPA study estimates that approximately 68 percent of woven
fabric dyeing and finishing operationsdischarge their wastes into a
municipal system without any treatment. Only 208 plants (32 percent)
have their own wastewater treatment facilities and retain sludge in un-
lined aeration ponds (EPA, 1976c). Of the 208 plants with treatment
systems, eighty-six (41 percent) disposed of sludge. Current disposal
practices used for the wastewater treatment sludge are lagoon disposal,
open dumping, landfill and landspreading. Most wastewater treatment
sludges are disposed or retained in unllned disposal lagoons. Open
dumping of sludge, both on and off-site is practiced by some plants.
Most landfilled sludge is mixed with municipal refuse and other organic
materials. A few plants dispose their sludge on-site by landspreading
on fields around the treatment facilities. One plant disposes the
sludge off-site by allowing an employee to haul the sludge to his farm
for use as fertilizer (EPA, 1976c).
3-158
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Current disposal technologies employed by the industry are consid-
ered to be environmentally inadequate, because sludge retention in un-
lined lagoons could result in percolation to groundwater supplies, and
land disposal of sludge by landfllling or landspreading in uncontrolled
facilities can lead to leachate and surface water run-off problems.
The textile Industry has claimed that the wastewater treatment
sludge is comparable to common municipal sludge. Apparently, heavy
metals in the sludge from the textile mills (Table 3.38) are higher
than the heavy metals in selected municipal mills (Table 3.42). Heavy
metal uptake by plants grown on the land used for sludge disposal and
incorporation into the food chain is likely. Surface water run-off
problems al9o may occur during heavy rain.
3.8.4.2	Best Available Technology
The best available disposal technology for wastewater treatment
sludge from woven fabric dyeing and finishing operations would be an
approved landfill. Presently, this disposal technique has not been
employed in the textile industries. An EPA study indicated that ap-
proved landfill liners may deteriorate and may not provide adequate
protection for long-term disposal (EPA, 1976c). In addition, there
are very few approved landfills near most textile industry plants.
Further discussions of approved landfill and its cost can be found in
Section 3.7.4.2.
3.8.4.3	Methods Suggested by Related Technology
At present, secured landfill is generally the best available land-
filling technique suggested by related industries. This technology is
considered adequate to prevent environmental damage to air, ground and
surface waters on a long-term basis. Detailed discussions of secured
landfill, including costs, were previously described in Section 3.2.4.2
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3.8.5 Recommended Treatment and Disposal Techniques
The most acceptable treatment and disposal methods for wastewater
treatment sludge from woven fabric dyeing and finishing operations in
the textile industry would be disposal of the dewatered sludge (20 per-
cent solids) in approved landfills. This technique provides environmen-
tally adequate disposal of this sludge and the technology is widely used
and demonstrated in this and other industries. Landfill liners may de-
teriorate and will not provide adequate long-term disposal, so secured
landfill may be the next best available alternative for ultimate disposal
of this waste.
3.8.6 Environmental Impact
Table 3.43 shows estimated emissions of chlorinated organics in
wastewater treatment sludge. MATE values were not available. Further
Investigation, such as actual chlorinated organic measurements, would be
necessary to determine emissions more accurately.
Table 3.44 compares metallic composition of wastewater treatment
sludge from woven fabric eyeing and finishing with State of Illinois
criteria. A narrative from the Illinois criteria which describes methods
for disposal for Alternatives I, II and III is given in Section 3.7.6.
From this comparison, assuming a high degree of leachability, the charac-
teristics of an acceptable disposal site may be determined.
From this analysis, it appears that Alternative III must be
chosen due to the high concentration of zinc in the sludge. Therefore
Alternative III disposal methods would probably have to be used for
disposal of this sludge in the State of Illinois.
3-160
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Table 3.42 Summary of Major and Minor Elements in Sludge (Dean et al, 1974)
(mg/kg dried sludge)+

Primary
Activated
Digested
Element
Sludge
Sludge
Sludge
Aluminum
5.1
10.0
17.9
Antimony
n.a.*
n.a.
0.9
Arsenic
1.2
1.2
n.a.
Barium
2.2
1.2
1.4
Beryllium
0.0025
0.0035
0.0025
Boron
0.10
0.70
0.046
Cadmium
0.19
0.35
0.26
Calcium
n.a.
13.0
33.5
Chromium
2.0
4.3
2.3
Cobalt
0.22
0.002
n.a.
Copper
2.0
1.1
1.6
Gallium
0.06
0.05
0.05
Iron
16.1
40.5
30.6
Lead
1.0
1.5
1.9
Magnesium
10.6
7.0
7.5
Manganese
0.78
0.31
0.98
Mercury
0.005
0.02
n.a.
Molybdenum
0.36
0.20
0.25
Nickel
0.52
0.38
0.38
Phosphorus
3.8
19.9
12.8
Potassium
n.a.
4.2
2.8
Silicon'
n *s*
40.0
162
Silver
0.24
0.15
0.20
Sodium
4.0
4.4
6.2
Strontium
0.13
0.16
0.26
Sulfur
n.a.
10.1
12.3
Tin
0.95
0.50
0.60
Titanium
14.8
11.8
14.2
Vanadium
2.1
0.7
5.2
Zinc
6.9
3.3
4.0
Zirconium
1.7
10.0
2.0
*n.a. not available
After Salotto et al, 1971
+Multiply by 1,000 to get mg/kg
3-161
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Table 3.43 Chlorinated Organlcs In Wastewater Treatment Sludge
Estimated Emissions
Current Practice Best Available Transfer of Technology
Media
MATE VALUES
Discharge to
unlined lagoon
Sludge dewater-
ing, disposal
in approved
landfill
Encapsulation, disposal
in secure landfill
Air,
mg/m-*
Health N'. G.
High
Medium
Low
Eco1o8)' n.g.
Water,
mg/1
Health N.G.
High
Med iura
Low
Ecology n.G.
Land,
ug/g
Health N,G*
High
High
Low
Ecology
N.G.
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Table 3.44 Comparison of Wastewater Treatment Sludge with State of Illinois
Criteria
mg/kg of	Illinois Criteria, mg/1
dry sludge	Alt. I Alt. II Alt. Ill
Arsenic
Barium
Cadmium
Chromium (total)
Cobalt
Copper
Iron
Lead
Manganese
Mercury
Molybdenum
Nickel
Zinc
1
39
4.4
1,196
26
652
4,910
36
128
0.35
17
32
2,370
25
75
225
150** 450**	1,350**
Cr+675 225 675
Cr+3500	2,000**	6,000**
500**	2,000**	6,000**
275** 825**	2,475**
25
75
225**
200** 600** 1,800**
250** 750** 2,250**
Total Heavy Metals
9,370
Aluminum
Magnesium
Potassium
Sodium
Strontium
4,640
2,820
3,580
51,300
16
Total Chlorinated Organic
15.2
Suspended Solids
0.88
Total Solids
1.26
*Average of 20 measurements from five plants
**Illinois criteria stipulates that allowable concentrations may double if
waste contains greater than 2.5 percent excess lime alkalinity and quad-
ruple if greater than 5 percent.
3-163
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3.9 SOLVENT-THINNED TRADE SALES PAINT PROCESS LIQUID WASTES
The paint industry (SIC 28511 and SIC 28513) comprises small busi-
nesses which are typically located in larger urban areas. An estimated
65,000 people were employed in these businesses in 1972, including 37,000
production workers. Simple technology and the relatively low capital
investment required to begin production operations have allowed many
small firms to thrive in the paint industry. More than half of the
approximately 1,544 manufacturing plants (who account for less than 5 per-
cent of total industry sales) employ less than 20 people. Approximately
41 percent employ fewer than 10 workers. The four largest firms, Sherwin
Williams, DuPont, PPG Industries and SCM-Glidden, accounted for 30 percent
of total industry sales in 1974 (Sludge Magazine, 1979). Approximately
3.6 million kkg (4 million tons) of paint and coatings were produced in
the United States in 1972 (EPA, 1976c).
Significant industry trends include a decrease in total number of
plants and an increase in average plant size. Small plants with less
than 10 employees lack the necessary capital to make changes in compliance
with safety requirements, including those under OSHA, and with air and
water pollution abatement regulations. The number of these plants is
therefore decreasing.
Larger plants have coped with these changes by making capital im-
provements or changing their production process to produce water-thinned
paints, thus trading off the safety and pollution problems associated
with solvents for the wastewater discharges associated with water-thinned
paints. Certain specialized uses for solvent-thinned paints will, how-
ever, remain until satisfactory replacements are found. For example,
paints used in marine environments are nearly always solvent-thinned.
Although many paint plants produce both solvent-thinned and water-
thinned paints, approximately 44 percent of the industry does not dis-
charge any wastewater, probably indicating exclusive solvent-thinned
paint, lacquer, industrial finish, putty and miscellaneous paint product
production. However, 75 percent of the 1,374 plants identified in the
3-164
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EPA Water Effluent Guidelines Development Document for paint manufactur-
ing produce some water based paint (Sludge Magazine, 1979).
3.9.1 Manufacturing Process and Wastewater Characterization
Batch processes involving sizing and mixing are utilized to produce
various solvent-thinned paint formulations. A general process flow dia-
gram is shown in Figure 3.18.
Although the process itself is simple, a wide variety of products
are produced for very specific end uses. This necessitates utilization
of up to 1,500 to 5,000 different raw materials, depending on size of
manufacturing operation, to produce a relatively complete line of paints.
Paint formulations are also varied to enhance certain desirable properties.
In Table 3.45, formulation changes for various paints are shown. High
gloss paints are very washable, but have low hiding properties; flat
paints, however, have better hiding power but low washability. Minor
ingredients such as antisettling agents, fungicides and leveling agents
are omitted because they vary depending on end use and never comprise
more than 1 percent by weight of product (Sludge Magazine, 1979).
There are no identifiable by-products normally associated with the
solvent-thinned paint manufacturing process.
Waste streams and 197A quantities are shown in Table 3.36. Process
liquid wastes include cleanings, spoiled batches and spills and total
92,300 kky/yr (101,400 ton/yr). Approximately 15 percent, or 14,265 kkg/yr
(15,734 tons/yr) of this waste stream sire solvents. Approximately 0.7 per-
cent, or 636 kkg/yr (700 tons/yr) are toxic chemical compounds in the
waste stream (EPA, 1976c).
Solvents are used for cleaning of process equipment prior to shut-
down and before a substantial change in color of paint or type of raw
materials used. Often solvents with higher boiling points than those
used in the paint being processed are used for cleaning, due to lower
cost and reduced evaporation losses. If the solvent used for cleaning
is identical to the solvent used in the paint, then reuse of cleaning
solvent in subsequent paint batches may be facilitated. Volume of
3-165
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PIGMENT AND
EXTENOER
STORAOE
OIL

*
HIGH SPEED

STORAOE


MIXERS





1
U>
I
CT
PLASTICIZER
STORAOE
U	
ADDITIVES
STORAGE
RESIN


BALL
OR
I
STORAOE


PEBBLE
MILL
¦~1
PREMIXINQ
TANKS
SAND
OR
ROLLER
MILLS
THINNING
AND TINTING
TANKS
I
T

CLEANING
SOLVENT TO
RECLAIMING
OR DISPOSAL
PACKAGING
OPERATION
zr
SPOILED
BATCHES
TO DISPOSAL
SOLVENT

STOHAGE

»	
BAGS a DUST
TO
DISPOSAL
Figure 3.18 Solvent-thinned Paint Manufacturing Flow Diagram (EPA, 1976c)
-------
Table 3.45 Typical Formulation Changes to Achieve a Variety of
Coatings (Percentage by Weight)*
Typical Alkyd Finishes

High Gloss
Semi-gloss
Flat
Titanium dioxide
30.0
25.0
20.0
Extenders
—
10.0
25.0
Alkyd solids
40.0
30.0
19.0
Solvents
28.0
33.5
35.0
Driers
2.0
1.5
1.0

100.0
100.0
100.0
Typical Floor Finishes




Clear Oak Stain Brown Enamel
Yellow iron oxide

5.0

Brown iron oxide

20.0
Extenders

5.0

Resin solids
50.0
28.0 40.0
Solvents
47.5
60.0 38.0
Driers
2.5
2.0
2.0

100.0
100.0 100.0
* EPA, 1976 C
3-167
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Table 3.46 Paint and Coatings Manufacture Summary of Total Wastes in 1974
kkg/yr (tons/yr) (Wet weight) (EPA, 1976)C
u>
i
cr«
00
Waste Stream
Cleanings
Raw Material Packaging
Air Pollution Collection
Spoiled Batches
Spills
TOTAL
Total WaBte
82,000( 90,000)]
302,000(333,000)
1,600( 1,700)
4,900( 5,400)'
5,400( 6.000)
395,900(436,100)'
Potentially
Hazardous
Waste Stream
82,000( 90,000)
2,000( 2,200)
1,600( 1,700)
4,900( 5,400)'
5,400( 6,000)
95,900(105,300)'
Hazardous
Solvents
In Waste
13,600(15,000)
580( 640)
85( 94)
14,265(15,734)
Toxic
Compounds
In Waste
590(650)
128(140)
80( 88)
41( 45)
5( 5)
844(928)
2 Includes	about	25 percent water.
^ Includes	about	5 percent water.
^ Includes	about	6 percent water.
Includes	about	22 percent water.
-------
equipment cleaning wastes requiring disposal depends more on frequency of
shutdown, frequency of color and raw material changes and the extent to
which recovery for reuse in the product or for reuse in subsequent equip-
ment washings is practiced, rather than on plant production. A typical
3,800,000 liter (1,000,000 gal) per year plant which produces both water-
and solvent-based products would normally use about 9 kkg (10 tons) of
waste cleaning solvent per year (EPA, 1976c).
According to a 1974 survey, finished products which cannot be sold,
or recycled to the process, due to quality control restrictions, comprise
a waste stream amounting to 0.2 percent of total production (EPA, 1976c).
Spills are normally collected and recycled to the process when
quality control requirements permit. If any portion of a spill cannot
be recycled, it is normally collected using absorbent materials and
disposed.
Warehouse stocks, unsold within their expected shelf lives, are re-
claimed for reuse in the process when economically feasible. The effort
required to open small containers and return the contents to the produc-
tion process probably exceeds the economic gains to be realized.
The quantity of spoiled batches, spills and stored product wastes
depends more on plant housekeeping and the types of products manufactured
than on production quantity. A lower volume of product wastes is gene-
rated from paints which contain significant amounts of toxic metals such
as cadmium and chromium because the value of the metals justifies the
effort to reclaim smaller quantities.
Variability of waste streams is high due to the variety of raw mat-
erials used in the industry, the batch operation of both process and
equipment cleanings, and the unpredictability of spoiled batches and
spills.
Waste streams include components of the paint product, solvents,
still bottoms and sludges from solvent reclaiming, and absorbent used
for spill cleanup. A typical paint formulation is given in Figure 3.19.
3-169
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More detail may be derived from lists of materials used in various paint
formulations tailored to a specific end use. Tables 3.47 through 3.51
show these materials. These tables refer to use in 1972, in the entire
paint industry. Therefore, the figures give only relative usage data
for the solvent-thinned trade sales portion of the industry.
Although process liquid wastes are normally considered ignitable
and volatile, these waste streams are difficult to assess accurately
because of the variety of components and their toxicities, as evaluated
in the Sax toxicity rating (Sax, 1975). Toxicity of raw materials used
in paint plants is shown in Table 3.52. As previously mentioned, the
presence of valuable constituents in paint products, such as heavy metals
and organic solvents, encourages reuse of waste streams in the process,
and recovery of solvents.
A further difficulty with handling actual waste stream is the wide
variety of products. Solvent-thinned paint, water-thinned paint, and
varnishes made by many plants, and many of the other waste streams are
usually disposed together.
3-170
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MATERIAL
Composition
Weight Percent Volume Percent
Pigment:
Titanium Dioxide	29	9
Solvent:
Mineral Spirits	15	22
Resin:
Long oil, tall oil alkyd (70% NVM)	52	65
Additives:
Suspension and flow agent	<1	<1
6% Cobalt naphthenate	<1	<1
4% Calcium naphthenate	<1	<1
6% Zirconium drier catalyst	<1	2
Antiskinning agent	<1	<1
100	100
Figure 3.19 Typical Solvent-thinned Paint Formulation (EPA, 1976) c
3-171
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Table 3.47 Estimated Pigment Usage by Paint Industry, 1972
LEAD
*Basic lead carbonate
*Basic white lead silicate
*Red lead
*Other lead pigments
Usage
Million lbs/yr	Thousand kkg/yr
0.91
2.44
5.94
4.70
0.41
1.10
2.70
2.13
WHITES
*Antimony oxide
Lithopone
Titanium dioxide, pure
Titanium dioxide, extended
(usually 50% HO2)
*Zinc oxide, leaded
Zinc oxide (pure)
Other white pigments
0.52
4.78
592.69
26.26
0.70
22.22
0.71
0.24
2.17
268.84
11.91
0.32
10.08
0.32
BLACKS
Carbon black
Lamp black
Other black pigments (except
black iron oxide)
6.08
2.03
1.57
2.76
1.00
0.77
YELLOW AND ORANGES - INORGANIC
*C.P. cadmium oranges and reds	0.07
*Cadmium lithopone	0.04
*Chrome yellow	29.06
*Molybdate orange	5.02
*Strontium chrornate	0.64
*Zinc chromate	7.33
Other inorganic yellow and orange
pigments	9.17
Organic yellows and oranges	1.67
0.04
0.02
14.35
2.48
0.32
3.62
4.53
0.83
BLUES AND VIOLETS
Iron blue (Milori-Chinese-Prussian)	0.55
Ultramarine blue	0.49
Other inorganic blues and violets	0.10
*Phthalocyanine blue	1.14
Other organic blues and violets	0.13
0.27
0.24
0.05
0.56
0.07
* Indicates hazardous materials.
Based on National Paint and Coatings Association Raw Materials
Usage Survey (EPA, 1976 d) .
3-172
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£
Table 3>.47 Estimated Pigment Usage by Paint Industry, 1972 (continued)
GREENS
*Chrome green
^Chromium oxide and hydrated
chromium oxide
*Phthalocyanine green
Pigment green B
REDS AND MAROONS - INORGANIC
(except iron oxide)
REDS AND MAROONS - ORGANIC
B.O.N, maroon
Chlorinated para reds
Lithol red and rubine
Other organic reds and maroons
FLUSHED COLORS
AQUEOUS DISPERSIONS
Hansa yellow
Iron oxides
*Phthalocyanine blue
*Phthalocyanine green
Toluidine red
Other aqueous dispersions
Other pigment dispersions
METALLIC
Aluminum pastes
Aluminum powder
Bronze powders
*Copper powders
Other metallic flakes
IRON OXIDES
Synthetic iron oxides (reds)
Synthetic iron oxides (yellows)
Synthetic iron oxides (other)
Natural iron oxides
Ochres, siennas, and umbers
EXTENDERS
Calcium carbonate - precipitated
Calcium carbonate - natural
Magnesium silicate (talcs)
Barytes - natural
Diatomaceous earths
Million lbs/yr
0.90
2.31
1.09
0.02
3.68
0.37
0.21
0.15
3.98
2.48
0.84
12.51
0.41
0.49
0.11
5.38
5.85
10.70
0.33
0.21
0.16
0.80
12.91
17.46
4.95
6.05
3.41
75.78
185.18
137.11
50.02
31.11
Thousand kkg/yr
0.44
1.14
0.54
0.01
1.82
0.17
0.10
0.07
1.80
1.12
0.38
5.67
0.18
0.22
0.05
2.44
2.65
4.85
0.15
0.09
0.07
0.36
5.86
7.92
2.25
2.74
1.55
34.37
84.00
62.19
22.69
14.11
3-173
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£
Table 3.47 Estimated Pigment Usage by Paint Industry, 1972 (concluded)
EXTENDERS (continued)
Koalin (calcined and other clays)
Mica, dry and water-ground
Silicas, ground
Other extender pigments
Usage
Million lbs/yr	Thousand kkg/yr
160.17
20.14
154.56
75.66
72.65
9.14
70.11
34.32
MISCELLANEOUS
*Cuprous oxide
Fluorescent pigments
Zinc dust
Other miscellaneous pigments
3.35
0.15
28.59
4.78
1.52
0.07
13.00
2.17
3-174
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Table 3.48 Estimated Resin Usage by Paint Industry, 1972a
RESINS FOR SOLVENT-THINNED
VEHICLES**
Acrylic, lacquer type
Acrylic, thermo-setting type
Alkyds
Epoxy resins
Epoxy ester resins
Hydrocarbon resins
Maleic resins
Phenolic resins, pure
Polyurethane resins
Silicone resins
Urea and melamine formaldehyde
res ins
Vinyl (formal and butyral)
acetal resins
Vinyl acetate solution-type
copolymers
Other solvent-phase resins
Usage
Million lbs/yr	Thousand
(Dry weight)c	kkg/yr
8.41
43.36
211.41
68.84
7.27
19.10
7.27
9.84
12.99
2.85
3.82
19.67
95.89
31.22
3.30
8.66
3.30
4.46
5.89
1.29
16.50
4.22
7.48
1.91
9.65
14.85
4.38
6.74
Based on National Paint and Coatings Association Raw Materials
k Usage Survey (EPA, 1976c).
Substantial amounts of cellulose nitrate, cellulose acetate,
cellulose butyrate, and ethyl cellulose are used as resins in
coatings, particularly lacquers. However, production data on
these products are withheld to protect the interests of a very
limited number of producers.
Most of these resins are normally sold in solution, so it can be
assumed that they are usually accompanied by an equal weight of
solvent.
* These materials are not considered hazardous by the industry.
3-175
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Table 3.49 Estimated Drying Oil Usage By Paint Industry, 1972a
OILS*
Castor oil, raw
Castor oil, dehydrated
Tung oil
Coconut oil
Linseed oil
Safflower oil
Soybean oil
Fish oil
Other oils
Usage
Million lbs/yr Thousand kkg/yr
3.50
8.08
15.21
6.24
88.63
15.32
62.16
1.17
22.22
1.59
3.67
6.90
2.83
40.20
6.95
28.20
0.53
10.08
FATTY ACIDS*
Coconut
Linseed
Soybean
Tall oil
Other fatty acids
0.62
6.06
4.55
46.87
8.36
0.28
2.75
2.06
21.26
3.79
a Based on National Paint and Coatings Association Raw Materials
Usage Survey (EPA, 1976 c).
* These are generally not considered hazardous materials.
3-176
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Table 3.50 Estimated Solvent Usage by Paint Industry, 1972a
ALIPHATIC HYDROCARBONS
Usage
Million gal/yr	Million liters/yr
*Mineral spirits, regular and
low odor	63.74	241.26
*Mineral spirits, odorless	12.28	46.48
*Kerosene	1.66	6.28
*Mineral spirits, heavy	5.17	19.57
*Other aliphatic hydrocarbons	30.69	116.16
AROMATIC AND NAPHTHENIC HYDROCARBONS
*Benzene	0.96	3.63
*Toluene	52 .'73	199.55
*Xylene	66.92	253.29
*Naphtha, high flash	13.90	52.61
*0ther aromatic hydrocarbons	29.57	111.92
TERPENIC HYDROCARBONS
(Pine Oil and turpentine)	0.98	3.71
KETONES
*Acetone	134.70	509.84
*Methyl ethyl ketone (MEK)	114.78	547.99
^Methyl isobutyl ketone (MIBK)	57.75	218.58
*0ther ketones	10.29	38.94
ESTERS
*Ethyl acetate	6.01	22.75
*Isopropyl acetate	5.81	22.14
*Normal butyl acetate	65.36	247.39
*0ther esters	43.12	163.21
a Based on National Paint and Coatings Association Raw Materials
Usage Survey (EPA, 1976c)-
* Indicates hazardous material by DOT.
3-177
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Table 3.51 Estimated Miscellaneous Materials Usage, 1972a
Usage
Million lbs/yr	Thousand kkg/yr
ANTI-SKINNING AGENTS	4.90	2.23
METALLIC SOAPS
Aluminum stearate	0.32	0.15
*Zinc Stearate	1.52	0.69
Calcium Stearate	0.23	0.10
Other metallic soaps	0.28	0.12
BODYING AGENTS, SOLVENT SYSTEMS
(other than above)	4.91	2.23
DISPERSING AND MIXING AIDS	25.51	11.57
DRIERS
Calcium soaps	1.90	0.86
*Cobalt soaps	3.97	1.80
*Lead soaps	5.40	2.45
Manganese soaps	1.53	0.69
*Zirconlum soaps	.1.73	0.78
Other driers	1.55	0.70
FUNGICIDES. GERMICIDES. AND
MILDEWCIDES
*Phenols, halogenated phenols, and
their salts	0.41	0.19
*Phenyl mercuric acetate	0.88	0.40
*Phenyl mercuric oleate	0.19	0.09
Others	3.19	1.45
£
Based on National Paint and Coatings Association Raw Materials
Usage Survey (EPA, 1976c)•
* Indicates potentially hazardous materials.
3-178
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Table 3.52 Toxicity of Raw Materials Used in Surveyed Paint Plants
Sax
Toxicity

°L
Antimony Trioxide
Antimony Trisulfide
Asbestos
Barium Carbonate
Barium Lithol
Barium Metaborate
Cadmium Selenide
Chlorinated Paraffin
Chlorinated Rubber
Chrome Oxide
Cobalt Naphthenate
Copper Naphthenate
Cuprous Oxide
Lead Carbonate
Lead Chromate
Lead Molybdate
Lead Monoxide (Lithage)
Lead Naphthenate
Lead Phosphate
Lead Silicochromate
Lead Sulfate
Lead Tetroxide
Mercury Drier
Pentachlorophenol
PMA
PMO
Copper Phthalocyanine
Phenyl Mercuric Succinate
Strontium Chromate
Tributyl Tin Fluoride
Zinc Chromate
Zinc Naphthenate
Zinc Peroxide
Zinc Phosphate
Zinc Resinate
Zinc Stearate
3
3
2
1
3
3
0
3
2
2
3
1
No reference
No reference
3	3	Var. 3
No reference
No reference
3	4	3	3
114	4
12	11
12	11
0	3	0	3
3	3	3	3
0	3	0	3
0	3	0	3
0	3	0	3
0	3	0	3
No reference
0	3	0	3
No reference
No reference
3	3	2	2
Primary irritant
No reference
No reference
No reference
3	4	3	3
No reference
3	4	3	3
Variable, generally low
Variable, generally low
No reference
No reference
Variable
A^ a Acute Local
Ag = Acute Systemic
C = Chronic Local
L
Cg = Chronic Systemic
3-179
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Table 3.52 Toxicity of Raw Materials Used in Surveyed Paint Plants
(concluded)
Acetone
N-Butyl Acetate
Ethanol
Diacetone Alcohol
Ethyl Acetate
Heptane
Hexane
Isopropanol
MEK
MIBK
Methanol
Mineral Spirits
Toluene
VM&P Naphtha
Xylene
Sax
	Toxicity		
tk S ft fs
2 2	11
12	11
12	11
12	11
12	14
1114
12	4 1
12	14
2 3	4 4
13	12
12	4 4
12	12
2 2	11
2 2	11
12	12
3-180
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3.9.2 Treatment Alternatives
3.9.2.1 Current Practice
Current practice is to dispose a large portion of liquid process
wastes on land. As of 1974, approximately 35 percent of plants recover
at least some solvents. Almost all plants disposed at least some wastes
off-site (EPA, 1976c). Based on the small number of secured landfills
in existence, disposal must be in either open dumps or sanitary landfills.
Although solvents are becoming more expensive with decreased availability,
it appears that a great number of small plants in the industry have not
solved the logistics of recovering solvents themselves or finding an
off-site solvent recovery contractor. Problems encountered by paint
producers include the capital investment necessary for installing an
on-site solvent recovery unit and/or incinerator, locating off-site sol-
vent recovery contractors, storing and handling small batches of wastes
to minimize workplace hazards, and optimizing the value of wastes by
keeping pure solvents and spoiled product batches in separate containers
for each product. Wastes in small quantities must be accumulated to make
hauling to the recovery site economical. For small plants, accumulation
of a full truck load of wastes may take days, not accounting for high
volume spills and spoiled batches that may occur at infrequent intervals.
Haste product collected on cleanup absorbents and still bottoms,
residue and waste scrubbing solution from on-site solvent recovery units
and incinerators are normally land disposed.
Cost of disposal has been estimated at $9 to $20 per metric ton
based on the necessity of hauling wastes to a site and disposing of it.
One major paint plant is paying as much as $87 per metric ton for flam-
mable liquid disposal. Variability in costs stems from disposal method
utilized and hauling distance. Cost information by disposal method was
not found in the literature. Another estimate can be obtained by assum-
ing $8 per cubic meter ($7 per cubic yard) for handling and storage at
the plant site and an additional $8 per cubic meter ($7 per cubic yard)
for disposal. Hauling costs are estimated at $0.20/ton-mile, which leads
to hauling costs of $20 for a 16,000 meter (100 mile) trip, which is
3-181
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likely to occur for some plants. On this basis, disposal costs could
easily reach $40 per metric ton ($36 per ton).
3.9.2.2 Best Available Technology
Although many plants incinerate their process liquid wastes, it
appears that a better use of a valuable resource is solvent recovery.
Many plants use contract haulers which recover solvents for resale or
"launder" them for reuse in the same plant. A few plants have recently
installed package solvent recovery units (see Section 4.0).
Additionally, spoiled product and spills should be reused in
the process where feasible. Residues from solvent recovery are
normally landfilled. Other process liquid wastes such as spills
collected on absorbents and spoiled product and spills that are not
reusable in the process are also landfilled.
Incineration of solvent recovery residue is complicated by fine
particulates which could make air quality compliance difficult.
Volume reduction achieved by incineration of paint residues may not
justify use of incineration in many cases. The presence of metals
in the residue may restrict use of incineration unless metals are
removed (Rollins Environmental Services, personal communication,
1979). So landfilling is recommended for solvent recovery residues
and other process wastes, volume is reduced considerably by solvent
recovery, thus reducing disposal costs.
Costs of solvent recovery depend on the use of off-site
contractors versus purchase of on-site solvent recovery equipment.
Purchase of equipment is becoming more attractive to the paint
industry, because small, low cost package units are being produced
and can be afforded by more paint plants.
Although an average cost has not been obtained for solvent
recovery equipment, off-site contractors normally pay for used
solvents and pick them up at the plant site. It is assumed that
3-182
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purchase of solvent recovery equipment is more attractive financially
than continuing to use off-site contractors.
Use of solvent recovery techniques is probably now feasible for
some, but not all, plants without process change.
Recovery and reuse of solvents, and process changes to permit re-
cycling of a wider variety of spoiled batches, spills, and stored prod-
ucts, are practices receiving increased attention in the paint industry
and may be currently achievable by some plants. Theoretically, wastes
from the industry should be reduced to residues from solvent recovery
operations and absorbed spills should be disposed with absorbent spill
control materials.
Problems in implementing this technology include a reluctance by
industry (particularly small plants) to change solvent-thinned paint
processes. One reason is the increase in use of water-thinned paints
resulting in decreased usage of solvent-thinned paints, thus diverting
plant funds to emphasize water-thinned paint production. Recent re-
search has resulted in some new paint products which contain as much as
60 percent less solvent and can be cleaned up with water. Although the
future looks bright for these and other reduced-solvent paints, their
performance has not been completely proven and much more research is
necessary to develop a replacement for solvent-thinned paints (National
Paint and Coatings Association, personal communication, 1979).
Not all spills and spoiled batches are recoverable by a given plant.
Quality control specifications required by the customer, particularly
color, limit quantities and types of paints which can be reblended in
the process. In addition, paint components such as polymers, silicones
and wetting agents must be compatible for successful recycling. Ease
of recycling is complicated by the increasing number of paint products
produced at a facility and decreasing product quantity required in a
given production run. Recycling in a plant of this type requires much
storage space and strict adherence to separation of waste product types
during storage. Most plants, particularly smaller plants, do not have
proper storage space to meet safety and environmental requirements and
do not have the personnel to give this matter their full attention.
3-183
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For successful implementation of best available technology,
plant operators must become aware of the disposal alternatives for
paints and solvents and be able to apply the best alternatives to a
particular plant. An industry trade group, the National Paint and
Coatings Association (NPCA), has recently taken steps to make
information on recycling and solvent recovery that complies with
current and upcoming regulations, and waste management in a small
plant, topics for discussion at their 1979 annual conference
(NPCA, personal communication, 1979). Cost estimates and engineering
aspects of this technology will vary tremendously. Most of the
technology consists of changes in operation to allow recovery of
valuable raw materials and product. Therefore, the relatively
small investment necessary may be offset to a large extent by the
value of recovered materials.
3.9.3 Environmental Impact
Table 3.53 gives estimated emissions from process liquid wastes.
More research is needed to provide better estimates. The environmental
impact of best treatment, storage and disposal technologies includes
possible air emissions from solvent recovery, and emissions to water
and soils from disposal of residues.
The impact of solvent recovery techniques is much less, because
small quantities of waste are disposed.
The environmental impact of other methods of disposal used in
the industry also should be considered. Some plants, particularly
in the Northeast, collect solvent washings in drums. The drums are
stored, allowed to settle, and used as supplemental fuel as needed.
The environmental impact could be as low as that for incineration,
depending on the combustion conditions. Assuming that compliance with
3-184
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Table 3.53 Process Liquid Wastes from Solvent-Thinned Trade Sales Paint Manufacture
Current Practice	Beat Available	 Transfer of Technology
Media
MATE Values*
Landfill
Recovery with land
disposal or incineration
of residue
More complete recovery
with land disposal or
incineration of residue
Air,3
mg/m
Health n.G.
High
Med ium
Low
Ecology N(,
Water,
mg/1
Health N-G*
High
Medium
Low
Ecology n.G.
Land,
Pg/g
Health N.G.
High
Medium
Low
Ecoiogy n.G.
*Many solvents arc possible; see Table 3.54.
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air quality regulations is the determining factor in successful use
of this method, the tradeoff in environmental impact is for on-site
combustion versus recovery.
Some work has been done on recovery of wastewater treatment
sludges from water-thinned paint production used in asphalt paving
materials and in cement production for its fuel value in cement kilns
(NPCA, personal communication, 1979).
3-186
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3.10 SCRAP CELLS FROM LI-S02 BATTERY PRODUCTION
Lithium metal SO2 batteries are dry cell batteries which are expand-
ing their market position because they have higher performance standards
than Ni-Cd or other dry cells, along with much longer shelf life and a
broader operating temperature range (-40° to 160°C).
3.10.1 Manufacturing Process and Waste Stream Characterization
The production process involves several proprietary operations
which have not been disclosed to date. The general reaction foT these
batteries is:
2 Li + 2S02-*Li2S204
Storage densities of 95 watt-hrs/lb are attainable for these high-
performance batteries at 2-3 volts. This compares to about 20 watt-hrs/
lb for conventional 1.5 volt carbon-zinc dry cells (EPA, 1975 and
Brunner and Keller, 1972). The amount produced is not known.
The production of Lithium-organic electrolyte -SO^ batteries results
in a waste stream of spent battery cells resulting from quality control
requirements of the production facility. This waste stream is expected
to contain about 1-3 percent, by weight, of the production of a battery
plant (Hehner, 1970).
Components of this scrap cell waste stream include the active in-
gredients of Lithium and S02> organic solvents and other materials. The
expected composition of the waste stream is presented in Table 3.56.
This table shows the contents of the Li-S02 battery both under normal
conditions and in a potentially hazardous form which might result from
reaction in a landfill situation. The table identifies the specific
toxic materials which must be recognized in proposing and evaluating
waste management options. Although disposal may be preceded by storage
or treatment, all waste management options for this waste stream ulti-
mately lead to land disposal. Examination of the characteristics of
land disposal sites as they relate to containment of hazardous compo-
nents of waste is useful in identifying specific disposal characteristics
3-187
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TABLE 3.54. Contents of Li-SC^ Battery (Ref. Slimak, M. et al. 1977b)
Casing: Variable, depending	on battery size and geometry.
Contents: Normal Conditions	(charged cell)
Component	Percent Of Weight
Lithium metal	8
Lithium bromide	4
Sulfur dioxide	46
Carbon	20
Teflon	5
Acetonitrile	16
Polypropylene	2
Hazardous Condition (Resulting from Land Proposal)
Component	Percent of Weight
Lithium	8
Bromine	3
Sulfur dioxide	46
Cyanide	10
Methyl compounds	6
3-188
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which are expected to be effective and treatment alternatives which
could contribute to waste n>anagement improvements through, modification
of waste form or reduction of migration potential. Emissions from
land disposal sites can occur either to air or to the landfill leachate
and runoff.
Atmospheric emissions from this waste stream may result from re-
leases of gaseous components or gaseous reaction products of the battery
wastes. Several potential releases by the gaseous route are presented
in summary fashion in Table 3.55. These air releases are identified as
potential, since their actual occurrence is dependent upon specific re-
actions occurring in the case of and CH^/CH^OH or adequate tempera-
tures being achieved in the case of SO^.
The release to the atmosphere of gas components identified in
Table 3.57 from this waste are likely to occur because of the low mole-
cular weight and small size of the molecules and lack of retention cap-
ability of many landfill covers.
Liquid releases from landfill sites are more complex because cer-
tain contaminants are retained when moving through the ground. This
phenomenon is due to filtration and/or exchange processes. Factors
influencing this retention process include soil properties, water pH,
water composition and water flow patterns.
Soil characteristics of a landfill can vary from clays to silts,
loams, sands or other soil types. Changes in soil types mean that soil
ion-exchange and groundwater/leachate flow characteristics also change.
The extent of the variations which are possible can be seen from the
soil characteristics presented in Figure 3.20 (Ferguson, 1976). It
shows the variation that can occur with critical ion-exchange capacity
and permeability.
Another aspect of soil retention characteristics is selectivity
+2
for certain waste components, such as selective removal of Sr over
K+ when both are present. In general, soils are negatively charged and
therefore act as cation exchangers. Anions (negatively charged particles)
3-189
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Table 3.55 Potential Air Releases from Li-St^ Battery Disposal
Release
Mechanism
Amount
Comment
Reaction product of
H20 and Li
0.14g metallic
Lithium
Fast reaction
S0„
Existing component
of waste
Not Available
Vapor pressure higher than HO
by a factor of 10-100, while its
density is over twice that of air
CH^, CH^OH Reaction products of
organic components
Not Available
Speed of reaction depends on land-
fill conditions
-------
Ion Exchange Capacity
5-100 meg/lOOg
100,
30 V'
loomy
rtr ctftt tond
100
Sond—2 0 to 0 05 mm diom«t*r
S«lt—0 05 to 0 002 mm diom«t»r
Cloy—imolfer ition 0 002 mm dioiMtor
Ion	5 meg
Exchange 100g
Capacity
Organic Matter
Has ion Exchange
Capacity 200 meg/lOOg
COMPARISON OF PARTICLE SIZE SCALES
Sieve openings in inches	U.S. Standard Sieve Numbers
3 2 114 1 % '/j V, 4 10 20 40 60	200
I I I I I I I I	1	1 II I I I III I I I
Ion
Exchange
Capacity
10-20 meg/lOOg
USDA
GRAVE
SAND
S0.T
CLAY
VeryL
coon#00"*
Med
e Very
Fin« 1 fine

G8AVB.
SAND

uses

SILT 08 CLAY
Coarse | Fine
Coarse| Medium |
Fine
"i»i»' «	nun 11 i	i	JJ	i	i j i
100 50	10 52 1 f 0.42 0.25 0.1 f 0.0
J	I	L
l
Excellent
0.05 0.02 aoi 0005 0.0002 0.001
05	0.074
Groin tiz* in
—Permeability	~
Practically Impervious
FIGURE 3.20 Comparison of Soil Characteristics. (Ferguson, 1976)
3-191
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and organic materials are largely unaffected by the ion-exchange process.
For cations (positively charged particles), the general order of prefer-
ence is trivalent ions before divalent ions before singly charged ions.
More specifically, the general ranking of selectivity is Li+2 battery waste stream are hazardous
because of potential detrimental human health effects resulting from ex-
posure. The relative hazards from disposal of this waste stream can be
developed by comparing mobility and toxicity characteristics of the com-
ponents. Table 3.56 provides this comparison, based on available infor-
mation regarding element toxicity and mobility. Several conclusions can
be drawn from the information presented in this table:
•	The toxic hazard is chiefly determined by sulfur and
hydrocarbons in the waste.
•	Cyanide is a moderate toxic hazard in the waste stream
coupled with the high mobility.
•	Lithium presents the least toxic hazard of the waste
constituents examined.
Another hazardous aspect of these waste materials is that they can
produce combustible gases. With Li-S02 battery wastes the sources for
combustible gases are Lithium metal, which can react with water to pro-
duce hydrogen, and the organic electrolyte and its combustion products.
These potential combustion products add inflammability to the hazards
from these battery wastes.
Analysis suggests that any processing performed on battery wastes
be designed to reduce the hazards and problems associated with SC>2,
organic (acetonitrile) materials and metallic lithium. The processes
should modify the sulfur compounds to a less hazardous and/or mobile
3-192
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Table 3.56 Comparison of Hazardous Nature of Li-SO^ Cell Components
CO
VO
OJ
COMPONENT
Molecules
S0r
MASS
TOXIC THRESHOLD
NO. OF DOSES MOBILITY
COMMENT
CH,
CH3OH
Ions
so3
CN~
Li*
ch3
Br"
max g/lOOg waste
46
6.4
12.8
1.1
57
10
8
6
3
13 mg/M
260 mg/H"
210 mg/l°
0.2 mg/l'5
5.mg/l'>
,28
20.3
3.68
.02
.63
High
High
High
High
High
High
Mod era te
High
High
Flammable
Flammable
a from Proposed Guidelines and Regulations and Proposal on Identification and Listing, Federal Register,
Dec 18, 1979, Part IV
b from EC0M-76-1752-1
c derived from 250 mg/1 limit for SO^ based on assumption of SO^ oxidization to SO^
-------
form. The organic materials should be modified to destroy both the
methyl group and the cyanide. Lithium should be converted to a less
environmentally reactive form. In addition, any waste processing
should not cause degradation of waste components into compatible or
toxic compounds.
3.10.2	Treatment
Treatment of this waste stream consists of processes which in some
way modify or fractionate the waste. A summary of these methods has
been listed previously by EPA (EPA, 1974c). Those with a potential
application to scrap cell wastes are the incineration processes, physi-
cal treatment and chemical treatment Included as Appendix C. Of these
waste treatment processes, incineration appears the most effective,
because it destroys cyanide and organic compounds. Other treatment op-
tions involve separation rather than destruction and so appear less
desirable. Of the various incinerator types, the simpler controlled
air type appears to be the most practical for Li-SOj battery scrap cells
because of few moving parts and reduced off-gas handling problems.
There does not appear to be a need for the complexity associated with
fluidized beds, rotary kilns or moving grates. Use of an incinerator,
regardless of its design, requires a pretreatment step to rupture the
battery container mechanically in a completely dry atmosphere to pre-
clude the possibility of battery explosion. An off-gas handling system
will also be required for removal of particulates and SOj from the com-
bustion gases. Lithium is not expected to volatilize, but entrained
lithium compounds could be removed by liquid scrubbers or mechanical
air cleaning devices. Lithium recovery from the air cleaning waste
might be carried out depending on concentration in the waste and the
total volume of waste.
3.10.3	Storage Alternatives
Storage of waste material may represent a hazard potential. If the
battery were to be ruptured, water from the ground, rain or even the air
could react with metallic lithium to form hydrogen (H^), which represents
3-194
\
-------
an explosion and fire hazard. In addition, if high temperature were en-
countered during storage, volatile components such as SO^ and organic
degradation products could rupture cell containers. This could lead in
turn to lithium reaction with atmospheric moisture to produce hydrogen.
Specific methods of waste storage are not as well established as
those for treatment or disposal because of limited use. Specific storage
options which might be utilized for scrap cells are package or bulk
storage.
In package storage, scrap cells would be placed in drums (55 or
30 gallon) or bags and the containers accumulated at a storage area.
It is possible to add material such as cement to the scrap battery cells
to form a more Integral package but it adds to the cost of storage and
increases costs of any reclamation efforts. Bulk storage is possible
utilizing either above or below-grade storage areas. This is a lower
cost storage method, but any hazardous constituents in the waste are more
subject to release.
Besides providing the mechanism for potentially hazardous reactions,
storage increases the costs of total waste management since storage
costs must be added to the costs of ultimate disposal. Storage can be
considered a necessary short term option because of economics of scale
for treatment or because of delays in disposal capacity. It may be more
cost effective to store waste material and wait for the industry.to grow
so that larger processing plants with lower unit cost can be built. In
such cases storage is a waste management alternative which becomes
necessary rather than a primary objective. It is expected that battery
cell storage, if used, will be an interim measure until means for re-
covery of all components are developed or until more cost-effective dis-
posal methods meeting existing standards are found.
Storage of these scrap cells must be accomplished without exposure
to moisture. It would be difficult to store scrap cells for long periods
of time without risking fires or explosions. Storage in inert media,
such as an oil bath, should be considered to reduce risk.
3-195
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3.10.4 Disposal Alternatives
Eventually, whether treated or untreated and whether stored or not
components from the battery waste stream must be disposed. Six disposal
options applicable to waste material have been identified by EPA solid
waste programs for disposal of hazardous wastes (Miarynowski, 1972). Of
these, one is a- storage option discussed in the previous section. Four
others are potentially applicable to spent Li-SC^ battery cells.
These options are landfill disposal, deep well disposal, subsurface in-
jection, land burial.
Landfill disposal is a well-controlled and sanitary method for dis-
posal of wastes upon land. Common landfill disposal methods are:
•	mixing with soil
•	shallow burial
•	combinations of these.
The design and operation of these landfills must integrate the
physicochemical characteristics of both site and hazardous waste.
Deep-well disposal is a system of disposing of raw or treated,
filtered hazardous waste by pumping it into deep wells where it is con-
tained in the pores of permeable subsurface rock separated from other
groundwater supplies by impermeable layers of rock or clay. The depth
of injection varies with local hydrology. Subsurface injection has been
extensively used in diposal of oil field brines. There are between
10,000 and 50,000 brine injection wells in the United States. The number
of industrial waste injection wells in the United States numbers more
than 100. Injection wells can be used by virtually any type of industry
that is located in a proper geologic environment and that has a waste
product amenable to this method. Some industries presently using this
method are chemical and pharmaceutical plants, refineries, steel and
metal industries, paper mills, and coke plants.
Land burial disposal is a method adaptable to those hazardous
materials that require permanent disposal. Disposal is accomplished
by either near-surface or, deep burial. In near-surface burial, the
material is deposited directly into the ground or is deposited in stain-
less steel tanks or concrete lined pits beneath the ground. In land
burial, the waste is transported to a selected site where it is
3-196
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prepared for final burial. At the present time, near-surface burial of
both radioactive and chemical wastes is being conducted at several AEC
and commercially operated burial sites. Pilot plant studies have been
conducted for deep burial in salt formations and hard bedrock. Land
burial is a possible choice for hazardous materials that require com-
plete containment and permanent disposal. This includes radioactive
wastes as well as highly toxic chemical wastes. At the present time,
only near-surface burial is used for the disposal of most wastes.
Ocean dumping utilizes the ocean as an ultimate disposal sink for
all types of waste materials, including hazardous wastes. There are
three basic techniques for ocean disposal of hazardous wastes. One is
bulk disposal for liquid or slurry-type wastes. Another is to strip
obsolete or surplus World War II cargo ships, load the ships with obsolete
munitions, and tow them out to sea, scuttling them at some designated
spot. The third technique is the sinking at sea of containerized
hazardous toxic wastes. The broad classes of hazardous wastes dumped
at sea include:
•	industrial wastes
o obsolete, surplus, and nonserviceable conventional
explosive ordinance
•	chemical warfare wastes
a miscellaneous hazardous wastes.
The technical viability of a specific alternative depends on the
degree of waste treatment, and local geology and hydrology. Deep-well
disposal is feasible only if the waste has been processed to slurries
or solutions and an acceptable injection site is available. The other
waste disposal options — landfill with its many alternatives, land
burial, ocean dumping and engineered storage — are all feasible regard-
less of pretreatment. Their usage depends upon the availability of
specific sites and the economics of each disposal method.
The cost of waste management depends on the nature of treatment
operations, transportation requirements and the disposal costs. These
cost elements are reviewed in the following paragraphs.
The cost of waste incineration includes both capital and operating
costs, which vary depending on specific incineration technology and
facility size. Figure 3.21, derived from a study conducted by General
3-197
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$30,000
v£) Three 100* Ton/Day Units
(Trumbull)
3
a
c	o
a	cq
6	a
a	cq
O
3
C
W (Q
"U
-a
e c
A3 o
C v>
u-i
o
CQ
O
u
25,000
20,000
19,000
10,000
5000
X Garrett
Legend*
# • Water-Wall Incinerators
with Precipitators
0 ° Refractorv Wall Incinerator
^ a Facto r> -Fabricated Incinerator
X ¦ Resource Recovery Processes
Zit}* Landfill (Ref 3>
.Three 175-Ton/Day Units
(Fairfield)
Garrett Frooi Ead Only
Hybrid Process
A. M. KinneyZBlKB^lswedB with
Fuel Drier and Glass/A1 Recovery
CPU-400 Front End
Modified St. Louis Process
J	L
i
X
J	L
_L
_L
X
J
200 400 S00 (00 1000 1300 1400 1800 1S00 2000 2100 2400
Input 
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Electric shows capital cost variation according to incinerator type and
capacity (General Electric Co., 1975). The figure also illustrates cost
changes for variations in off-gas treatment technologies.
Operating cost for municipal incinerators are reported to average
$5/ton. The combination of these costs, when a twenty-year life is
assumed, results in unit processing tests of $10-20/ton of material.
Disposal of solid waste including treated or untreated battery
wastes can be accomplished in a variety of ways. Cost estimates for
the various disposal methods collected from a variety of sources are
presented in Table 3.57.
From the data in Table 3.54 it appears that the most reasonable
waste management options involve landfill disposal with or without
waste incineration. The reasons for these conclusions are:
•	Treatment alternatives other than incineration are
less well developed and offer no potential for re-
ducing the toxicity of the waste.
•	Disposal alternatives other than landfill are very
expensive and do not appear necessary.
It is assumed that decisions on where to locate waste management
activities are made by waste producers on an individual economic basis.
Specific analyses are not done in Lhis section, but could be performed
comparing on-site treatment and disposal costs with off-site trans-
portation, treatment and disposal costs. Costs are expected to vary
with the volume of waste anu the distance between waste generator and
disposal site. An example of the results which might come from such
analysis is presented in Figure 3.22 which is taken from EPA's
Hazardous Waste Analysis (EPA, 1974 b) .
Landfill disposal with and without incineration can be compared
using a cost-benefit technique which presents in clearer fashion the
cost of reducing the waste 9tream hazard using incineration. If only
the liquid leachate hazards are considered, it can be seen from Table
3.56 that there are a potential 4.33 threshold doses in 100 grams,
or 39316 per ton of battery cell waste. Incineration will destroy
the cyanide but probably not SO^. The latter will be captured in a
3-199
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DISPOSAL OF HAZARDOUS WASTES
SOURCE SIZE (lltart/yr)
37,880	378,900	3,785.000	37,890,000	378,900,000
1,000
1,810
ON-SITE TREATMENT
100
1S1
SMALLEST
SOURCE
LARGEST SOURCE
16.1
10
MEAN SOURCE
OFP-SITE TREATMENT
	11.6
100,000,000
100.000
10,000.000
10.000
SOURCE SIZE (0^/yr)
Figure 3.22 Example of the Results of Specific Siting Analysis
3-200
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Table 3.57 Cost Estimates for Various Disposal Methods
DISPOSAL COST SUMMARY
Cost ($/ton)
Reference
Remark
Landfill
1.50 - 2.00
8
Macbeth and Hickman, 1974
Schneider and Piatt, 1974
Deep Well
25-50
Macbeth and Hickiuan
For liquid or slurry
waste form
Land burial
(engineered
structure & con-
tainers)
35
4000-8000
EPA, 1974 b
Macbeth and Hickman, 1974
Surface management
deep geologic management
Ocean Dumping
Note:
Costs scaled to 1979 using Chemical Engineering Plant Cost Index.
-------
In a scrubber and disposed In a landfill. Assuming negligible change in
total waste mass upon incineration, Table 3.58 presents a cost-benefit
comparison for the two procedures. The table shows significant cost
increases for a small potential dose reduction. It should be noted that
leachate rate or transporation costs were not considered in the analysis,
but these will probably not change the net result. It shows incineration
to be the best available technology but possibly not the best practicable
technology based on cost.
3.10.5	Environmental Evaluation
At present, disposal of Li-SC^ scrap cells is in landfills. Esti-
mated emissions to air, water and land from this disposal method are
given in Table 3.59. Air emissions are based on the reaction between
lithium metal and water to produce hydrogen. Water emissions are based
on the formation and release of cyanide in the disposal environment.
3.10.6	Best Available Technology
The best available technology for disposal of the Li-SC^ scrap cell
waste stream is incineration of its disassembled components. Fluegas
scrubbing and land disposal of incineration residue are required.
The most environmentally sound technology would be recovery and
reuse of disassembled parts. Based on practices in other industries,
it appears that this technology is feasible although much research would
be needed to determine the best methods for safely disassembling the
sealed cells.
3-202
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Table 3.58 Cost-Benefit Comparison of Landfill With and Without Prior Incineration
Basis: 1 Ton Cell Waste, 1979 Costs
ALTERNATIVE
Landfill
Incineration & Landfill
COST ($)
5
20
15
POTENTIAL DOSES
39316
393134
182
REMARKS
$5.00/ton for Landfill
$15.00/ton for incineration
Incremental Cost-Benefit Ratio $.08/Potential Dose
Baseline Cost-Benefit Ratio $.00013/Potential Dose
-------
Table 3.59 Li-SC^ Scrap Cell Treatment and Disposal
Estimated Emissions
Current Practice Best Available Transfer of Technology


Landfill
Disassembly, in-
cineration with
fluegas scrubb-
ing and land
disposal of re-
sidue
Disassembly, recovery
of components for
reuse
Media
MATE VALUES



Air,
mg/m^
Health N.C.
High
Medium
Low
Ecology N.G.
Water,
Health N.G.



mg/1
Ecology N.G.
High
Medium
Low
Land,
Health N.G.
High
ledium
Low
"g/g
Ecology N.G.
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3.11 SUMMARY OF WASTE STREAM STUDIES
These ten waste screams coupled with the explosives wastes addressed
in Chapter 5 and solvent studies in Chapter 4 form the basis for evalu-
ation of regulatory options and identification of future research needs.
3.11.1	Manufacturing Processes and Waste Characterizations
An understanding of the manufacturing processes producing the waste
streams studied enabled a better characterization of waste streams based
on estimated variability of the process due to start-up and shut-down,
production of off-specification items, process changes necessary for
different products, necessary equipment cleanup, and housekeeping prac-
tices. Recommendations of process charges to reduce quantities and haz-
ardous properties of wastes produced could result from further studies
of manufacturing processes.
Key references for characterization of the waste streams were the
Assessment of Hazardous Waste Practices series of reports from the EPA
Office of Solid Waste. Apparently further efforts to characterize waste
streams by EPA or industry have not been made.
An important item for future research is the characterization of at
least the most significant IRV wastes. Chemical constituents would be
important, although key properties of entire waste streams such as vapor
pressure at 40°C, flash point, solubility, reactivity, and toxicity may
reveal much about how the waste stream would act in a given treatment,
storage, or disposal environment.
3.11.2	Treatment, Storage and Disposal Options
Incineration, the treatment most often recommended as best available,
will have a financial impact on industry. Normally, industry invests
in equipment that can be used 24 hours a day, seven days a week and has
a payback on the investment of 12 to 18 months. Anticipated regulations
may force industry out of this pattern and into handling wastes with
little or no intrinsic value as if they had great value due to the con-
sequences of mishandling. Some ideas for decreasing the financial
impact of incineration include recovery of heat and recovery of valuable
products of incineration such as HC1.
3-205
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Plants that do not have IRV waste streams that require use of an
incinerator for 24 hours a day, seven days a week will probably incin-
erate other wastes to get as close as possible to continual use. Plants
that do not have large volume IRV wastes are probably better off con-
tracting out the incineration of their wastes. Equipment manufacturers
are beginning to offer much smaller waste incinerators which would allow
more flexibility in the choice of off-site versus on-site incineration.
Equipment malfunctions and maintenance shut down and air emissions
are other potential problems. According to one waste disposer contacted
(see Section 6.9) incineration of IRV wastes is still more an art than a
science. However the same disposer reported that by carefully choosing
which wastes to incinerate and careful blending of wastes with fuel, use
of supplemental fuel has been limited to incinerator start-up and mal-
functions and air emissions have been minimized.
Little specific information on storage of IRV wastes was found. No
storage of IRV wastes was found except for storage in steel drums for
ease of handling. Anticipated regulations may encourage more bulk
storage, which will require further investigation to determine if steel
drum storage will remain an acceptable and cost effective storage
method and if more acceptable and cost effective storage methods exist.
Disposal of IRV wastes is generally clearly defined in the waste
stream discussions. Apparently a wide discrepancy exists between current
disposal methods and those anticipated in the hazardous waste regulations.
Further investigation is needed to determine if adequate disposal areas
will be available to meet the demand.
Costs for implementing treatment, storage and disposal techniques
were in many cases available only on a dollars per quantity of waste
basis. More detailed cost information would require further investiga-
tion, and may not be available. Also, cost/benefit analyses such as
that given in Section 3.10 would allow a more quantitative comparison
between disposal options.
3-206
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3.11.3 Achievement of Most Environmentally Sound Practices
For many waste streams, recovery of valuable constituents or chemi-
cal treatment to convert waste to a salable product comprised the most
environmentally sound practice. Many of the processes mentioned require
further investigation or adaptation to insure broad applicability for
each waste stream.
3.11.4 Environmental Impact of Treatment, Storage and Disposal
Very little quantitative information was available to estimate
emissions, except for the properties of known chemical constituents of
the wastes and its form Csolid, liquid, sludge, tar) for disposal.
The comparison of estimated emissions with Minimum Acute Toxicity
Effluents (MATE's) (Cleland & Kingsbury, 1977) provided a good first
step in attempting to characterize emissions from a waste disposal
environment. However, comparisons with MATE's has its drawbacks, such
as:
•	lack of consideration of the disposal environment
•	lack of consideration for waste form
•	many substances) in waste streams studied were not
covered in MATE's
•	only pure substances are covered in MATE's
•	worst cases were assumed by choosing the most
critical components of wastes for comparison
•	MATE's considers concentration only and does not
consider mass of wastes disposed or emitted, thus
rate of release and dilution are critical factors.
Further investigation is necessary to more accurately determine
estimated emissions and to determine if a more meaningful means of com-
parison exists.
3-207
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4.0 SOLVENT USE AND RECOVERY IN INDUSTRY
Solvents are used extensively by various industries as part of pro-
duct manufacture, purification or application. Associated with the wide
range of solvent uses are varying degrees of solvent recovery. In some
instances solvent recovery and reuse is greater than 99 percent, while in
other cases no solvent recovery is practiced.
In many continuous operations where a solvent is used as part of the
manufacturing or purification process solvent recovery and recycling is a
common practice. In the petroleum refining industry, solvents such as
sulfolane or tetraethylene glycol are used for the recovery of aliphatic
compounds from a mixture of aliphatic-aromatic material (EPA, 1976b).
Similarly, in the metal extraction industry solvents such as organic phos-
phates, amines or ketones are used for recovery and purification of metals
such as uranium, thorium, copper, zirconium, cobalt and rare earths
(Schweitzer, 1979). The explosive manufacturing industry utilizes solvents
such as alcohol and ether in their production processes, and these are re-
covered and recycled to the process for reasons of economics (Shreve, 1967).
The textile industry utilizes solvents such as trichlorobenzene, perchloro-
ethylene and other chlorinated aromatics as dye penetrant aids. These
solvents are not currently recovered but are drummed for disposal (EPA,
1976a). Because of solvent losses that can occur due to water solubility
or vaporization, secondary solvent recovery from these streams may also
be practiced. In batch operations where throughput is generally lower,
solvent recovery is frequently practiced. In the paint manufacturing
industry solvents are a part of the product and spills, reject paint
batches and equipment cleaning represent the only sources of solvent
that might be recovered. Surveys of the paint industry suggest that
about 25 percent of the paint plants perform solvent recovery on site
(EPA, 1976b). The ink and dye industry utilizes solvents in a manner
similar to the paint industry with solvent recovery being the exception
rather than the rule. Metal degreasing operations in almost all metal
handling industries utilize solvents as wash or leach solutions to
remove mill oils and other residue from various metallic items. The
solvent accumulates residues of both a soluble and insoluble nature.
4-1
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Such solvents may be disposed or recovered depending on local regulations
and economies of scale of the operations (EPA, 1976a).
Some of the major solvents which are utilized by the various indus-
tries are identified in Table 4.1. This table shows the formula of the
solvent as well as its boiling point and solubility in water. These
parameters are Important indicators of the solvent's transport potential
by air or water. Several of these solvents are included in Appendix A
which shows vapor pressure, toxicity and NIOSH standards for selected
substances.
Specific amounts of solvents used by the industries are unknown
but some partial data presented in Table 4.2 illustrate that the uses
are large.
It can be seen from this brief review that many solvents are used
in many industries with varying degrees and techniques for recovery.
The next section of this report addresses the solvent recovery techni-
ques that are practiced in various industries.
4.1 SOLVENT RECOVERY METHODS
The recovery of solvent from waste and effluent streams involves the
use of separation technology to either remove the solvent from the contam-
inants or remove contaminants from the solvents. The applicability of
certain technologies depends upon the nature of the separation required.
In examining solvent recovery methods it is useful to characterize the
separation as being liquid-liquid, gas mixture or liquid-solid (Schweitzer,
1979).
Figure 4.1 is adapted from Drew (1975) and is a generalized flow
diagram which shows the feed types and the operations which may be per-
formed as appropriate in solvent recovery. It also serves to identify
the various recovery methods which will be discussed in this section.
Operations on the diagram which are addressed are identified with an
asterisk (*).
Liquid-liquid separations can involve distillation, solvent extrac-
tion, adsorption or decanting.
4-2
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Table 4.1 Typical Solvents
and Selected
Properties

Solvent
Formula
B.P.°C
Solubility in H?0
Trichloroethylene
cihccci2
87
slightly
1,1,1 Trichloroethane
H3CCCI3
74
insoluble
Perchloroethylene
CI3CCCI3
186
insoluble
Methyl Chloride
h3ci
-24.2
400 ml gas/100 ml H2O
Trichlorotrifluoroethane
ci3ccf3
45.8
insoluble
Benzene
C6«6
80
slightly
Toluene
c6h5ch3
110
insoluble
Xylene
c6H4(CH3>2
138-144
insoluble
Cyclohexane
c6h12
81
insoluble
Orthophenylphenol
C^HgOH
286
insoluble
Mineral Spirits



Acetone
ch3coch3
56.2
infinity
Methylethylketone
C2H5COCH3
79.6
very soluble
Methyl isobutyl ketone
ch3-co-c3h9
115.8
1.91 el 100 a
n-Butvl Acetate
CH3COOCAHg
125
I el 100 e
Methvl ether
ch3och3
-23.6
3700 ml eas/100 ml H2<
Methanol
ch3oh
65
infinity
Dioxane
C^Hg02
101-105
infinity
-------
Table 4.2 Solvent Consumption by Selected Industries
-o
i
Industry
Paints
(EPA, 1976 c)
Solvent Metal Cleaning
(EPA, 1977 c)
Electronic Components
(EPA, 1977 e")
Solvent Group
Aliphatic hydrocarbons
Aromatic hydrocarbons
Ketones
Esters
Halogenated
Aliphatic hydrocarbons
Aromatic hydrocarbons
Ketones
Halogenated
Non-Halogenated
Usage 10^ liters/year
(lp6 gallons/year)
428	(113)
621	(164)
1,313	(347)
454	(120)
416	(110)
227	( 60)
45	( 12)
15	( 4)
0.8 (0.2)
1.1 (0.3)
-------
gas mixture
liquid-liquid mixture
liquid-solid
FROM t—
PROCESS—~
.r-
I
Ln
Solvent
Vapors
in Air
X£oncentrate
-------
For distillation there are several alternatives which are considered
here. The alternatives involve different methods of supplying the neces-
sary heat to the solvent solution which is to be evaporated. These methods
are:
1.	Direct Injection of Steam. Steam is injected directly into the
liquid to be evaporated. Solvent vapors pass from the evapora-
tor into a condenser where liquid solvent is collected. This
method is only suitable for those solvents which have low boil-
ing points, are not miscible with water, and can be readily
separated from water. Because of these limitations, this type
of still is not commonly used and is normally confined to small
specialized operations.
2.	Coil Still. The vessel containing the material to be distilled
contains a coiled tube through which steam or hot fluid is passed
to heat the contents. Electric heating coils are also used.
Heat transfer is fast and efficient, providing no fouling occurs
on the heat transfer surface. This type of equipment is not
suitable for reprocessing solvents which have a high solids con-
tent (roughly 5 percent or more) or contain resinous materials
which could polymerize on the colls and require expensive hand
cleaning. Evaporated solvent passes to a non-contact water-
cooled condenser where liquid solvent is collected.
Stills of this type are widely used for reprocessing solvents
such as chlorinated hydrocarbons used in dry cleaning operations.
They range from 28 to 950 liters (8 to 250 gal.) per hour
capacity.
3.	Scraped Surface or Wiped-Film Evaporator. In this device, the
distillation tank is surrounded by a heating jacket and the in-
terior of the cylindrical heated surface is continuously wiped
by blades attached to a central rotating shaft. This is best
suited for use with solvents containing sludge or solids and in-
sures a clean heat transfer surface by its use of mechanical
energy from the agitator.
In addition to utilizing one of the three types of heat addition
systems, a distillation or fractionating column will be required if sepa-
4-6
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ration of volatilized components is necessary. Such a column may utilize
either internal plates or packing to enhance separation.
Solvent extraction involves the use of a second solvent to recover
either the desired solvent material or the undesired contaminants.
The separation technique involves two immiscible liquid phases. It
is an indirect separation technique because two components are not sepa-
rated directly. A foreign substance, the second solvent, is introduced to
provide a second phase. This is in contrast to direct separation tech-
niques, e.g., distillation, where heat is used to provide a vapor phase,
or melt crystallization, where cooling is used to provide a solid phase.
A separation can be performed by solvent extraction whenever the
ratio of one component to another is different in the two liquid phases.
This is the same as performing a separation by distillation whenever the
relative volatility is greater or less than 1.0. The simplest separation
in extraction is when an immiscible solvent can be used to remove one com-
ponent from a binary mixture. For this application, an example is solvent
extraction of solvent from wastewater. This is similar to a stripping or
an absorption step in distillation where mass is transferred between phases.
Solvent extraction is useful as a separation technique when the
material being recovered shows an adequate selectivity or preference for
the second solvent. Efficiencies are attained by staging the contact
operations in the same manner as in multicomponent distillation.
Adsorption involves the retention of the material of interest (in
this case the original solvent) on a solid phase material (the adsorbent).
Activated carbon is the most commonly used adsorbent, particularly for
organic molecules, which most solvents are. The adsorbent is regenerated
using hot gases to reverse the adsorption process. This results
in a vapor phase solvent mixture, more concentrated than the original feed.
This stream will generally have to be treated further before solvent re-
covery is complete.
Decantation is the operation where two liquid phases are separated
on the basis of density differences. The separation may be strictly
gravitational or it may be aided by centrifugal effects or wetting agents.
It will produce a solvent stream which may require further purification if
soluble contaminants are present that restrict subsequent uses.
4-7
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Gas mixture separation includes adsorption, absorption and condensa-
tion.
Gas phase adsorption is similar to liquid phase adsorption in that
material (the solvent) is collected on the exterior surface of an adsorb-
ent. Again it is usually activated carbon which can be regenerated by
purging the equipment with hot gases or steam.
Gas absorption involves the transfer of solvent molecules from the
gas phase into a second solvent phase. The transfer process must be re-
versible in order to recover the primary solvent from the secondary sol-
vent. The operation takes place in mass transfer equipment similar to
distillation and solvent extraction.
Condensation can be used to recover solvent from a vapor phase.
For this to be effective as a separation technique for vapor recovery the
gas phase composition and dew points of non-solvent components must be
such that relatively pure solvent can be condensed.
Liquid/solid separations are useful for material such as used
degreasing solvents which contain solids. The technical alternatives in-
volve variations on filtering. There are three major variations: cake
filtration, depth filtration and surface filtration.
Cake filtration occurs when a liquid containing solid particles is
forced through a porous filter medium which is open enough to allow the
passage of the liquid, but tight enough to retain the solid particles. As
more and more liquid is forced through the medium, the solids form a thick-
er and thicker filter cake. The main characteristic of cake filtration is
that the cake which is formed must be porous enough to permit continued
fluid flow through it as filtration progresses.
In depth filtration, the liquid containing solid particles is forced
through a bed of porous material. The solid particles are trapped within
the relatively coarse interstices of the bed, allowing relatively clear
liquid to pass through. Sand filtration and cartridge filtration exemplify
depth filtration. As solid particles continue to accumulate within the
filter bed, there comes a time when either fluid flow is restricted below
acceptable limits, or solid particles are forced through the bed into the
filtrate. At this time the bed must be regenerated, or the cartridge re-
placed.
4-8
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Surface filtration is essentially a straining mechanism where the
solid particles are stopped by a matrix of controlled pore size. This
case differs from cake filtration in that the flow rate decreases because
of plugging of the matrix pores. The matrix becomes plugged before any
significant cake thickness is attained.
From this review of solvent recovery technologies it is obvious
that there are a large number of techniques available but that specific
process selection must hinge on the nature of the spent solvent, its
contaminants and the purity required in the recovered material.
For example, selection of distillation or adsorption/desorption
methods for solvent recovery would depend on solvent properties, such as
whether single or mixed solvents are to be recovered, and the boiling
points of the solvents.
Treatment at the recovery facility visited as part of this study
was primarily simple decanting. Waste oils and solvents were decanted
and blended to rough equivalents of Number 2 and Number 4 fuel oils and
sold to nearby industries. Oily wastewaters are treated and discharged
to the sanitary sewer. Some distillation of waste solvents is performed
in a pot still, but fractionation has not been attempted. Sludges from
decanting and distillation are removed to one of two company owned secure
landfills. (Visit of February 21, 1980 and Easterbrook, 1979.)
A.2 SOLVENT RECOVERY SYSTEM PERFORMANCE
The effectiveness of a solvent recovery system will vary with the
technology of the system (distillation versus adsorption), with the design
of the system (simple vaporization-condensation versus vaporization-
rectification-condensation) and the method of operation. Generalization
of system performance is not possible, but systems not capable of greater
than about 25 percent recovery are not practical. Some examples of exist-
ing operations which illustrate this point are:
• contract solvent recovery operations average 75 percent
solvent recovery rate (EPA, 1976c).
4-9
-------
•	vinyl monomers and mineral oil are recovered in plant at
99+ percent efficiency (Environmental Science and Technology,
1970).
•	practical activated carbon removal efficiencies are 80 - 95
percent even though 98 percent is possible (Schweitzer, 1979).
4.3 STORAGE OF FEED SOLVENT, WASTE RESIDUES AND RECYCLE SOLVENT
The storage of material is necessary when there is a mismatch be-
tween material generation rate and material consumption. Solvent recovery,
like any other process, has the potential for this mismatch.
When solvent recovery is an integral part of the plant process,
in line tankage is used sparingly except for the recycle solvent storage.
Design of the tanks is done in accordance with American Petroleum
Institute (API) and National Fire Protection Association (NFPA) standards.
Vapor emissions rate is predominantly a function of storage temperature,
and cooling costs have been provided at plants where it has been deemed
necessary. The storage tanks may also have a vapor recovery system
(adsorption or condensation) if the material is valuable enough to justify
the capital expenditures (Newton, 1978).
|
When solvent recovery is not an integral>part of a production plant
containers such as 55 gallon drums are generally used for storage. These
serve as a common package readily handled by both solvent producer and
solvent receiver (EPA, 1976 c; Randall et al, 1976).
The practice of using 55 gallon drums may become less viable when
RCRA is implemented because of the increased sampling requirements. For
liquids, bulk or tank storage may become more viable, because fewer samples
will require analysis, thus a cost savings is realized. The 55 gallon
drum will probably remain in common usage for solid and heavy slurry
wastes. Use of floating roof tanks for bulk storage may be feasible,
although the seal between the floating roof and tank wall is critical and
its integrity must be maintained. Storage of extremely volatile sub-
stances in floating roof tanks may not be feasible due to possible atmos-
pheric emissions.
4-10
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Floating roof tanks are especially applicable for temporary storage
of volatile wastes due to frequent liquid level changes. Evaporation
losses are reduced by limiting the space above the surface of the liquid.
Floating roof tanks are constructed with or without fixed roofs above the
floating roof. The fixed roof design (expansion roof) would be more
amenable to collecting volatile emissions from the tank and routing them
through a carbon adsorption bed for removal of hydrocarbons. In the past,
floating roof tanks have been used to store very large quantities of bulk
volatile liquids. For example, Peters and Timmerhause (1968) listed a
"small" expansion roof tank capacity of 1,500,000 t (400,000 gal.). As
previously mentioned, storage temperature is just as important as tank
design for limiting volatile emissions. Storage tanks may be insulated
or installed entirely or partially underground to keep temperatures as
low as possible. Refrigeration costs are expected to be prohibitively
high, except under special circumstances.
Volatilization of wastes can be reduced by designing tanks so that
their intake pipes are submerged during most of the tank filling opera-
tions. This limits volatilization by not allowing free falling and
splashing of liquids as tanks are filled.
For fire protection all tanks storing combustible wastes must be
grounded.
A solvent recovery facility was visited as part of this study. The
plant itself used to be an old specialty chemical production facility
that was purchased and is still being refurbished in stages according to
need. Its location is such that it is near many industries that use and
dispose of solvents and other chemical wastes. As of May 1979, the
plant was receiving about 50,000 gallons of liquids per day. In addi-
tion to waste solvents and oils, the plant receives and treats acids,
industrial wastewaters and organic wastes. Prior to receiving a waste,
the plant requires specific information from the generator on waste
constituents. Samples are then taken and analyzed before the waste is
transported from the generator. Then wastes are run through a laboratory-
scale process to help determine ease of treatment/recovery and to set
4-11
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fees for handling the waste. These fees range from 11 cents to 3 dollars
per gallon, and are very waste-specific.
Once laboratory analysis is complete, the site operator hauls the
waste to the recovery facility and additional testing is performed before
the waste is pumped from the truck to verify that the waste in the truck
matches the lab analysis.
Finally, oily wastes and solvents are pumped into storage tanks
prior to treatment or recovery. Various tanks are used to store wastes
by NFPA standard levels of reactivity, ignitability and corrosivity.
Tanks are well insulated and are above ground. The tanks are closed.
Empty tanks as well as tank trucks are cleaned frequently. Sludges are
sent to one of two company owned landfills. Liquids are treated in the
plant and discharged to the sanitary sewer. (Visit of February 21, 1980
and Easterbrook, 1975.)
4.4 WASTE TREATMENT ALTERNATIVES
The major treatment option for nonrecoverable waste solvents, sol-
vent sludge and solvent vapors is incineration. Incineration oxidizes
the solvent material to CO2, H2O and oxides of metallic contaminants (ash).
Selection of the most appropriate incineration configuration depends upon
the heating value, solids content and composition of the waste. In addi-
tion, requirements for the incineration of material besides spent solvent
can weigh heavily on selection of incinerator equipment. The major equip-
ment choices are multicell, rotary kiln, fluidized bed and vortex incin-
erators (Witt, 1972; Bowerman, 1970; Dunn, 1975). A brief discussion of
each of these is presented in the following paragraphs.
It is generally considered that two types, namely the multi-
chamber, multicell units and the rotaries, are the most flexible. The
"inline" units have a distinct advantage of allowing the products of com-
bustion from one cell to be used to bring succeeding cells up to tempera-
ture, as well as allowing considerable flexibility for the arrangement of
firing equipment and ash removal on either side of the plant.
4-12
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Rotary-kiln-type furnaces have been used with success in Europe
and the U.S., and are now firing mixed residues that include up to 30
percent plastics in the feed material. The furnace consists of a refractory-
lined cylinder slightly inclined to the horizontal at an angle usually
variable between 2-5° and rotating at slow speed (4-5 rpm). By vary-
ing both the speed of rotation and the inclination of the furnace, the
flow of material through the cylinder and the retention time for combus-
tion can be controlled. When liquids are being fired as well as mixed
solids then these are usually counter-fired at the opposite end of the
furnace from the solid waste feed. Afterburning facilities can be in-
corporated in a separate chamber, and the equipment generally lends itself
to flexible plant layout.
Rotary kiln incinerators offer the advantage of a gentle and
continuous mixing of the incoming wastes, but capital and maintenance
costs are high. These derive from the rigidity of the cylinder and close
tolerances for the roller path drive as well as the high-temperature
seals between fixed and moving parts. Another major disadvantage is that
the cascading action of the burning waste, as the kiln rotates, gives all
the fine ash in the charge ample opportunity to become entrained in the
exhaust gases. The linings suffer both from abrasion and from contact
with distillation products that can penetrate the surface before burning,
thus making it necessary to install dense refractory material of higher
grade than normally required in stationary furnaces.
Rotaries can, in some circumstances, be extremely suitable for
sludge burning. There are also examples to be found of rotaries installed
in combination with separate liquids furnaces, providing a higher degree
of flexibility in the overall design of a multi-purpose destruction unit.
The fluidized bed incinerator is simple and compact, using sand
or some other solid noncombustible material for the bed medium. Limita-
tions are that bed temperature must be less than the fusing temperature
of the bed material and the gas flowrate must be less than the terminal
velocity of the sand. Advantages can be claimed for this type of unit.
The enriched oxygen of the bed coupled with mixing of the sand and waste
aids combustion rate, prevents carbon monoxide emissions and minimizes
4-13
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hydrocarbon emissions; the low uniform temperature within the bed limits
the formation of nitrogen oxides. Addition of limestone to the bed mater-
ial means that the emission of HC1 and sulfur oxides can be reduced.
To date, the principal field of fluidized-bed incinerator appli-
cation has been in the refinery and paper industries where, despite high
installed costs, the economics, with waste-heat recovery, are acceptable.
In other fields, such as burning of municipal sludge, operating costs
have proved to be very high in comparison with other designs and, in
consequence, their use is presently restricted. However, most development
work is at present being undertaken in order to apply the theories to
refuse-burning boiler plants, and there is no doubt that in the course
of this work, acceptable solutions will be found to some of the existing
problems. As a method, the fluidized bed process cannot be considered,
at this time, to have a high degree of flexibility in handling a wide
range of wastes, and power consumption will of necessity remain inherently
high.
The vortex incinerator is a cylindrical refractory-lined vessel
that utilizes several tangentially firing modified oil burners. The gas
flow pattern moves spirally upward. Secondary air is also introduced to
further promote combustion and control the vortex. Such an incinerator
is ideal for solvents with a low solids content and a high heating value.
Increases in solids contents introduce operational problems with equip-
ment erosion and ash removal rates.
Depending on the nature of the incinerator feed and the gas-
solid dynamics within the incinerator, varying degrees of off gas
treatment will be required. Incinerators with high gas flow rates
require significant particulate removal equipment while feed material
with phosphorus, halogens and sulfur will require acid gas removal.
In Denmark, all the municipalities have banded together to construct
and operate a central waste oil and chemical treatment and disposal facil-
ity called Kommunekemi A/S. The operation, which began in 1971, is now
operated by a private firm under contract to the national government.
The treatment and disposal process for waste solvents includes distil-
lation or decanting followed by incineration of residues in a rotary kiln
incinerator. Residue from waste oil recovery is incinerated while
4-14
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water removed in the recovery process is sprayed into a post-
incineration chamber. No information was given in literature on
disposal of incinerator residues. Examples of fees charged for wastes
are given in Table 4.3. (Henriksen, 1974)
4.5 WASTE DISPOSAL ALTERNATIVES
The disposal of solid solvent processing wastes,,whether they be
sludges from recovery, loaded absorbents or incinerated ash, will involve
either landfilling or land treatment. These two disposal alternatives
are examined briefly in the following paragraphs.
4.5.1 Landfill
Landfilling is presently the most widely used method for disposing
of a wide range of industrial waste products. The environmental adequacy
of this method is contingent not only upon the types and characteristics
of generated wastes, but also upon methods of operation and on specific
site geologic and climatologic conditions. Landfilling operations range
from open dumping of waste and debris to controlled disposal in secure
landfills. The range of variation may be realized by considering three
levels of control, which are secure landfill, sanitary landfill and land
burial. Secure and sanitary landfill are described in Sections 3.2 and
3.7. Secure landfill represents excellently engineered burial techniques
coupled with excellent site geohydrology. Sanitary landfill represents
excellently engineered burial with less favorable site geohydrology.
Land burial sites have inadequate protection of water quality, where
wastes would enter directly into ground or surface waters and are accept-
able only for inert wastes which are non-water soluble and non-decomposing.
In general, the environmental adequacy of landfill site of any type
is affected by the following operational and management practices:
(1) The extent of segregation of wastes to prevent mixing of
incompatible compounds, such as solids containing heavy
metals with acids, or solutions with other wastes which
together produce explosions, heat, or noxious gases.
4-15
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Table 4.3 Charges Levied for Treatment and Disposal of Wastes Oils
and Chemicals in Denmark (Henriksen, 1974)
Type of Discard	Rate Per Ton*
• Oil wastes (under 5% water)	$0
Oil wastes (5%-10% water)	$ 3.75
Oil wastes (20%-50% water)	$ 7.50
Oil wastes (over 50% water)	$10.50
Halogen-containing organic solvents	§37.50
Other organic solvents in tankers	$22.50
Other organic solvents in drums	$30.00
*Rates based on approximate Danish kroner-U.S. dollar exchange
4-16
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(2)	The extent to which liquid or semi-liquid wastes are
blended with soil or refuse materials to suitably absorb
their moisture content and reduce their fluid mobility
within the landfill (co-disposal).
(3)	The extent to which acids or caustic sludges are neutralized
to minimize their reactivity.
(4)	Selection of sites in which the active fill area is large
enough to allow efficient truck discharging operations,
as well as to assure that blended wastes may be spread,
compacted, and covered daily with approximately six inches
of cover soil.
(5)	The routing of ground and surface waters around the landfill
site and sloping of cover soil to avoid on-site runoff and
erosion.
4.5.2	Land Treatment
The second major waste treatment alternative for solvent wastes is
land treatment.
Land treatment is a relatively inexpensive method of disposal of
industrial wastes, and is being used by a growing number of waste
handlers. The success of land treatment in the warm southwestern states
has prompted many U.S. industries in colder climates to experiment with
this method of disposal. Species of bacteria, yeast and fungi attack and
break down a multitude of organic compounds. The rate of organic break-
down is a complex relationship between organic content of waste material,
soil water content, microbial population and soil pH.
The operation of a land treatment facility involves the application
of biodegradable material to the land so that it can be broken down by
the microbes. Application rate and material composition must be controlled
in order to maximize organic breakdown rate.
4.5.3	Emissions From Disposal
A recent study performed for the EPA Office of Air Quality Planning
and Standards estimated emissions from disposal of wastes from the syn-
thetic organic chemicals manufacturing industry (SOCMI) (Cudahy and
4-17
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Standifer, 1979). These secondary emissions account for 2 Co 5% of
the total volatile organic compound (VOC) emissions from the SOCMI in
1978. Estimated emissions from waste disposal for 34 of the most
significant organic chemicals, including many high production volume
and high volatility chemicals are shown in Table 4.4. The product
chemicals shown are less than 10% of the industry in number, but
account for more than 70% of the total industry production.
The estimates given were primarily based on the physical and
chemical properties of the major waste components and estimates of waste
compositions and quantities disposed of. Significant sources of
emissions include aqueous waste handling, storage, pretreatment and
final treatment. Additional emissions result from landfilling, surface
impoundment, and incineration of liquid and solid wastes. Handling,
storage and treatment of aqueous wastes account for 50 to 90% of second-
ary emissions.
Additional analysis was performed to relate emissions from waste-
water treatment systems, landfills and surface impoundments. A
theoretical sensitivity analysis performed for hexachlorobenzene,
p-dichlorobenzene, benzene, acetone and acetic acid suggests that for
low water solubility, low vapor pressure chemicals, most of the secondary
VOC emissions will be from wastewater treatment. It was also suggested
that for low water solubility and high vapor pressure chemicals such as
benzene, an increase in secondary VOC emissions from landfill would
occur when compared with wastewater emissions. Secondary VOC emissions
may be higher from landfills than from wastewater when liquid chemicals
with higher vapor pressures and water stability, such as acetone and
acetic acid, are used for comparison. No conclusions were drawn for
surface impoundments, except that secondary VOC emissions from surface
impoundments are potentially significant when compared with landfill
emissions.
Table 4.5 shows a summary of control methods for VOC emissions
from secondary sources. Waste source controls result in reduction or
elimination of emissions by changing waste generating processes. Resource
recovery is performed between the generating process and terminal treat-
ment to recover organics for recycle, for sale as byproducts or for
4-18
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Table 4.4 SOCMI Secondary Emission Sources and Estimated Emissions (Cudahy and Standifer, 1979)
.p-
I
Product
Acctaldchyrie
Acetone/phenol
Acetic onh^dride
Acrylic acid and
cstora
Total
Primary Process
Est im	Waste
Secondary Emission Source
Estimated Secondary
	Emissions	
Ratio	Fate
(kg/Hq)
Ethylene oxidation
Acetic acid
pyrolysiB
Propylene oxidation
450
900
600
410
Aqueous
Liquid
Aqueous
Aqueous
Solid
Aqueous
Liquid
Solid
Biotreatment or deep-well
Incineration or deep-well
Diotreatment
Biotreatment
Landfill or incineration
Biotreatment
Incineration ^
Incineration /
b
b
1.6
b
b
0.05
0.001
(Hg/yr)
b
b
1300
b
Ac ryJonitr ilc
Total
Propylene oxidation
BIS	Aqueous	Holding pond, deep-well
Liquid	Incineration
5.34
0. 36
5. 71
4650
Adiplc acid	Hitric acid	855	Aqueous	Holding pond, deep-well	Neg.	Neg.
oxidation
*kg of emission per Mg of product produced
''information not available.
C0uca not Include emissions resulting from IIjSOj recovery
-------
Table 4.4 SOCMI Secondary Emission Sources and Estimated Emissions (Continued)
-p-
l
to
O
Product
Alky)benzene
Butadi ene
Primary Process
Est1mated
1978
Prodaction
(Gg/yr)
Type of
Waste	
Secondary Emission Source
Estimated Secondary
	Emissions
Ratio	Rate
(kg/Hq)"	(Hq/yr)
Olefins
Chlorination
ji-Butane dehydro-
genatlon
Oxidative dehydro**
genation
By-product of ethy-
lene manufacture
250
260
265
975
Aqueous
Solid
Aqueous
Liquid
Solid
Aqueous
Solid
Aqueous
Solid
Aqueous
Solid
Deep-well injection \
Landfill	j
Biotreatment \
Incineration \
Landfill J
Biotreatment
Incineration
Biotreatment^
Incineration
Biotreatment^
IncinerationJ
0.033
0. 253
0. 150
0. 240
0. 150
3.0
45.0
48
40
Total
64
146
250
Caprolactam
Cyclohexanone
400
Aqueous
Liquid
Biotreatment
Incineration
-------
Table 4.4 SOCMI Secondary Emission Sources and Estimated Emissions (Continued)
Product
Primary Process
Estimated
197B
Production Type of
IGg/yr)	Waste
Estimated Secondary
	 Dm s s i o n s	
Secondary Emission Source
(kq/Hq)'
Rate
(Hg/yr)
Chlorobcnzcnes
Total
Benzene chlorina-
tion
220
Aqueous
Solid
Biotreatment
Landfill
0. 28
Neg.
63
Neg.
62
I
N
Chlorocncthonos
Cumune
Methano chlorina-
tion
Phosphoric acid
catalyst
Aluminum chloride
catalyst
930
966
Aqueous	Di3poe.il	|
Liquid	Incineration J
Aqueous	Biological treatment
Solid	Landfill
Aqueou9	Biological treatment
0.13
b
0. 23
Tota 1
120
b
67
75
Cyclohexnnol/
cyclohoxanone
Cyclohexane
1,012
Phenol hydrogenation 178
Aqueous	Biological treatment ]
Liquid	Incineration	J
Aqueous	Biological treatment
Liquid	Not indicated
0.0911
Neg.
Neg.
92
Neg.
Tota 1
-------
Table U.U SOCMI Secondary Emission Sources and Estimated Emissions (Continued)
Product
Ethanolamines
Ethylene
-C>
I
ro
ro
Primary Process
Estimated
1970
Production
(Gq/yr)
Estimated Secondary
Emissions
Type of
Waste
Secondary Emission Source
Ratio
|Kq/Mq)'
Ethylene oxide and	165
dmmonia
Ethane/propane	'6,100
feed
Naphtha feed
Gas oil feed
3,000
3,000
Aqueous	Biotreatnent
Liquid	Landfill, incineration, sales b
Aqueous	Phase separation and bio-	0.02
treatment
Solid	Landfill	Neg
Aqueous Phase separation and bio-	0.04
treatment
Solid	Landfill	Neg
Aqueous	Phase separation and bio-	0.07
treatment
Solid	Landfill	"eg.
Rate
IHq/yrl
Total
b
122
b
122
b
224
450
Ethytbenzene/	Benzene alkylation 3,200	Aqueous	0.079	253
styrene	dehydrogenation
Liquid^
Total
_ ) Incineration 0.009 29
Solid J				
0.088	282
-------
Table 4.4 SOCMI Secondary Emission Sources and Estimated Emissions (Continued)
-p-
1
NJ
UJ
Product
Ethylene dichlo-
ndc/vinyl
chloride
Ethylene glycol
Total
Primary Process
Estimated
1970
Production
(Gg/yr)
Estimated Secondary
	Emissions	
Type of
Waste
Secondary Emission Source
Patio
Direct chlorina-
tion
Ethylene oxide
hydration
4,900
1,960
Aqueous
Liquid
and/or
solid
Biotreatment
Incineration
Aqueous	Biotreatment
Liquid	Incineration of landfill
0.027
0.095
0.122
0.772
Neg.
Rate
IHg/yrl
130
470
1513
b
1513
Ethylene oxide
Ethylene oxidation 1,460
(air)
Ethylene oxidation	729
(oxygen)
Liquid
Solid
Liquid
Solid
Incineration
Landfill
Incineration
Landfill
0.0116
Neg.
0.013
Neg.
17
10
27
-------
Table U.U SOCMI Secondary Emission Sources and Estimated Emissions (Continued)
Product
Primary Process
Es t i ma t ed
1970
Production Type of
(Gg/yr)	Waste
Estimated Secondary
&tu salons
Ratio	Rate
Socondary Emission Source	(kg/Hg)a	(Hg/yr)
Formaldehyde
Total
Metallic silver
catalyst
Metal oxide
catalyst
2,250	Aqueous
750	Aqueous
Biotreatment
Diotreatroent
0.01
0.05
2 3
38
61
Glycol ethers	Reaction of	201	Aqueous	Biotreatment	0.0019	0.5
•O	alcohols with
^	ethylene and/or
£*>	propylene oxide
Total
Liquid	Not specified	0.025	7.0
7.5
J	0.05	6.0
Maleic anhydride	Benzene oxidation	135	Aqueous	Handling and biotreatment J
Liquid	Incineration
Solid	Catalyst reclamation	Neq.	Neg.
Total	6-8
Methanol	Low pressure	335	Aqueous	Biotreatment	0.00044
Liquid	Incineration	0.00006		
0.0005	1.7
Total
-------
Table 4.4 SOCMI Secondary ftnisslon Sources and Estimated Emissions (Continued)
.o
I
N>
Ln
Product
Primary Process
Est J mated
1970
Production Type of
(Gg/yr)	Waste
Estimated Secondary
Emissions
Secondary Emission Source
Patio
(fcq/Hq)'
Methyl methacrylate Acetone cyanohydrin
Nitrobcntena
Benzene nitration
Tcrcliloroethylcne/ Oxychlorination
trichloroethylene
Propylene oxide
Chlorohydronation
i-Butane peroxida-
" tiond
Ethylbenzene per-
oxidation
Total
398
434
300
13S
500
280
130
Aqueous
Liquid
Solid
Aqueous
Aqueous
Liquid
and/or
solid
Aqueous
Aqueous
Liquid
Aqueous
Liquid
Solid
/ery*^
]
Biological treatment
Sulfuric acid recovery
Incineration or landfill
Sulfuric acid recovery"!
Wastewater treatment
Biotreatment
Incineration
Biotreatment ^
Biotreatment
Incineration
Biotreatment
Incineration
Landfill
b
b
b
0.33
b
2.6
2.6
Rate
(Hq/yrl
b
b
b
141
b
2100
2100
t-Dutenol produced as co-product.
-------
Table 4.4 SOCMI Secondary Emission Sources and Estimated Emissions (Concluded)


Estimated
1978
Production
(Cg/yr)


Estimated
Emi s:
Secondary
lions
Produce
Primary Process
Type of
Waste
Secondary Lmission Source
Ratio
(kq/Hq)a
Rate
(Hq/vO
Tercphthalic acid
(crude)
Air oxidation
1,989
Aqueous
Biotreatment
0.004
e



Liquid
Incineration
0.006
12
Total





20
1,1,1-Trtcliloro-
ethane
Vinyl chloride
310
Aqueous
Liquid/
solid
Biotreatment
Incineration
0.001 ^
<0.001 J
0.62

Ethane
IB
Aqueous
Biotreatment
0.001^
0.04



Liquid/
solid
Incineration
<0.001 /
Total





0.66
-------
Table 4.5 Applicable Control Methods (Cudahy and Standijfer, 1979)
Waste Source Control
Resource Hecovcry
Alternative
Term n«J
Trcotnent
Adi-On Cnntroll
-CN
I
hJ
Secondary Emission
Source Operation
ecu
H	H	J
k
V
&
S 3
3
C
S
"'hysjcal separation






















Disci 1)atlon/stean itripping
X
X
X
X

X
X
X




X






X
X
X
Liquid/liquid phase separation
X
X
X
X
X
X
X
X
X









X
X
X
X
Solid/liquid separation
X
X
X
X
X
X
X
X
X





X
X
X

X
X
X
X
Chemical treatment






















Neutrallration
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X

X
X
X

Precipi tation/coagulation
X
X
X
X
X
X
X
X
X
X
X
X

X
X
X
X

X
X
X
X
Chemical oxidation
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X

X
X
X
Thermal destruction






















Incineration
X
X
X
X
X


X

X
X
X
X
X

X

X




biological treatment






















Activated sludge reaction
X
X
X
X
X
X
X
X
X

X
X
X
X
X
X
X

X
X
X

C1 ari fication
X
X
X
X
X
X
X
X
X

X
X
X
X
X
X
X

X
X
X

Thiikeninq/dewatermq
X
X
X
X
X
X
X
X
X

X
X
X
X
X
X
X

X
X
t

Terminal storage






















L*ndf ill
X
X
X
X
X


X
X
X
X
X
X
X
X
X

X
X


X
Surface impoundnent
X
X
X
X
-X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
L>eep-well disposal
X
X
X
X
X
X
X
X









X




Discharge to natural waters
X
X.
X
X
X
X
X
X









X




u.ean dumping
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X


X

-------
burning to recover heat. Alternative terminal treatment methods offer
choices that may apply where resource recovery and waste source control
do not. Add-on controls are used to lower emissions from waste treat-
ment and disposal operations.
Reduction of VOC emissions by using additional controls at waste
treatment and disposal facilities is shown in Table 4.6. Although many
have not experienced wide use, they offer significant reductions in
emissions.
4.6 CONCLUSION
Industrial activities in the area of solvent recovery are many and
diverse. The diversity arises because of difference in solvents used,
methods of use,scale of operation and regulations.
The evolution of waste disposal regulations such as RCRA will have
an effect on solvent use practices primarily through the economic mech-
anism. Specific practices which are expected to evolve from more res-
trictive waste disposal regulations and higher costs are:
•	review of 'solvent selection and use methods in order to
render the material more recoverable - i.e., less discharges
and emissions
•	review of housekeeping practices to assure that they do not
result in excessive losses or degrade recoverability through
unnecessary contamination
a review of disposal practices to examine land treatment of bio-
degradable solvent wastes and the secure landfilling of non-
biodegradable material.
These reviews and the subsequent evolution of practices will be
more readily accomplished by the smaller companies if they are made
aware of the options available to them for solvent handling and recovery.
To reduce capital requirement for plant modification, equipment or ser-
vice leasing arrangements may be encouraged.
4-28
-------
Table 4.6 Secondary VOC Emission Reductions by Various Control
Techniques or Methods* (Cudahy and Standifer, 1979)
Control Option
Reduction Range
(%)
Organically contaminated wastewater

Source control
10—90
Resource recovery
10—90
Immiscible organic cover
50—90
Floating plastic spheres
70—90
Floating plastic cover
>99
Collection/carbon adsorption
>99
Collection/thermal destruction
>99
Organic liquid and solid

Landfill
i

Soil cover
75—99+
Plastic cover
>99
Surface impoundment

Immiscible organic cover
50—90
Floating plastic spheres
70—90
Floating plastic cover
>99
Based on the limtea data available plus engineering experience and
judgement.
4-29
-------
5.0 WASTES FROM EXPLOSIVES MANUFACTURE
5.1 INDUSTRY OVERVIEW
Current regulations governing air, water, and land emissions from
commercial and military explosives manufacturing may not address all
hazards associated with explosives manufacture. Effluent limitations
and guidelines for the Best Practicable Control Technology Currently
Available (8PCTCA) set by the Environmental Protection Agency in 1976
provide the only standard available for wastewater for subcategories:
A. Manufacture of Explosives; B. Manufacture of Propellants; and
D. Manufacture of Initiating Compounds. Guidelines for subcategory
C. Load, Assemble and Pack Plants have not yet been published (EPA, 1976'd).
These guidelines fail, however, to cover various constituents known to
be characteristic of explosive wastewater streams, such as extreme pH,
sulfates, color, and toxic metals. In addition, air and land emissions
resulting from the manufacturing process and treatment method will also
require standards that have not yet been promulgated. Toxic metals,
cyclotrimethylene trinitramine (RDX), trinitrotoluene (TNT) and other
explosives in the form of particulates, and oxides of nitrogen (NO^)
have been observed following destruction of explosives munitions (U.S.
Army, 1978), Open burning, one of the oldest and universally utilized
disposal methods for pyrotechnics and detonators, emits large quantities
of NO^ and particulates. Characterization of these air and potential land
emissions is necessary to determine the magnitude of environmental pollu-
tion that occurs.
In light of the potentially hazardous nature of explosives, and
because of their ignitability, reactivity and volatility, air, land,
and water criteria must be established which reflect these significant
concerns. The following chapter describes the military and commercial
explosives industries, the waste streams they generate and current
and alternative methods of handling them.
The explosives industry manufactures over 120 different chemicals
and formulations which can be considered useful. Approximately 45 are
5-1
-------
used by the industry in mining, quarrying, ditching, in oil and gas
wells, in road building and for sporting ammunition. Forty-five have
military applications in weapons, rockets, missiles, and space vehicles
and 15 are useful for both military and commercial uses. The distribu-
tion of commercial uses is shown in Table 5.1. Explosives are charac-
terized by their rate of transformation (burning rate), ease of initia-
tion (sensitivity) and the maximum explosive energy available for useful
work. They are usually classified in two groups: low or deflagrating
explosives, exhibiting low burning rates and used primarily as propel-
lants; and high or detonating explosives, exhibiting great shattering
strength due to production of high velocity detonating waves. High
explosives are further sub-classified into primary and secondary explo-
sives. The primary or initiating group of explosives, such as lead
azide, are sensitive to heat, impact or friction. They undergo decom-
position when subjected to these, and develop detonation waves in ex-
tremely short time periods. Secondary or non-initiating explosives
require detonators (fuse caps) and/or boosters for detonation. Boosters,
more sensitive secondary explosives, are typically TNT, RDX, or TNT and
pentaerythritol tetranitrate (TNT-PETN). They are usually required for
less sensitive secondary explosives, such as the 94/6 (94 percent to
6 percent ratio) prilled ammonium nitrate and oil mixture and the "slurry
blasting agents," comprised of ammonium nitrate, coarse TNT and water.
Explosives are manufactured by both the commercial and governmental
sectors. SIC 2892 refers to plants owned by both sectors, but operated
by private firms including government-owned, commercially operated (GOCO)
plants. Government-owned and operated operations (GOGO) are not included
in SIC 2892. Figure 5.1 summarizes the geographical distribution of
these facilities within the United States. Both sectors manufacture
high explosives and initiating compounds and perform loading operations.
They utilize similiar, and sometimes identical, production processes,
but differ in plant size, major projects, end uses, and production rates.
The commercial sector primarily provides ammonium nitrate based explo-
sives, dynamites and nitroglycerin (NG); the military makes TNT, cyclo-
tetramethylene tetranitramine (HMX), RDX, NG and the NG-containing com-
ponents of military propellants.
5-2
-------
Table 5.1 Percentage Distribution of Commercial Explosives Use (EPA, 1975a)
Coal	Quarrying and	Railroad and	Metal	Seismographic	Other
Year mining non-metal Mining Pther Construction mining	exploration	purposes
1963
34.7
22.0
21.0
17.4
4.2
0.7
1964
33.0
21.7
19.9
19.1
5.5
0.8
1965
31.6
19.7
21.8
18.9
7.4
0.6
1966
31.4
20.1
22.2
17.9
7.7
0.7
1967
34.7
21.5
21.7
17.2
4.5
0.4
1968
35.1
20.4
21.1
20.7
2.1
0.5
1969
36.8
19.7
20.0
21.1
1.8
0.6
1970
40.2
19.0
18.7
20.0
1.1
1.0
1971
42.0
19.2
18.7
17.9
0.7
1.5
1972
45.4
18.5 •
17.5
16.1
0.7
1.8
-------
/
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LEGEND:
O MILITARY I\S —ALL AT ION
• commercial ;'.stall at ion
A MILITARY INSTALLATION MANUFACTURING EXPLOSIVES

'LOUISIANA,
(GEORGIA
^FlorToa
Figure 5.1 Major Explosives and Propellant'Facilities In the U.S. (Booz-Allen Applied Research, Inc., 1973)
(EPA, 1977 b)
-------
In developing guidelines for wastewater effluents and atmospheric
emissions, EPA has divided the explosive industry by production process
and explosives type, into four subcategories:
A.	Manufacture of Explosives, such as dynamite, NG, RDX, HMX, TNT,
and nitroguanidine (NGu).
B.	Manufacture of Propellants, such as rolled powder, high-energy
ball power, and nitrocellulose (NC). Propellants can be single-,
double-, or triple-based.
C.	Load, Assemble and Pack (LAP) Operations, which include plants
blending and marketing a final product and those filling shells
and blasting caps; plants manufacturing ammonium nitrate and
fuel oil (ANFO), nitorcarbonitrate (NCN), slurries, water gels
^nd shells are examples.
D.	Manufacture of Initiating Compounds, including such highly-sensi-
tive explosives used for detonation as PETN, lead styphnate,
tetryle, mercury fulminate, lead azide, nitromannite (HMN) and
lsosorblde dinitrate.
Solid wastes from explosives manufacture are chiefly wastewater
treatment sludges and waste product. Little information was available on
wastewater treatment sludges, particularly for commercial explosives.
Waste product is typically released in the production process where quality
control standards allow.
5.2 MANUFACTURE OF COMMERCIAL EXPLOSIVES
Commercial explosives are nitrogen-based organic compounds which
decompose rapidly and spontaneously under the influence of thermal or
mechanical shock, releasing large quantities of heat and gas. They
are categorized according to their behavior as high or low explosives
(see Table 5.2.). Primary high explosives function by the application of
fire on slight impact. They are used in small quantities in primers,
detonators and percussion caps, are dangerous to handle, and are typically
mercury or lead compounds (mercury fulminate, lead azide, styphnate, or
diazodinitrophenol). Secondary high explosives are relatively insensitive
5-5
-------
to mechanical shock and flame, but explode with great violence when set off
by explosive shock from detonation. Decomposition then proceeds rapidly
by chemical reaction progressing through the mass of secondary explosive.
Low explosives only burn and therefore differ in their rate of decompo-
sition. The reaction proceeds in layers parallel to the surface, rather
than throughout the body of the explosive, and is therefore slower in
action with less shattering force.
Table 5.2 Examples of
Primary High
Explosives
blasting caps
detonation cords
electric matches
lead azide
mercury fulminate
safety fuses
;h and Low Explosives
Secondary High
Explosives
dynamites
NG
PETN
Low
Explosives
ammonium nitrate
(prilled or grained)
AFNO
black powder
NCN
smokiess powder
water gels & slurries
Low Explosive
Sensitizers
amine nitrate
dinitrotoluene (DNT)
TNT
The final explosive product may contain a variety of absorbents, coating
agents, fuels, oxidizers and other materials. Both high and low explosives
involve either single organic compounds or mixtures of these and inorganic
salts.
The explosive NG, produced by nitration of glycerin with nitric
and sulfuric acid, and NC are both extremely sensitive to impact. For
that reason, they are usually manufactured into dynamites for safe handling.
Dynamites, which contain a mixture of ingredients depending on their speci-
fications for use, are usually comprised of wood flour, ammonium or sodium
nitrate (to absorb the NG), oxidizers and ethylene glycol (see Table 5.3).
5-6
-------
Table 5.3 Common Ingredients of Dynamites
sodium nitrate
sodium chloride
sulfur
phenolic resin beads
NG
ammonium nitrate
sawdust and wood flour
coal
commeal and starch
trace inorganic salts
grain and seed hulls and flours.
PETN, produced by nitration of pentaerythritol with concentrated
nitric acid, is one of the most shattering and sensitive high explosives.
For this reason, if used as a booster explosive, it must be desensitized
by the addition of TNT or wax. PETN lends itself to the manufacture of
detonating cord. Ammonium-based explosives, which consist of prilled or
grained 99.5 percent nitrate mixed with a carbon fuel, have replaced
others for the surface mining, quarrying and construction industry.
Premixed ammonium nitrate (94 percent) and carbon fuel (6 percent),
frequently containing powdered aluminum, stabilizers, and inhibitors,
form ANFO. This is blended to customer-specification and transported by
truck in bulk, bags, "or cylinders to mine fields. NCN is used primarily
for seismic exploration and is similar in composition to ANFO, containing
mineral oil, sodium nitrate, DNT or TNT, plus some proprietary ingredi-
ents.
Water gels and slurries are basically a mixture of oxidizer, fuel,
and sensitizer in an aqueous media, thickened with gum and gelled with a
cross-linking agent. They exhibit an infinite number of formulations.
Smokeless powder is used as a propellant in ammunition and as an
addition, in small quantities, to water gels and slurries and some dyna-
mites. It is manufactured by nitrating cotton or specially prepared
wood pulp with concentrated nitric acid, purified, and colloided with
nitrated cellulose. This last step transforms the product into a uni-
form mass with a reduced surface, for greater rapidity of explosion.
The commercial explosives industry has three divisions:
• Complex facilities manufacturing a variety of intermediates
and products such as ammonium nitrate, nitric acid, NG,
dynamites, water gels, ANFO.
5-7
-------
•	Small plants usually near mining fields, blending explosives
for nearby use (ANFO, water gels) with intermediates received in
bulk, and formulating compounds to customer specification.
•	Specialty product plants manufacturing selected ingredients such
as lead azide, blasting caps, and electric matches.
Generally, large volumes of water are used for cooling and processing
effluents. These are typically high in biological oxygen demand (BOD),
oil and grease, ammonium- and nitrate-nitrogen, and solids, and have pH
extreme. Their hazardous nature is further increased by the frequent
appearance of trace quantities of dissolved and particulate explosives
products.
I
5.2.1 Ammonia-Nitric Acid Production Processes and Waste Stream
Characterization
Most of the major explosives manufacturers produce their own ingre-
dients for formulaiton and selected intermediates. On-site production
of ammonia, ammonium nitrate and nitric acid is common to the industry.
Raw materials include natural gas, air and sterna, which are catalytically
reformed to produce nitrogen, hydrogen, CO and COj. The impurities are
scrubbed and removed, and the reaction proceeds catalytically to produce
ammonia, which is stored as a gas or aqueous solution. The ammonia is then
oxidized to produce nitric acid (HNO^). Cooling water is required at each
step and is discharged with any other leakage or clean-up water as waste.
The waste stream itself is highly acidic and contains appreciable quantities
of nitrate- and ammonia-nitrogen. Current treatment practices rely solely
on pH adjustment. Nitric acid can also be concentrated by the continuous
distillation of weak nitric acid in the presence of sulfuric acid.
Process effluents form the absorber tail gas, can contain appreciable
quantities of NO^. These are probably due to an insufficient air supply,
leaks, or temperatures exceeding design capabilities in the absorption tower.
Wastewater effluents are characterized by low pH, high ammonia- or nitrate-
nitrogen (NH^-Nj, NO^-Nj), and high sulfate levels. Treatment practices
involve acid neutralization and calcium sulfate sludge removal.
5-8
-------
Spent acids from NG, PETN, or TNT manufacture, are also processed
to recover nitric acid. However, they may exhibit high levels of dis-
solved solids, high sulfate, and quantities of nitrogen salts. This would
contribute to variability in NO^ emission from nitric acid production.
5.2.2	Nitroglycerin Production Process and Waste Stream Characterization
Nitroglycerin is a highly unstable explosive very sensitive to
shock. The safest method of production involves the controlled nitration
of very pure glycerin required for safety and stability with concentrated
sulfuric and nitric acids. (See Figure 5.2.) The product, which contains
about 0.5 percent water, is stored in lead-linked tanks. The Biazzi
process, a continuous nitration process, is already being used by the
military and is rapidly being adopted by the commercial industrial sector.
This process is shown in Figure 5.3.
The waste effluents associated with nitration are similar in both
processess. They are NOx and nitric acid fumes of unknown quantity.
These are vented through the absorber to the atmosphere. Wastewaters from
building and equipment clean-up contains trace amounts of pollutants.
However, the dilution effect from various wastewater streams precludes
characterization of each stream separately. Spent acid effluents are
identical to other spent nitration acids. After nitration, the product is
neutralized, washed and separated. The latter produces a 3 percent sodium
carbonate residual requiring disposal. Washing produces "sour water,"
which proceeds to a catch tank for further treatment.
5.2.3	Dynamite Production Process and Waste Stream Characterization
It was the extremely high sensitivity of NG to shock that originally
led to the formulation of dynamites. Major ingredients are NG and
ammonium nitrate. Table 5.4 shows the typical composition for dynamite.
Ammonium nitrate is first mixed with minor ingredients (wood pulp, sawdust,
flour, starch) and a small amount of antacid (CaCO^ or ZnO) to form a
"dope" to which nitroglycerin is added. The "dope" is oxygen-balanced for
maximum strength and minimum fumes. Varying amounts of NG are used. For
example, a 40 percent straight dynamite contains 40 percent NG, 44 percent
5-9
-------
CQNC.
HNOj
<99%)
TO MIXED
ACID
PREPARATION
MIXED
ACID
GLYCERIN
NITRATION
WEAK
STEAM
SPENT ACID
RECOVERY
SPENT ACID
NO
NEUTRALIZATION
H,SO.
AND WASH
WASTE
TO RECYCLE
OR
DISPOSAL
TO
DISPOSAL
WASTE
FINISHED
NG
TO
DISPOSAL
N6
EMULSION
3%
Na2C03
' ACID '
CONT A MINATEI
SEPARATION
CONCENTRATION
NITRIC ACID
Q, UOUD EMBSOK3
~ SOUO SMSSIONS
O OASEOUS CM3SONS
T
TO STORAGE. LAP
OR
PflOPELLANT
FORMULATION
Figure 5.2
Flow Chart for Nitroglycerin Production (EPA,
5-10
197"t>)
-------
TO MAGAZINES
BUGGY
Ml, - *
*3 j 1%
CANNING BAY	: AGITATION BAY
	i"
$

SEPARATOR
TANK
OIVERTER
BUILDING
DESICCATOR
CATCH TANK
DESENSITIZING
BUILDING
fl
RECEIVING
TANKS
t ACft CONSTANT NUB UNI
CATCH TANK
1 tttAStlfllHQ fO?
4 NI1RIT0I
> lim C0NT80LUI
•	StPAIAION
1 SODA WAVEI WASHERS
I ftlSN WAUI WASHERS
•	ii (vuisiriu
10 SOOA WAVIN TANK
tl NOV WAtCI TIN*
INTERRUPTER 1 K
FUNNEL
i
SMALL
MIX BAY
CAST PREMIX
BAYS
MuLTIBASE
PREMIX BAYS
SODA DISSOLVER
& REFRIGERATION
BUILDING
SPENT
TANK
SOOA
DISSOLVER
SPENT ACID
BUILDING
I SOOA WATER
TANK STORAGE •—

BIAZZI PROCESS
BUILDING
MIXED ACID
STORAGE
TANKS
///
*
I UNDERGROUND
I ACETONE STORAGE
CATCH
TANK
h
SPENT ACID
TANK ROOM
GLYC
STORA
TRIACETIN STORAGE TANKS
TANKS
AY HOLDING
TANK ROOM
CATCH TANK
ROOM
Figure 5.3 Biazzi Nitroglycerin Process (Courtesy, U.S.
(EPA, 1976 d)
Naval Ordnance Station, Indian Head)
-------
sodium nitrate, 14 percent carbonaceous material, 1 percent antacid and
1 percent moisture. A AO percent ammonia dynamite contains 15 percent
NG, 32 percnet ammonium nitrate, 38 percent sodium nitrate, 4 percent
sulfate, 9 percent carbonaceous material, 1 percent antacid and 1
percent moisture. Straight dynamites usually contain 20-60 percent NG.
NG may also be gelatinized with 7-8 percent collodion cotton to make
blasting gelatin, Gelatin dynamites are mixtures of gelatin and "dope"
ranging from 20-90 percent grades (gelatin:dope). These haive the greatest
shattering action.
Liquid nitroglycerin for the formulation of dynamite is handled in
small lots in rubber pails. The products are packaged by automatic
machinery into waxed cardboard or plastic tubes and then boxed in sawdust
for transportation.
5.2.4	Smokeless Powder Production Process and Waste Stream Characterization
Smokeless powder is colloided NC containing approximately 1 percent
diphenylamine to improve storage life, plus a small amount of plasticizer
such as dibutyl phthalte. (See Figure 5.4.) Cotton, or specially pre-
pared wood pulp is nitrated with concentrated nitric acid, purified, and
the nitrated cellulose is disintegrated. The product is colloidized by
mixing with alcohol, ether diphenylamine and other agents to transform it
into a dense uniform mass with a reduced surface area for greater rapidity
of explosion. NC is obtained from an outside supplier.
Scrap powder is stored as a water slurry to reduce the potential
hazard. Overflow from this storage contributes to the waste stream
as does the filter backwash in its last step of preparation. These are
both discharged to the wastewater production stream, and would be removed
in sludges from wastewater treatment. However, wastewater is generally
not treated.
5.2.5	ANFO Production Processes and Waste Stream Characterization
The major ingredients of ANFO explosives are ammonium nitrate,
ferrophosphate, calcium silicate, fuel oil, aluminum, coal and mineral
oils. The only source of wastewater arises from clean-up of spills and
5-12
-------
Table 5.4 Typical Composition of Dynamite (EPA, 1975a)
Component	Percent, Wt.
Ammonium nitrate	50-55
Nitroglycerin	15-18
Sodium nitrate	0-17
Trace ingredients	10-35
5-13
-------
WET BLENDING
BLENDING
DRYING
ROLLING
PACKING
ADDITIVES
GRAIN
COATING
DEWATERING
SURFACE COATING
SIZE
SEPARATION
DRY SCREENING
NITROGLYCERIN
BASE GRAIN
PREPARATION
Figure 5.4 Smokeless Powder Process Flow Chart (EPA, 1975 a)
5-14
-------
and equipment. NCN is similar in constituents to ANFO, but it may also
contain sodium nitrate, proprietary ingredients, and DNT or TNT (which is
usually purchased from a supplier). The wastewater stream is restricted
to clean-up of spills and equipment and may or may not be hazardous
depending on the presence of DNT or TNT in the stream. Wastewater is
generally not treated; therefore, sludges are not produced.
5.2.6	PETN Production Process and Waste Stream Characterization
Production of PETN involves the nitration of pentaerythritol by
94 percent nitric acid (see Figure 5.5). Waste effluents from nitration
are similar ot the nitric acid recovery process. Stabilization produces
a final product which is 40 percent water. The effluents are combined
with those from washing, filtering, and still bottoms to form the waste-
water stream. The slurry is hot-dried before being used in explosives
formulation. Although air and water emissions data were not found in
literature, it is likely that the wastewater effluent is contaminated
with traces of basic salts from the stabilization step, nitrates from
the basic salts reacting with nitric acid, and acetone. Solid wastes
are mainly still bottoms from steam distillation in the acetone recovery
process.
5.2.7	NC Production Process and Waste Stream Characterization
NC is characterized by its degree of nitration. Uncolloided dry
cellulose nitrate is a violent and sensitive explosive. Treatment with
special plasticizers produces a colloidal form which is less sensitive
and more prone to burning than detonation. Production involves pre-
purification of cotton linters or specially prepared wood pulp, nitra-
tion by nitric/sulfuric acid in special reaction pots, centrifugation of
the crude NC, and dumping in a "drowning tub" to stop the reaction. Any
N0x from the reactor and centrifuge goes to the absorber where it is
oxidized to produce weak nitric acid. This is subsequently concentrated.
Air emissions of NO from the first absorber vent, and NO and SO
X	XX
from the systems's second absorber result. The concentrator and reactor
pots would also emit NO and SO . Wastewaters from clean-up are characterizec
X	X
by low pH, high levels of suspended solids, and high nitrate-nitrogen.
(See Figure 5.6.)
5-15
-------
CONC. HNO
CONTINUOUS
NITRATOR
PETN
CENTRIFUGE
FILTER
SLURRY
PENTA
ERYTHRITOL
HNO, TO
PETN
RECOVERY
ACETONE
DISSOLVER
SODIUM
CARBONATE'
ACETONE
STORAGE
GRAINER
CAUSTIC
STILL
FILTER
ACETONE/WATER
' PETN
DIGESTOR
PETN
STILL
BOTTOMS
Figure 5.5 PETN Production and Acetone Recovery (EPA, 1975a)
5-16
-------
CONC.
TO MIXED
ACID
PREPARATION
I HNO3
H2so4 or\(99*)
UgfNOjlj ^""T^
NITRIC ACID
NITRATION
CONCENTRATION
HNO
STEAM
CRUDE
NC
SPENT ACID
SPENT
ACID
RECOVERY
PURIFICATION
FINISHED
WET NC
(30%H20)
TO RECYCLE
OR
DISPOSAL
O GASEOUS EMISSIONS
^ LIQUID EMISSIONS
~ SOUD EMISSIONS
TO
PROPELLANT
FORMULATION
Figure 5.6 Flow Chart for NC Production (EPA, 1977b)
5-17
-------
Purification of NC is vitally important to production. Residual spent
acids trapped by the cellular structure during nitration will render the
explosive unstable during storage. A number of distinct steps are involved.
The NC water slurry undergoes acid hydrolysis to remove unstable sulfate
esters and nitrates, and is beaten and reduced to a desirable degree of
fineness. It is poached with sodium carbonate solution, blended with NC
fines from settling pits for various grades, and finally centrifuged.
The finished wet NC contains 30 percent water.
All of these processes require huge amounts of water which must
eventually undergo treatment and disposal. Washwaters from acid hydroly-
sis and acidic wash water drains into settling pits. There, NC fines
are removed. Pit overflow is neutralized by calcium carbonate as a
lime slurry in the acid neutralization facility and then transferred to
settling lagoons or discharged directly. Sludge from the lagoon is
buried on-site on land adjacent to the plant.
5.3 MANUFACTURE OF MILITARY EXPLOSIVES
The military explosives industry as a whole is involved in two
operations:
•	Manufacturing and production of explosives, propellants,
or intermediates, such as TNT, NG, NC, nitric acid.
•	Loading, assembling, and packing of explosive or propellant
products into munitions. This usually involves blending various
ingredients.
Three major categories of products are included: acids, which are
intermediate products, and explosives and propellants, which are final
products.
About 17 "Army Ammunition Plants" (AAP), located mostly in the
east and the south, have a role in one or both of these two activities.
Seven are involved only in manufacturing; eight in loading, assembling
and packing (LAP) activities; and two in both. (See Figure 5.7.) The
5-18
-------
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Figure 5.7 The Military Explosives and Propellants Industry (EPA, 1976d)
-------
Army also supplies other government defense agencies with high explosives
and propellant products. All explosives, with the exception of NG used by
the Air Force, are manufactured by the Army. They also load, assemble
and pack munitions for these agencies. Two Navy facilities produce
casting powder and NG, but obtain loaded explosives from the AAP network.
The Navy also loads and assembles solid rocket motors with propellants
obtained from AAP or manufactured in-house. It is also the Navy's
responsibility to load most of the bombs for the other defense agencies.
There are four major steps in munitions manufacture:
•	manufacture or purchase of ingredients such as NC, NG, TNT, or
HMX
•	combination of ingredients into blends, grains, or formulations
such as composition B
•	loading of warheads, bombs and rocket motors with blends or
fortnulat ions
•	final assembly and packing of complete munitions.
Explosives and propellants manufacture uses operations similar to
those in dther chemical production operations. However, they are housed
in plants occupying a much greater area for safety consideration. They
are generally isolated geographically.
Four materials account for most of the tonnage produced. They are
TNT, NC, RDX and NG. These are rarely used alone, but are used for
blending and in formulations. The manufacture of nitration acids,
particularly nitric acid and sulfuric acid, is also significant.
Wastewater streams associated with these manufacturing processes
are also similar to those from a chemical manufacturing operation. They
result from acid drippings, solvent spills, stack scrubber drainings and
floor washdown. Waste streams unique to mulitary explosives manufacture
will be discussed in following sections. In general, acid manufacture
produces small volume wastes that originate from leakage and drainage
from air pollution abatement scrubbers. Their composition includes
5-20
-------
the following:
•	acid waters which are neutralized with lime or soda ash
•	azeotroping agents such as n-propylacetate
•	heavy metals from equipment corrosion
•	nitrobodies from acid recovery.
The worst problems and the greatest quantity of waste originate
from the basic explosives manufacturing process. These consist of acid
matters, chemical washes, spills and washdowns. Red water, a waste-
water stream unique to the military, is the major by-product from TNT
manufacture. It is a brick red solution composed of sodium nitrate
(NaNO^), sodium sulfate(Na2S0^), sodium sulfite (Na2S0^), sodium
nitrite, sulfonated or sellited nitro-compounds, and complex unidentified
dye-bodies in varying proportions. Other streams form manufacture in-
clude pink water which is dissolved TNT in water (=100 PPm) from
equipment washdown and work area clean-up, and is found wherever TNT
is made or handled; suspended explosive particles in the form of dust
and chips;and sometimes solvents such as acetone, benzene and dimethyl
aniline. Efforts are currently being made to eliminate these waste
streams by installing effluent treatment units, replacing outdated
process equipmet, automating production lines, recycling and use of
newly developed, more environmentally sound processes. Major waste-
water problems from the military explosives industry are shown in Figure
5.8.
5.3.1 TNT Production Process and Waste Stream Characterization
TNT, one of the most important military explosives, is produced
by treatment of liquid toluene with mixed nitric and sulfuric acids.
The undesirable isomers are removed by treatment with a sodium sulfate
solution. Residual DNT, used for the manufacture of propellants, is
removed by conversion to a soluble salt and subsequent extraction.
Two process variations exist: the conventional stepwise batch
process, shown in Figure 5.9, and the new Canadian Industries Limited
(CIL) continuous process, shown in Figure 5.10. Both include the nitra-
tion of toluene by a mixture of oleum, nitric and fuming sulfuric acid,
5-21
-------
Wastes
Manufacture of Chemicals
Loading

Trinitrotoluene * DNT
Tetryl
Primer materials |
RDX/HMX
Nitrocellulose
Nitroglycerin
NC-based propellants
Ball powder
[Black powder
Acid manufacture
Pilling of warheads
Mfg. of extruded rocket grains
Mfg. of cast rocket grains j
Acid waters, nitrate A
sulfate salts, etc.

+

+
+
+



+



Red Water
+












Pink Water •










+


Other dissolved
explosives and/or
dust and chips
+
+
+
+
+
+
+
+
+

+
+
+
Organic solvents
and resins



+


+
+




+
Chromium and other
metals from corrosion









+
+


Perchlorate and
other oxidizers












+
Figure 5.8 Major Wastewater Problems in the Military Explosives
Industry (EPA, 1976d)
-------
Toluene
60# Nitric Acid
1 A
Mono-House
(First
N itration )
Mono-Oi
Bi-Waste
Bi-House
(Second
N itration)
Bi-Oll
Tri-Waste
Mixed Acids
and Oleum
Tri-House
(Third
Nitration)
Spent Acid
Flake TNT
Storage or
Shipment
Water*
Sellite-
Filter Water—
Wash ho use

4

p -p
O
9t

Waste Acid
Red Yellow
Water Water
3
o-
Figure "5.9 Batch Process for TNT Manufacture (EPA, 1976 d)
5-23
-------
Weak HNO
Recycle HNO^ •"
Weak HNO_ — Yellow Water
Strong HNO,
Ln
I
ro
4>-
uene
Strong HNO
Legend
Strong HNO
Nitrator
Crude TNT
f I Separator
	I
Spent Acid
Figure 5.10 CIL Continuous Process for TNT Manufacture (EPA, 1976 d)
-------
followed by purification and finishing of the product. Gaseous
emissions from nitration are released from the nitrators and separators
and are composed of CO, CC^, NO, NO2, ant^ trinitromethane (TNM) ,
a violent explosive. TNM is currently vented to the atmosphere. Before
discharge, the effluent is passed through a fume recovery system to
recover the NO as nitric acid. Traces of TNM have also been found
x
in this acid and fume recovery system. The final effluent vented to
the atmosphere contains quantities of unabsorbed NO^ and some TNM.
Spent filter media is an occasional solid waste from the batch process.
Yellow water, which is a dilute solution of crude TNT in water
plus acids, results from the first crystallization and water wash in
the CIL nitration step. It is recycled to the second nitrator for
consumption within the process. The spent acid waste stream is not
discharged. Nitric acid is recovered from the waste and reused. Any
residue water is sold for commercial use. Waste acids resulting from
spillage and floor drainage are neutralized with lime or soda ash and
then discharged to a chemical waste sewer for further treatment. Waste-
water from the nitration step is carried through the acid recovery system
and then discharged.
Following nitration, TNT undergoes purification with a number of
water washes, neutralization with soda ash, and treatment with a 16
percent aqueous sodium sulfate (sellite) solution to remove the contami-
nating Isomers.
The waste streams generated in TNT manufacture, in order of decreasing
strength, are red water, pink water and yellow water. In terms of
production amounts, approximately 0.34 kg/kg TNT waste is produced con-
sisting of 0.26 kg process water, 0.06 kg organics (nitro-toluenes and
nitrotoluenesulfonic acid salts), and 0.02 kg dissolved inorganics (NaNO^
and Na2SOx). The red water consists of extraction waters and the sell-
itic solution. Ti is concentrated to 35 to 40 percent and sold to the
paper industry as a source of sulfite liquor, or water is removed by
evaporation and the waste is incinerated. Red water contains approxi-
mately 77.6 percent water, 17.3 percent organics, 5.2 percent NaNOx, and
approximately 2.9 percent Na,S0 . Approximations are due to conflicting
4 X
analytical methods.
5-25
-------
Incineration produces atmospheric emissions containing NO and SO,
X	z
and solid waste as ash, primarily sodium sulfate, which is approximately
90 percent soluble. When this ash is landfilled or stockpiled, the
current practice, the ash is susceptible to leaching by rain water and
could cause contamination of both surface and ground water.
TNT manufacture, and LAP operations, also generate pink water
which, like red water, is of variable composition. Pink water may
contain isomers of DNT, TNT, and usually has high nitrobody content.
Sources include: nitration fumes, scrubber discharge, red water con-
centrate distillates, finishing operation hoods, scrubber and washdown
effluents, and possible spent acid recovery washes.
Treatment practices involve removing the solids with a sump,
and treating the effluent by carbon adsorption or evaporation/leaching.
Risk of explosion has been reported for adsorping high concentrations of
TNT on carbon. Ultimate disposal of the sump sludge is by open burning.
Yellow water, which is excess water from the first washing that
has not been returned to the nitration pvocess, is combined with other
waste process water for final treatment.
Finishing is the final step in TNT production. The TNT crystals
resulting from purification are slurried with water, melted, re-evaporated,
solidified, flaked and packaged. Waste streams generated include waste
acid and wash waters. The acid stream from the finishing process results
from spillage, floor drainage and washings in the work area. Treatment
of the effluent consists of neutralization with lime or soda ash and
subsequent discharge to a chemical sewer for further treatment. The
average waste stream contains NO , SO , high COD, and a-TNT. Additional
X X
minor wastes produced by the finishing step Include waters associated •
with sellite manufacture, from gaseous effluent scrubbings,
spills of soda ash and sellite solution, and floor washdowns.
5.3.2 DNT Production Process and Waste Stream Characterization
DNT is an explosive by-product of TNT manufacture which can be
produced on-site at the TNT plant. The crude discharge undergoes
5-26
-------
"sweating." This is a controlled step-wise temperature change to
produce pure DNT crystals in a contaminated liquor. The liquor
is subsequently drained off. The liquor undergoes further sweating,
combined with the pure DNT, screened, and packaged in drums for
storage. All impurities from the process are fed back into the TNT
manufacturing process. Uncontaminated cooling water is the only aqueous
effluent.
5.3.3 RDX-HMX Production Process and Waste Stream Characterization
RDX (cyclonite) is the third most important military explosive
and has replaced tetryl as a base charge in military detonators.
It is about 50 percent more powerful than low-density granular TNT,
and more stable than PETN and tetryl. It is never handled in a pure
and dry state because of its sensitivity. RDX is usually incorporated
into formulations such as Composition B, which is RDX crystals with
TNT and/or was, and desensitized with beeswax or polyisobutylene.
It is used for pres9-loading into shells, slurried with TNT for
casting, or mixed with a special oil to make plastic explosives for
commercial demolition work. It is always shipped water or solvent
wet.
Manufacture is started with the nitration of hexamine, a rela-
tively non-toxic compound purchased from the civilian sector. (See
Figure 5.11.) The hexamine is nitrated using a nitric acid - ammonium
nitrate mixture in the presence of acetic anhydride and acetic acid.
Acid vapors from the reactor vessel, aging tank and simmer tank are
vented to a scrubber, recovered and recycled back into the reaction.
HMX is produced as a by-product of the reaction.
If a 110 percent yield were assumed, 0.32 pounds of hexamine would
produce 1 pound of RDX (Tucker, 1972), 0.2023 pounds hexamine would
produce 1 pound HMX, with 35 to 40 percent of the hexamine tied up in
unwanted bv-oroducts.
5-27
-------
Acid
Concentration
Ammonia
Oxidation
Hexamine
Store
Weak HNO
Acetic
Anhydride
Mfg.
hno3
Concn
Cone HNO
Mix
NH ,NO
Mfg. & Mix
Nitration
Acetone or
Cyclohexanone
Wash
Evaporate
~l i	
Recrystallize
Bottoms
Distill
Caustic
Wax, e.g.
TNT, e.g.
Melt, Mix
Mix
Comp C-4, e.g. Comp B, e.g.
Disposal or Recycle
Figure 5.11 RDX-HMX Process (EPA, 1976d)
5-28
-------
The atmospheric emissions from the scrubber vents contain NO^,
acetic acid, traces of formic acid and methyl nitrate. Stripped
sludge from the acetic acid is treated with sodium hydroxide, converting
the ammonium nitrate in the sludge to sodium nitrate and ammonia.
Residual acetic acid is also converted to ammonia, formates, amines
and sodium nitrate. The ammonia is either vented to the air in small
amounts as a vapor or discharged as a condensate with traces of
impurities in the effluent wastewater. Methylamine and demethylamine
and any sludge residue, largely sodium nitrate, are used as fertilizer.
Cooling water, pump seal water and condensate washdown which are
relatively uncontaminated, are discharged to catch basins and then
to sewers ultimately destined for surface waters. Catch basin residues
are currently disposed of by open burning. The wastewater discharge
from the actual RDX/HMX process is typically recycled for recovery
of substantial amounts of product, by-product, or spent reactants.
Refinement, the final step in the manufacturing process, produces
fugitive emissions which are vented to the atmosphere from the organic
solvent distillation step. Wastewaters associated with this step
arise from recrystallization and dewatering.
5.3.A Tetryl Production Process and Waste Stream Characterization
Tetryl (2, 4, 6-trinitrophenylmethylnitramine) is used as a
booster explosive or as the explsovie ignited by a detonation charge.
This in turn detonates the bursting charge. Its extreme sensitivity
and toxicity hazards of handling the dry product (like RDX) has elimi-
nated any current production, even though Joliet AAP is equipped to
handle the manufacture.
Like the preceding explosives, tetryl is produced by the nitra-
tion of an aromatic feed-stock in mixed nitric and sulfuric acid. (See
Figure 5.12.) The product is then washed and recrystallized. Specifi-
cally, demethylaniline (DMA) is sulfonated with 93 percent sulfuric
5-29
-------
DMA H_SO.
2 4
Spent Acid
Sulfa tor
DMAS
Nitrator
Cool ing Water
Floor Wash
Acid Tank
Acid
Neutch
Drainage
Wash Water
Water
Neutch
Cool ing
Water
Crude Tetryl
Refining
Water
Neutch
Water
HNO /H.SO . Mixture
3 2 4
Acid
Recovery
Bubble Cap Water
Cooling Water
(to Nitrating Ditch)
H2S04 and HN03
(to NAC/SAC Units)
SelliteTank Cleanout
Floor Wash
Flush of decomposition unit
with 40- 50$ HNO„
( To Tetryl Ditch )
Acetone

Lag

Dry

Pack

House
*
House

House

Storage




Pure Teti
Wash Water
Floor Wash
Dry House
Ditch
Tetryl Ditch
"Outfal I
Figure 5.12 Tetryl Manufacturing Process at Joliet AAP (EPA, 1976d)
5-30
-------
acid forming dimethylaniline sulfate (DMAS). DMAS is subsequently
nitrated with sulfuric and nitric acid, washed, dissolved in acetone,
evaporated and purified. The major waste stream is composed of nitric
and sulfuric acids. These acids are recovered and sent to the concen-
trating facilities.
Hastes originate from tetryl purification, chemical spills,
tank clean-up, cooling water and the sellite solutions used for floor
washdown and equipment clean-up.
5.3.5	NC Production Process and Waste Stream Characterization
NC constitues the second larges volume of explosive product
manufactured by U.S. Army Ammunition Plants. Manufacturing involves
treating cotton linter or wood pulp cellulose with mixed nitric and
sulfuric acid. (See Figure 5.13.) The resulting slurry is acid-
boiled, washed and recovered, and re-slurried. It is then beaten
with sodium carbonate, slurried and poached, and allowed to settle.
The water is then drained off.
In the near future, NC manufacture will be converted from the
batch process to a continuous process in which almost all water
will be recycled and the acid neutralization plant eliminated.
Minor wastewater streams will result only from typical washdown
procedures, spills and leaks and the sweepings from the dehydration
press. NC is used as the fundamental ingredient in gun and rocket
propellants. (See commercial explosives sections for greater detail.)
Solid wastes will result from process clean-up and wastewater treat-
ment.
5.3.6	NG Production Process and Waste Stream Characterization
NG is an explosive plasticizer used as the military's primary
ingredient in double- and triple-based propellants and for casting
plastisol double-base rocket motors. The continuous Biazzi Process
5-31
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Nitrator
I
Wringer
Recovered
Water
No2C03
Water
Press
Damp NC
•Spent Acids to Recovery Plant
Drowning Tub




Boiling Tub


Boiling Tub Pit



Beater




Poacher


4

Wringer


Poacher Tub Pit

~Acid Water to
Neutralization
Plant
"Water To
Recovered
Water Tank
Figure 5.13 Batch Nitrocellulose Manufacture (EPA, 1976d)
5-32
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shown in Figure 5.3 is used. NG is manufactured when it is used.
This avoids the shipment of extremely hazardous product.
Wastewater from the process contains NG, transfer waters and
uncontaminated cooling waters.
5.3.7 NC-Based Propellant Production Process and Waste Str*"""
Characterization
The majority of NC and NG manufactured by the AAP is incorpor-
ated Into single, double, or multi-based propellants for shells and
rocket motors. A rocket is an energy conversion device in which
propellant chemical reactions occur generating heat and gases. The
gases expand through a nozzle, producing thrust to propel the rocket
system.
Two types of propellants exist, solid and liquid. Both require
an oxidizer and a fuel. Hybrid propellants, a combination of both
solid and liquid types, are also used. The solid becomes the pro-
pellant fuel and the liquid, the oxidizer. Manufacturing involves
colloiding the ingredients and then molding them like a plastic.
Single-based propellants are NC-containing compounds with minor
amounts of plasticizer, stabilizers and burning-rate catalysts.
Double-based propellants consist of NC swollen by a nitrato plasti-
cizer (nitrate ester), usually NC, forming a rubbery, gelled structure
with visoelectric properties. The NC densitizes the shock-sensitive
NG so it can be used. Stabilizers and catalysts are also part of the
formulation. Multi-base propellants are combinations of several
nitrate materials, such as NC, NG, NGu, triethylene glycol, dinitrate
and stabilizers.
Military NC is also cast into smokeless powders for shells and
casting powders for missiles. Manufacture of these powders utilizes
a solvent extrusion process. In this process, the NC fibers are
masticated with solvents to form a dough, blended with other ingre-
dients and extruded into strands. These are then cut, dried, and washed.
Ball powder propellant formed with spheres, is also manufactured
5-33
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in small quantities at the APP's. Cooling water used in ball powder
manufacture is entirely recycled, but process water, containing benzene,
ethyl acetate, NC, NG, sodium sulfate and collagen is usually discarded.
Pyrotechnics and primer mixes, which consist of various initiator
materials such as lead azide, lead styphnate, tetracene, and others,
are produced in very small quantities on a bench scale.
5.3.8 LAP Operations Waste Stream Characterization
The remaining major waste streams associated with the military
explsives industry are those arising from compounding of explosives
and propellants. These streams typically contain dust and chips, dis-
solved explosives to about 100 ppm, solvents, organic materials, and
ammonium nitrate or perchlorate.
A small waste stream is generated from LAP Operations, the final
operation in the military explosive manufacturing process. Table 5.5
lists wastewaters associated with LAP Operations. These operations
generally include:
•	melt-pour loading of high explosive warheads
•	extruded, NC-base rocket motor grains
•	cast-in-place rocket motor grains
•	pressed explsive and pyrotechnic charges.
In melt-pour loading, ordinance items are filled with molten TNT
or other high explosives and allowed to solidify. Pink water is pro-
duced in the catch basin. The basin also contains dissolved TNT and
other explosive ingredients. These are periodically removed and burned.
Exhaust fans with wet scrubbers catch dust produced by the flaked
explosiveand are vented to the atmosphere. Scrubber drainings are
added to the catch basins.
Extruded, NC-base, rocket motor grains are formed when double-based
(NC/NG) propellants are extruded, dried, and cured. Their exteriors are
painted and they are boxed and shipped for further assembly.
Cast-in-place rocket motor grains consist of high-energy plastic
sol-cast grains used in ICBM's and polymerization-cured grains cast
5-34
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Table 5.5 Waste Waters Generated in LAP Operations (EPA, 1977b)
AAP
Activities
Raw Materials
Flow
m'/day
Pollutants
Discharge
Load
W'r
Comments
CAAP load 8-inch shells TNT
Load 500-.750-,
and 1,000-pound
bombs
Laundry
Overal1
Tntonal (805 TNT
and 201 flaked A1)
75.. 7C
54.8
131
57 mg/1 TNT
M.3(TNT)
Disposal in evapor-
ation ponds
2.7 mg/1 TNT MD.13(TNT) Disposal in dry
streams
4.4(TNT)
IAAP Shell loading
Laundry
Hold booster
charges from bulk
explosives
Overal1
341
(94.6)
30.3
0.814
371
Pink waterH
1 mg/1 TNT
145 mg/1 R0Xc
20 mg/1 *DX«
10 mg/1 TNT
Tetryl
0.34(TNT)
49.4(R0X)C
6.8(RDX)d
Wastes subjected
to diatomaceous
earth filtration
followed by adsorp-
tion on granular
carbon columns
0.31(TNT)c Discharged to
surface streams
0.64(TNT)
49.4(R0X)
fi.8(R0X)d
InAAP Fabricate cloth N.A.	N.A.	N.A.	N.A.
bags and paper
' tubes and load
propdlants into
these containers
for shipment
JAAP Loading of medium
caliber ammunition
and ammunition
components
Compositions
being loaded into
105 mi shells at
a rate of 200,000
shelIs per month
23.5	TNT	3.4(RDX)cd Filtered through
145 mg/1 RDXC 0.45(ROX) diatomaceous earth
20 mg/1 RDXd	and then through
two granulated
charcoal
KAAP Load explosives,
primarily formu-
lations of TNT and
ROX, into ordnance
items
Detonators for
105 mi howitzer
shells
TNT, ROX	N.A.
Lead azide, lead N.A.
Styphnate, ROX
TNT, ROX	N.A.	Currently waste-
waters are disposed
of by trucking them
to evaporative
ponds
N.A. '	NaNOj, acetic acid,
and NaOH used to
deactivate the lead
azide
5-35
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Table 5.5 Waste Waters Generated in LAP Operations (.Continued)
Activities

Raw Materials
Flow
m /day
Discharge
Load
Pollutants kg/day
Coimients
Helt-pour
(Area
0)
Composltion-B
N.A.
Pink water N.A.
NOj.TOC,color,
TNT.pH
Discharged to
lagoon system
Melt-pour
(Area
C)
Compositlon-B



Melt-pour
helt-pour
(Area
(Area
E)
G)
TNT and Compos 1-
tion-B
Octyl.TNT, and
Composition-B
75.7e
Pink water N.A.
NOi.TOC,color,
TNT.pH
Recycled
Load Line
Load Line
(Area
(Area
P)
Q)
Lead azide
Lead azide
N.A.
N.A.
N.A. N.A.
N.A. N.A.
Batch destruction
by use of cerfc
ammonium nitrate
Black-powder load
Black powder
None except N.A. N.A.
raw sewage
and storm-
water runoff ,
Spilled powder Is
dumped Into surface
waters
LHAAP Mixing, processing N.A.
N.A.
BOD,COD,Mn,
Cn- ,N0j. POi, i
Fe.Cd.poly-
sul fide
polymers,
aluminum pow-
der, black
powder, and
antnonlum per-
chlorate
N.A.	Aimionlum perchlor-
ate goes to surface
water. All solids
go to evaporative
ponds and are even-
tually Incinerated.
Remaining wastes
go to surface water
LAAP Shell-loading
N.A.
5 22
80 mg/1 TNT <1-7
Haste Is trucked
to leaching ponds
on the plant
grounds
MAAP N.A.
Shell washout
Overall
N.A.
N.A.
N.A.
1,510
2.10
1,510
{i
5 mg/1 ROX
.0 mg/1 TNT
{145 mg/1 ROX
40 mg/1 TNT
X1 jo.31
» jo. 23
90(R0X)
36(TNT)
(ROX)
239{TNT)
1.22(RDX)
1.58(TNT)
Wastewaters are
discharged to a
drainage canal
which flows to
surface water
RaAAP N.A.	N.A.	N.A.	N.A.	N.A.
'Acronym used to Identify Arty Amnunltlon Plants (AAP):
cue	Comhutkcr	ikaaP	Lonj Horn
IMP	low J	LSAAP	Lone Sur
InU'	Indian*	fMP	Mfla-i
JJir	Joliet	RaAAP	Ravenna
VA«	Kentas	VAAP	Volunteer
Louisiana
^riBarlly xaihdoun waters
Hffor* treitnent
After treatment
'includes raw sewage and stom-water runoff
Source: The American Defense Proparedneat Aaan., 1975
H.A. • Oita not available
5-36
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for vacuum bell shaped motors. No water is used for the plastisol
cast grains. Polymerization-cured grains use water only for heating
and cooling coils.
Pressed explosive and pyrotechnic charges are used for illumi-
nating flares, black powder, and developmental explosive blends of dry
granular ingredients to be loaded into shells. Water is not used in
the process. Solid wastes are reused in the product,
5.3.9 Nitrating Acids Production Process and Waste Stream Charac-
terization
Since most basic explosives are nitrated products, it is economi-
cal for each manufacturing plant to make its own acid. The waste
streams are small and similar to those of the commercial explosives
industry.
5.4 CURRENT TREATMENT FOR WASTE STREAMS FROM COMMERCIAL EXPLOSIVES
Waste streams associated with the commercial explosives industry
consist of wastewater effluents, gaseous emissions, and solid waste
such as sludge, ash and explosive items. Waste streams vary according
to the production process and end products as described in the following
sections. Because explosives manufacturing processes demand large
volumes of water, wastewater effluents constitute most of the total
waste output.
5.4.1 Commercial Waste Water From Explosives Production
Within the commercial explosives industry, wastewater results
from the production process, equipment clean-up and cooling. Explo-
sives production effluents result from tfre nitration and product
finishing steps (the latter being the major factor). These product
finishing operations include washing, refinement, and drying or de-
watering. The constituents of most concern are extreme pH, BOD^,
suspended solids, oil and grease, nitrogen forms, residual explosives
(NG), and high levels of dissolved solids, primarily sulfate (SO^).
Attempts to remove suspended solids using settling tanks and sumps
have proven ineffective (EPA, 1975a).
5-37
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Efforts to treat oily wastes associated with the manufacture or
maintenance results in effluents with high levels of suspended solids.
The type of facility producing the wastewater, however, is a major
factor in the level of suspended solids output. Complex facilities
discharge effluents with lower average levels of suspended solids than
on-site plants. Complex facilities dilute suspended solids containing
wastewater with cooling water, avoiding product and intermediate product
loss to wastewater, and use dry clean-up procedures (sweeping and wiping
of equipment instead of water washing) prior to final equipment wash-
down. A complex facility might average a 30.7 mg/£ suspended solids in
its discharge, as opposed to the industry average of 93.A mg/S.. This
represents a three-fold reduction of components in wastewater such as
ANFO, or other explosives, leakage from pumps and motors, and chemical
residuals appearing as oil, much as NG. Adherence to proven procedures
such as these in other plants will help eliminate the need for more sophis-
ticated technology to handle the problem. Suspended solids from this
type of plant are primarily nitrogenous and organic.
Oil skimmers have been effective in the separation and removal of
non-emulsified oils from wastewaters. (The collected oil is generally used
for spraying on dirt roads to control dust.) However, poor design and
maintenance of the separators at many plants has made these skimmers
ineffective.
Neutralization has been employed to rectify pH extremes at complex
facilities. On-site facilities exhibit near-neutral pH, and waste-
water is discharged without neutralization. Process waters from acid
production and recovery, nitration, and finishing operations for explo-
sives such as NG or PETN, are highly acidic. Percolation of the first
washwater from NG production through crushed limestone beds to neutralize
the acid, has proved ineffective. Accompanying high sulfate concentrations
encouraged formation of precipitates which subsequently coated the lime-
stone and eliminated its neutralizing properties.
Other wastewater streams exhibiting extreme pH, such as acidic
wastes form acid manufacture, alkaline wastes from acetone still
bottoms, and sodium carbonate wash solution for NG (pH 9-10) are
5-38
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diluted with other plant wastewaters and released without treatment.
Alkalinity of the wastewater streams promotes a high level of dissolved
solids such as nitrates and sulfates, and also allows increases in
effluent NG, BOD, and oil content. The combination of alkaline and acidic
waste streams in these plants, could help correct the extreme pH condi-
tions and, with additonal treatment, pollutant discharge would be dra-
matically reduced. Additional methods for effective pH control for
acid wastes for commercial explosive operations have been well estab-
lished (EPA, 1976d). Some of these include:
•	passing acidic wastewaters not containing sulfates
through limestone beds
•	mixing acid wastes with lime or dolometic lime slurries
•	addition of concentrated caustic or soda ash to acidic
wastewaters.
Dissolved NG, high nitrate, sulfate and dinitroglycemia (DNG)
levels are present in waste water from NG manufacture in addition to
extreme pH, BOD and suspended and dissolved solids. Since a decrease in
temperature of the waste stream would precipitate dissolved NG, creating
an explosive hazard, precautionary attempts are made to "catch" the
precipitated NG by directing the wastewater flow through settling
boxes. This has limited effectiveness. It has been possible to reduce
effluent levels from several thousand mgfi of dissolved NG to 100-
1000 mg/£, but these concentrations are still too high to eliminate
the explosive hazard.
5.A.2 Treatment Alternatives For Commercial Explosives
Biological treatment has been studied as a potential solution to
wastewater problems for commercial explosives manufacturers (EPA, 1976).
Successful decomposition to nitric from a raw waste load of 400-500
mgIt of NG was reported following preliminary settling of the wastes
and treatment by activated sludge. Quicklime has also successfully de-
composed NG, forming calcium sulfate, sulfite and calcium salts of low
molecular weight (EPA, 1976d). The effluent formed was alkaline, but
the resultant sludge was stable and free of explosive properties.
The commercial explosives industry has apparently not investigated
5-39
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means of treating its wastewater. However, intreased interest in bio-
logical and chemical treatment of wastewaters to rencve NG and DNG has
been shown by the Army. For wastewaters containing approximately 1500
mgIt NG and 850 mgIt DNG, biological treatment has not proved effective.
Physical/chemical treatment has been attempted with the addition of lime
and calcium sulfate to the neutralizing wash to counteract sodium,
carbonate and bicarbonate alkalinity. The NG was removed, but the sul-
fate level was increased to indescribable levels.
Other explosive wastes (such as smokeless powder) have been
treated biologically through extended aeration with activated sludge,
followed by lagooning. Preliminary results report BOD^ removal greater
than 95 percent. Ultimate disposal of the lagoon effluent is achieved
by spray irrigation on a field.
Biological treatment of high ammonia- and nitrate-nitrogen levels
in explosive wastewaters has been successful and effective. Treatment
of dilute and concentrated ammonia wastewater and low level <60mg/£
nitrate-nitrogen wastewater effluents with activated sludge nitrifica-
tion has also proved effective. High nitrate levels, however, which
are common to explosives industry wastewaters, require combined bio-
logical nitrification-denitrification treatment for effective removal.
At the present, a nitrate abatement technology for the commer-
cial explosives industry does not exist. Initial feasibility studies
by the U.S. Army mention biodenitrification, ion-exchange and reverse-
osmosis as promising treatment methods. Various nitrate treatment
methods are shown in Table 5.6.
Table 5.6 Nitrate Treatment Methods (.EPA, 1976)

Removal
Approximate
Method
Efficiency (%)
Cost, $/mg
Biodenitrification
70-95
3.45-30
Algae harvesting
50-90
20-35
Ion exchange
80-99
170-300
Electrodialysis
30-50
100-250
Chemical reduction
33-90
-
Reverse osmosis
50-96
100-600
Distillation
90-98
400-1000
Land application
5-15

5-40
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Pilot scale studies on reverse osmosis of nitrate wastewaters
showed effective nitrate recovery, depending on pH, and efficient sul-
fate removal. The sensitivity of the reverse osmosis membranes to
temperature, pressure, bacteria, chemical change, hydrolysis and sur-
face coating may limit potential application of this method. Reverse
osmosis, with or without subsequent treatment methods, could eliminate
the need for neutralization while allowing product recovery and reuse.
Energy requirements, use of membranes tolerant to varying pH, and use
of corrosion resistant materials, all need further investigation.
The recent availability of nitrate-selective in exchange resins
may permit removal of nitrates from wastewaters. A full scale continu-
ous counter-current (chem-seps) ion exchange system is on-line for a
plant manufacturing ammonium nitrate (EPA, 1976d). Reduced nitrate and
ammonium nitrogen levels with effective ammonium nitrate recovery, has
been reported. This method would be particularly appropriate for com-
plex facilities utilizing ammonium nitrate as an intermediate in explo-
sives manufacture.
Biological denitrification is rated by the Army as the most prom-
ising and efficient type of treatment at present. Pilot scale studies
indicated excellent nitrate reduction (>90 percent for wastewaters con-
taining methanol, provided pH and temperature are carefully controlled).
The commercial explosives industry does not attempt to remove
sulfates from wastewaters although high levels are characteristic of
explosive wastewater streams. Feasibility studies by the Army show
that even though a proven treatment process does not exist, reverse
osmosis, ion-exchange, evaporation and calcination methods show some
promise. The reverse-osmosis option has been used for nitrate removal
but suffers limitations of membrane specificity. Sulfate removal
efficiencies of 99+ percent have been reported. To retain membrane
integrity, pH must be controlled. Waste stream neutralization somewhat
reduces membrane specificity requirement. Following sulfate removal,
the resulting water effluent can be reused in the production process,
and the brine reclaimed (EPA, 1975a). Using sulfate-specific resins,
ion-exchange can produce reusable water. The resins can be regenerated
with the sulfate by-product for reuse.
5-41
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A method proposed to recover sulfuric acid utilizes a combination
of reverse osmosis and evaporation. Reuse in the acid or explosives
manufacturing process is possible. Calcination, the most promising
method, precipitates the calcium in the acid stream to produce a
sludge. High temperature calcination, which follows, recovers the
lime and produces	SC^ must be catalytically converted to SO^
for sulfuric acid production. The only disadvantage appears to be the
high solubility of the calcium sulfate in the treatment system (EPA,
1975a)• Economic feasibility of the process has not been proven.
Since treatment methods for nitrates and sulfates have not yet
been proven technically and economically feasible, some commercial
explosives plants are practicing disposal by spray irrigation on land.
One complex facility manufacturing ANFO, dynamite, a variety of inter-
mediates, and specialty products, treats its wastewaters by sedimenta-
tion and oil skimming. The resultant wastewater is then sprayed on a
pasture used to graze cattle. This plant is located In an arid region.
Another complex facility in the upper midwest pretreats the waste with
activated sludge and lagooning before disposal by spray irrigation.
The method is not as effective at this facility, however, since only
half of the wastewater percolates into the soil. The remainder is
runoff. A precautionary monitoring study should be instituted for
effluent leachate should the effluent possess any potentially hazardous
constituents. One on-site facility formulating water gels, collects
its relatively small amount of waste in a tank car and sprays it into
an abandoned mine overburden disposal site on their property. It
appears reasonable that land disposal of explosives, wastewaters, pro-
vided there is some pretreatment, has some applicability. Soil and
climate conditions must promote physical adsorption and microbial
action and crop utilization of nitrates. Use of large amounts of land
would be a limiting factor in more densely populated areas or for
plants not owning a large tract of property. Ground water contamination
might also be a possible deterrent to land application. On-site formu-
lation of water gels in a process with wastewater streams that could
cause groundwater contamination.
Evaporation in ponds has been used as a land disposal alternative.
For example, a complex facility in an arid region ponds a small part of
5-42
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its wastewater from ANFO blending equipment, clean-up, and NG neutra-
lizer washes. Percolation and evaporation facilitates water loss.
Care has been taken to prevent any overflow.
One northern midwest on-site facility discharges all of its
wastewaters to a natural basin on its property. Water loss occurs by
percolation and evaporation in the summer months. A third plant, manu-
facturing water gel explosives in the central southeast, utilizes
evaporation ponds for its process waters. The pond has a projected
life capacity of 13 years. All other process wastes and cooling
waters are discharged directly to surface streams. Most explosives
producers are located in remote areas on large tracts of land for
safety considerations, so land availability for evaporative ponding
does not appear to be a problem.
Propellant manufacturers usually have greater waste loads than
those manufacturing explosives. The wastewaters show high levels of
total suspended solids (TSS). This is especially true during NC manu-
facture, where nitrocellulose fines escape into the wastewater streams.
Propellant wastewater effluent are also characterized by high BOD, COD
and high total organic carbon (TOC) from the organics and solvents used
in the processes. High nitrogen levels from nitric acid and organo-
nitrates, and high sulfate levels from sulfuric acid, also prevail.
There appears to be no significant treatment of these manufacturing
wastewater effluents, and if any pollution abatement program is utilized,
it usually consists of neutralization and sedimentation.
LAP operations generate a smaller, but more hazardous, volume of
wastewater due to the presence of explosive particulates. Wastewater
effluents associated with manufacture of initiating compounds, gene-
rate the highest waste load volume due to product specificity. Ini-
tiating compound demands are small and customer specific, and on a
small scale. It is not economical for the industry to attempt recovery
of spent materials, nor to have wastewater treatment facilities. The
variability of the operations also causes sudden changes in waste
effluents. High pollutant concentrations may be followed by periods
of low pollutant concentration. Heavy metals are characteristic of
these waste effluents. High levels of lead and mercury (lead azide,
lead styphnate, and mercury fulminate) are often found in these waste
streams. Therefore, such alternatives as spray irrigation for these
wastes do not appear appropriate.
-------
Gaseous emissions are usually composed of NO^ and oxides of sul-
fur (S0x) and acid mists. They result from manufacturing and concen-
tration and acid recovery operations during the nitration process.
Air pollution abatement measures have not been taken by the industry,
even though some absorption towers for gas scrubbing have been tested.
Some of the emissions contain hazardous and explosive substances. TNT
manufacturing emissions contain toluene and the explosive, TNM, which
are vented to the atmosphere. TNM has also been found in the acid and
fume recovery system, and also presents an explosive hazard.
Fugitive hydrocarbon emissions contribute co the gaseous effluent
from explosives manufacture. These emissions result primarily from
solvent recovery operations.
Finishing processes and propellant formulation also contribute
organics to the gaseous waste stream. Controls have not been instituted
or indicated for either type of emission.
Solid wastes generated during manufacturing are currently dis-
posed in sanitary landfills by surface dumping. These waste streams
include the sulfate residue from sellite incineration and sludge from
settling lagoons. Long term pollution problems could arise with
leaching, if these wastes contain heavy metals such as lead or mercury,
or explosive fines (NC). Usually, wastes contaminated with explosive
material, such as scrap, off-spec, items, contaminated packaging, dust
and chips, are not reclamable, and are disposed of by open burning.
This method is unacceptable, even though commonly used, since uncon-
trolled emissions of N0x and particulate matter result. There are
alternative methods for disposal of solid wastes which appear safer
than open burning. Technically and economically feasible methods of
disposal have not yet been proven, even though several are under
development.
5.5 CURRENT TREATMENT METHODS FOR THE MILITARY EXPLOSIVE INDUSTRY
Waste streams associated with the military explosives industry
are similar to those produced by the commercial sector. The waste-
water effluents, gaseous emissions and solid waste depend on the pro-
duction process and end products. The following section describes the
5-4 A
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significant waste effluents and their current and alternative treat-
ment methods.
5.5.1 Current Treatment of TNT Wastes
Some waste streams unique to military explosives manufacturing
preclude the generalized treatment methods discussed previously under
Section 5.4. TNT manufacture and loading into munitions produces
three major wastewater streams: red water, pink water, and acid wastes,
including spent acids.
Red water results from the sellite purification of crude TNT.
The sellite, a 16 percent concentrated sodium sulfate solution, re-
moves 3-5 percent of the unwanted TNT isomers and a nitro group in the
3 to 5 position. The sellite residue is melted with the remaining rinse
waters from this step. Typically, red water contains about 25 percent
dissolved solids, approximately 17.3 percent organics,' 2.3 percent sod-
ium sulfite, 0.6 percent sodium sulfate, 3.5 percent sodium nitrite
and about 1.7 percent sodium nitrate. Batch and continuous process red
water differ in volume and composition. A neutralization wash with
soda ash preceeds the sellite wash in batch operations, but not in the
coninuous process. The continuous process, on the other hand, uses a
water wash prior to the sellite wash step and produces "yellow water"
by washing out the nitrating acids. This operation reduces wastewater
volume by returning yellow water to the nitration process. It also
reduces the discharge constituents found in the batch process wastewater.
Excess yellow water is combined with the process waters and treated by
neutralization or incineration. Efforts to reduce the wastewater volume
by modifying the process, recycling transfer waters, returning yellow
water to the process and then segregating waste streams with similar
t
characteristics, have been initiated to facilitate treatment and dis-
posal methods.
The current treatment method for red water first involves water
evaporating in a rotary kiln to achieve 35-40 percent solids. The
residue can then be sold to the paper industry or incinerated with
subsequent land disposal of the ash. Both appear unsatisfactory as far
as treatment and ultimate disposal are concerned. Both concentration
and incineration are energy intensive methods of treatment. Although
5-45
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the condensate liquor retains a pink color, which indicates the presence
of nitrobodies, it is discharged directly without any further treatment.
Finally, incineration produces significant quantities of ash, which must
be land disposed. The potential for surface and groundwater contami-
nation then arises. Joliet AAP stockpiles these residues on land; and
about 200 million pounds have been stored to date. Since the ash is 90
percent soluble, runoff caused by rainwater poses a significant contami-
nation problem. The paper industry is reducing their need for red
water, so the total amount of ash resulting from incineration will rise,
adding to an already existing ash disposal problem.
Inefficient incineration operation also leads to potential at-
mospheric pollution problems. Gaseous emissions of N0^ and SO^ have
been detected from red water incineration at Radford AAP. These might
be reduced by further treatment of the pink condensate or other modi-
fications to the treatment process.
Volunteer AAP is pretreating its red water by pH adjustment,
concentrating it by reverse osmosis and recovering the water for re-use.
Desulfonation along with DNT recovery has been attempted by Radford
AAP unsuccessfully.
A fluidized reduction system which chemically converts the red
water ash to sodium carbonate and hydrogen sulfide has been shown to
be technically feasible on a bench>rscale level. In this process, red
water incineration ash is ground for fluidization, incorporated into
the fluidizing bed, and reacted with the reducing gas, water and
carbon dioxide.
The most promising option for treatment of red water, is the
Tampella process, which reduces the concentrated liquor and carbonates
and hydrogen sulfide. These compounds can then be recycled to produce
sellite.
5.5.2 Treatment Alternatives For TNT Wastes
Activated carbon and chemical destruction have been proposed as
alternative treatment technologies for red water. Activated carbon is
effective in removing DNT and TNT from red water, but somewhat ineffi-
cient for other constituents. They are hexanitrodiben zye, TNM, ajanic
5-46
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acid, trinitro benzoic acid, dinitrocresol, phenol and various nitro-
toluene sulfuric acids. The chemical treatment alternative, uses
chemical oxidents, chlorination, bromination, ozonation and uv-catalyzed
ozonation for reduction and ultimate destruction of nitrobodies (and
red color) in the red water, with some success. No effort to prove this
on a pilot scale has yet been undertaken.
5.5.3 Current Treatment Practices for Pink Water
Pink water wastes from TNT manufacturing and LAP plants arise
from nitration fume scrubber discharges, red water concentration dis-
tillates, finishing and building hood scrubber and wash down effluents,
and spent acid recovery wastes. LAP-pink water has been well charac-
terized as containing «-TNT, RDX, HMX, wax and additives. However,
pink water resulting from other operations has not been well charac-
terized.
Both waste streams are usually combined for treatment. Carbon-
adsorption has been used successfully for pink water treatment. Carbon-
adsorption systems are currently in operation at Joliet and Iowa APP.
Raw pink water is high in solids and explosives, and is alkaline.
Carbon treatment of the waste stream is a two-step process. The'waste-
water is routed to sumps to remove settleable solids, followed by a
diatimaceins earth filter, which removes about 21.5 percent of gross
suspended solids. Next, it is pumped through carbon columns to remove
dissolved TNT and RDX contaminants. Single or multiple carbon beds may
be connected, either in series for downflow system, in parallel for an
upflow system, or a combination of the two. Uniform design criteria
are lacking. The bulk of the removal occurs in the first of the carbon
columns.
Each type of activated carbon has its own sorption capacity. When
that limit is reached, the column integrity is broken and the carbon
must either be replaced or regenerated. Since an economically and tech-
nically sound method for regeneration of the pink water carbon does not
exist, the waste carbon is incinerated.
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Disadvantages in using carbon treatment for pink water waste
include:
•	the costs of carbon use are very high
•	potential for recovery and reuse of a-TNT is eliminated
•	air pollution problems from carbon incineration
Thermal and solvent extraction regeneration of the carbon have
been investigated. The temperature range in which thermal treatment
can be safely performed is limited because of the explosion potential
of the a-TNT within the carbon's cavities. Under favorable conditions
it could explode, although no incidents were found in literature. It
also emits NO^ and methane as components of the regeneration off-gas.
After treatment, the regenerated carbon is reported to recover only about
60 percent of its original capacity.
Solvent extraction shows much more promise for carbon regeneration
because of the following:
•	regeneration occurs in a fixed bed
•	TNT contaminated solvent can be reused In regeneration or
as input to TNT mamufacture
•	a greater degree of carbon saturation can be achieved.
Studies using methanol, acetone, and toluene as a TNT stripper, show
acetone as the best choice, although conflicting results were reported
for acetone (22.3 percent removal versus 92 percent removal). However,
regenerative capacity, is only partially adequate. Further investigation
on these techniques is necessary. There is also need for a carbon or
other sorbent with greater sorption capacity and increased specificity.
Use of polymeric resins as an alternate sorbent or in combination
with the carbon is a potential alternative, since it can be regenerated
to a constant performance level many times. In addition to its regener-
ative advantage, resin use would reduce the amount of carbon undergoing
incineration.
Evaporative treatment is also a current method of pink water dis-
posal. Soil and climate conditions govern the quality of the method,
since overflow could result in sever leaching problems and potential
of surface or ground water contamination. Evaporative ponding does
present an economically viable pink water treatment method.
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5.5.A Treatment Alternatives for Pink Water
Several alternatives for pink water treatment have been investi-
gated. They includes
•	solvent extraction
•	reverse osmosis
•	fly ash adsorption
•	ion-exchange resins
•	biological treatment
Treatment of wastewaters at Iowa AAP with solvent extraction or
toluene by two stage countercurrent extraction has been shown to remove
and recover up to 97 percent of the TNT contaminant. A proposed full
scale system, however, does not look economically feasible. (Brown and
Shapiro, 1979.)
The reverse osmosis process is effective in concentrating pink
water, but early membrane failure has been a problem.
Adsorption capacity of fly ash is less than carbon and ultimate
disposal of spent fly ash will remain a problem.
Investigated ion-exchange resins have shown good potential for
multiple regeneration and reuse. However, carbon appears more effective
in removal of color.
Biological treatment studies have shown successful biodegradation
of a-TNT with the addition of large amounts of supplemental nutrients.
However, color development increases the wastewater's resistance to this
method. The toxicity of TNT in the environment represents a severe
disadvantage of this method.
5.5.5 Current Treatment of NC Wastes
Spent nitrating acids from NC manufacture undergo separation or
settling to remove NC fines. Neutral wastes from several other manu-
facturing operations are discharged to a different set of settling
tubs because of the drastic difference in NC fines concentrations
(<10 mg/for neutral wastes, and =100-500 mg/i for the nitrating acid
wastewater stream). Particle size precludes complete removal of fines.
The NC fines which are insoluble and appear as suspended solids make
the wastewaters potentially hazardous. No effective means of removal
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have yet been found.
Other NC wastewaters are, for the most part, acidic to near-
neutral, with moderate sulfate and nitrate concentrations and high COD.
They are treated with lime to affect neutralization.
5.5.6	Treatment Alternatives for NC Wastes
Since the most hazardous constituent of NC wastewater effluents
are the insoluble NC fines, centrifugation and coagulation technologies
are effective in solids removal. Centrifugation also has the advantage
of NC recovery. These, when coupled with water management plans already
proposed, will provide almost complete recycling and reuse of waters
with accompanying NC recovery.
5.5.7	Current Treatment of RDX/HMX Wastes
Wastewaters from the RDX/HMX manufacturing and LAP operations
are contaminated with various explosives such as TNT, KDX, and HMX.
Sources of these waste streams include: dewatering and decantation
operations, floor and equipment clean-up, and contaminated waters from
dust control scrubbers.
Current treatment methods are generally limited to catch basins
or baffled sumps. Activated carbon treatment of LAP wastewaters is
performed at Joliet AAP, while some inoperative ponding takes place at
other LAP facilities. Holsten AAP discharges its untreated catch
basin effluents, contaminated with RDX, HMX and TNT directly into indus-
trial sewers. These sewers discharge into a surface stream, the
Holsten River. Joliet AAP has shown some success in treating waste-
waters containing TNT, RDX and HMX with activated carbon. However,
analysis has shown preferential removal of TNT with less adequate effi-
ciency for HMX and KDX.
5.5.8	Treatment Alternatives for RDX/HMX Wastes
The following methods are under consideration for RDX and HMX
control:
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•	reverse osmosis
•	activated carbon adsorption
•	anaerobic biological degradation
•	polymeric resin adsorption
Reverse osmosis and activated carbon adsorption have been discussed in
previous sections. Anaerobic digestion is extremely sensitive to toxic
wastes, but degrades non-toxic complex organic components very well.
Provided HMX/RDX toxicity is low, anaerobic degradation might prove a
successful treatment method. Polymeric resin adsorption has been
promising when accompanied with hydrolysis and prior concentration of
the RDX or HMX on the resin. At present, carbon adsorption appears to
be more reliable for TNT and RDX control.
5.5.9 Current Treatment of NG Wastes
Wastewater streams from KG batch manufacture result from soda ash
solution and water washes following the nitration step and from NG
storage when dilute soda ash solution is decanted before NG use. The
batch process, as opposed to the continuous Biazzi system, is only in
operation at Badger AAP. The streams are similar in both the military
and private sector.
Wastewater from NG manufacture shows variable pH, is high in
nitrate, sulfate, NG, and DNG. The current limited treatment method
consists of catch basins, with eventual discharge to evaporative ponds
or waterway systems. Proposed alternate treatment methods have proved
ineffective for both NG and DNG.
Radford AAP has proposed use of sodium sulfide treatment followed
by treatment with activated sludge. Several disadvantages exist to
this treatment method. They include toxic residual ion (sulfide) which
exist in the process effluents, undesirable sulfide odors that arise
during decomposition, and potential explosive hazards created by the
exothermic reaction. Attempts to find alternative treatments may
relieve this problem, and offer- a potential means of NG and DNG
recovery.
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5.5.10	Current Treatment of Wastes From Propellants Manufacture
Solvent, solvencless, and composite propellants are formulated
into single, double and multi-base compositions in various ways with
a variety of ingredients. Typical ingredients which might be reflected
in the waste stream include NC, NG, NGu, ammonium perchlorate, HMX,
powdered aluminum, stabilizers and catalysts.
Solvent propellant manufacture produces a relatively small
volume of associated wastewaters, which are high in organic solvents
and dissolved propellant constituents. Lack of treatment prior to
discharge has led to increased efforts to reduce water use by recycling
and to recover waste product. Investigation indicates two effective
and reliable possibilities: activated carbon and biological treatment.
Biological treatment has been used by a commercial producer and is pro-
posed for two Army AAP's (Radford and Badger). However, the biotrans-
formation of propellant wastes and the "toxic nature" of the final end-
products have not been thoroughly explored.
Solventless propellant wastewater effluents, resulting from
building clean-up and equipment washdown, are characteristically high
in BOD, nitrate, suspended solids, NG, DNG, and lead. With the exception
of lead removal, the wastes are discharged directly, without any prior
treatment. Badger AAP is the exception. At this point, effluent
volume is reduced by improved water management so that percolation/evap-
oration ponding can be utilized. Potential pollution problems for this
method, including leaching and contamination of surface and ground
waters, always arise with land use, but the method appears to be sub-
stantially effective.
An alternative pilot-scale biological treatment study is underway
at Radford AAP, but inconclusive information on ultimate end products
makes this method still questionable.
5.5.11	Treatment of Wastes From Miscellaneous LAP Activities
Wastewater effluent associated with load and pack operations
characteristically contain TNT or HMX and RDX, or the explosive being
loaded. They result from casting of propellants, processing of secondary
ingredients of pressed explosives, and casting of plastic bonded
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explosives, and include wastes from building and equipment clean-up
procedures and air pollution treatment. Explosives are brought in from
outside the plant, and treatment focuses on the operations for incor-
porating the explosives into munitions.
Dust abatement procedures are usually required by activities
such as grinding of ammonium perchlorate and HMX, size reduction by
hammermllls, size control screening, and by evergoing operations. At
Radford AAP, duct systems remove the dust, which is carried to a wet
scrubber. The flow from the scrubber is discharged without treatment.
A dry dust collection system, with subsequent incineration, has been
proposed at Radford AAP, but has not been implemented. Venting of
explosive dusts to wet scrubber systems is also used at a number of
other LAP plants, including Longhom AAP and Redstone Arsenal. Longhorn
dumps its scrubber wastes into a sump, the contents of which undergo
evaporative ponding. Clean-up water is discharged to surface ditches
on-site. Redstone Arsenal ships Its scrubber wastes to the scrap
propellant burning grounds for disposal. Building and equipment wash-
down effluents are discharged through sumps to creeks.
Wastewaters from LAP activities involving pressed propellants
characteristically contain powdered aluminum, and ammonium picrate.
Those from detonator LAP process usually contain lead azide and lead
styphnate. LAP activities also produce wastewaters from building
and equipment uashdown and dust scrubber systems but information
concerning Its characteristics or treatability are lacking. Kansas
AAP routes Its water effluents to holding pits, treats them with
caustic to attack the lead styphnate, and discharges the waters Into
a holding pond. In effect, little is known about wastewater streams
from LAP activities or their treatment. Such efforts need to be
undertaken.
5.5.12 Treatment of Acid Manufacturing Waste
Acids manufacturing waste streams are discussed in Section 5.2.1.
Recycling reuse and treatment efforts are similar in nature to those
in the commercial explosives Industry.
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5.5.13 Treatment Methods For Bulk Propellants, Explosives, Pyro-
technics (PEP)
A U.S. Department of Defense study recently reported an inventory
of approximately 168,000 tons (about 35 weight-percent PEP) of surplus,
obsolete, or unserviceable munitions awaiting disposal. About 56,300
tons are generated annually, over and above that being stockpiled. The
report states that 48,350 tons are demilitarized (demil) each year,
showing a net inventory increase of some 10,000 tons. Since approxi-
mately 35 percent of the weight of munitions is represented by PEP,
these figures mean that about 17,000 tons of PEP accumulates in un-
wanted munitions each year.
Logistically speaking, the problem is severe. About 2.4 million
square feet of covered storage space with an equivalent replacement
value of $127,000,000 is being tied up by the stockpile. Disposal of
these unwanted munitions requires removal of the PEP's from the
munitions treatment/disposal of the PEP's, and treatment/disposal of
inert parts of disassembled munitions. Examples of bulk PEP include:
TNT, Composition-B, RDX, HMX, NC and double-base and composite pro-
pellants. The majority of PEP inventory, taking into account the
U.S. manufacturing capacity, contains the following:
PEP	Percentage
TNT	49
NC	29
RDX	10
all others	12
Until 1971, obsolete munitions were disposed of by deepwater
ocean dumping. The Secretary of Defense, in response to increased
environmental concern, subsequently imposed a ban on all ocean dumping.
The oldest, most universally used, disposal option for bulk PEP's,
other than ocean dumping, is open burning. It is a relatively simple
operation with minimal labor and fuel cost. Unwanted materials,
scrap, wastepaper, surplus rocket motors, shells, and other materials
are piled up in a remote, open field with starter fuel, and ignited.
The operation is smokey, polluting (N0X and particulates), and unsafe
(chunks of burning propellants can be thrown into the air to fall back
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and finish burning on Che ground. Air emissions from this process are
unknown at present. More specific uses of open burning include des-
truction of high explosive and propellant wastes, and incinerating
primary explosives wastes.
When disposing of various forms of NC by open burning, fiberboard
and metal drums with leakproof liners filled with NC are covered with
water, transported to an approved burning ground, and placed on a non-
combustible pad made of asbestos. The drums are drained of water,
covered with fuel oil, and ignited by firing a device into the wastes.
Considerable NO^ is produced. Gelatinized NC or plastisol NC (PNC) is
disposed only by this method,. Bulk PETN and TNT is also disposed by
open burning.
Detonators and primers such as lead, 2.4-dinitroresorcinate or
lead styphnate are placed on flammable substances such as straw dn
burning pits and detonated by applying heat from a fire by electrical
ignition. Personnel and other explosives should be shielded behind a
barricade for safety with overhead protection and at a distance. The
practice is unsatisfactory because un-detonated components present a
hazard to personnel during clean-up, in addition to uncontrolled
emission of NO^ and toxic metal particulates into the air.
Though unsafe and environmentally damaging, open burning still
remains an economically viable disposal alternative.
Incineration is also currently used for disposal. The Army
incinerator (APE-1236/1276 "deactivation furnace pollution abatement
system") is the only fully developed design in use, although other
systems are being developed. It consists of a steel rotary furnace
30 feet long, and 4 feet in diameter, with spiral internal flights
carrying debris through as the tube rotates. It has an oil or gas-
fired burner, and a stack mounted over the feed end. Temperatures
are characteristically 1200°F near the burner, 600-900°F in the middle
and 400-500°F in the stack. Pollution abatement is achieved by a
baghouse preceded by a cyclone and flame arrester to eliminate
visible smoke emissions. An NO^ or gaseous emission abatement system
has not yet been developed. Feed rates are approximately one item
per second.
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Other systems under development include a rotary kiln inciner-
ator designed to burn bulk PEP. It is similar to the APE-1236 deact
furnace, but lacks the internal flights and is lined with firebrick.
Radford AAP has demonstrated its capabilities. It is essentially
smokeless and discharges about 200 ppm NO^, which is the only signi-
ficant gaseous emission. A fluidized bed incinerator under develop-
ment for bulk PEP is a commercial adaptation of the system used for
military explosives. PEP, as a 25 weight percent slurry, is injected
into the hot fluidized alumina. Smoke is not visible and NO emissions
x
are low due to a NO^ decomposition catalyst. The batch box is an oil
fueled trash incinerator adapted for use in handling small PEP items
and PEP-contaminated dunnage. It is expected to produce little or
no smoke. NO abatement measures have not been undertaken. The
x
SITPA-II incinerator is similar to the APE deact furnace currently in
use, but it has been adapted for the feeding of bulk PEP. The APE-2048
Contaminated Waste Processor, originally a flashing furnace, shows po-
tential for handling bulk PEP mixed with contaminated combustibles.
It is to be a smokeless incinerator with negligible NO^ emission.
Additional conventional, well-developed processes used either
for destruction of PEP's and munitions, or for removal of PEP from
munitions, and newly developed demilitarization processes are listed
below.
Conventional, Well-Developed Processes
•	Hot-water steamout (APE 1300)
•	Steam washout (Army-Navy)
•	Steam meltout (sweatout)
•	High-pressure water washout
•	Open burning
•	Open detonation
•	Deactivation Furnace Incineration (APE 1236)
•	Contour drillout (Navy)
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Newly-Developed Processes
•	Fluid bed bulk PEP incineration (Picatinny)
•	Rotary kiln (Radford) bulk PEP incinerator
•	Wet air oxidation (Zimpro) (Navy)
•	Microwave Meltout (Tooele)
•	Batch box incineration (Navy)
•	Contaminated Waste Processor (CWP)
•	Magnesium reclamation (Crane)
•	Colored flare reclamation (Crane)
•	Photoflash reclamation (Crane)
•	Flashing chamber (Hawthorne)
•	Continuous flashing furnace (Hawthorne)
The waste streams associated with each of preceding operations
are determined by the method of disposal and the particular PEP being
demilitarized. Demilitarization processes utilizing open burning and
incineration result in emissions of NO^ and particulate matter to the
atmosphere. Open burning does not employ any emission control devices
or systems. Incineration designs, on the other hand, employ cost-
effective baghouses (in the case of APE 1276) for particulate removal.
N0x emissions are uncontrolled, at present, but control methods are
under development.
Rotary and kiln and fluidized bed incinerators are designed for
destruction of PEP already removed from the munition. Their control
of air emissions is uncertain. Recent conversations with military
installations reveals severe pollution problems resulting from incin-
eration (AEO, Ft. Detrick, Maryland and Tooele Army Depot, Utah). Bag-
house collection devices have shown the presence of TNT, RDX, HMX
and toxic metals in the gaseous effluent as well as the solid waste
residues. The extremely hazardous and potentially explosive nature
of these contaminants presents a dangerous situation. Attempts to
localize and correct this hazard have already been undertaken. Deto-
nation of munitions in earth-covered pits has shown no harmful air
emissions.
Wastewater effluents result from operations using hot water,
steam, or high-pressure water for washout of PEP from munition housing
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parts. These waste streams are characterized by suspended or dis-
solved explosives or propellants. Current treatment methods for
wastewater effluents from specific PEP's have been discussed in pre-
vious sections.
Demilitarization processes for PEP removal which are non-
contaminating to the air or water, do exist. These are: contour
drillout, a standard technique; microwave meltout, the safety of which
has not been demonstrated; and pyrotechnic processes developed at the
Crane Naval Facility in Indiana (NWSC, Crane). The solid waste stream
from these demilitarization activities consists of scrap metal and
inert furnace ashes. For the most part, it is inert and harmless to
the environment if the processes are carried to completion. Scrap
metal is typically sold. No information is available on the ultimate
disposal of the ashes.
5.5.14 Treatment Alternatives for Bulk PEP
Other means of reducing the waste inventory are being used, but
are not really viable forms for ultimate disposal. For example, the
Navy has sold bulk PEP's (propellant powder, TNT, Composition-B) to
commercial blasters, explosives manufacturers, and fireworks companies.
Table 5.7 shows the quantities of bulk PEP sold for commercial use
between 1974 and 1977.
Table 5.7 Bulk PEP Sold to Commercial Users
Year
Composition-B
(pounds)
TNT
(pounds)
1974
1,533,343
1,812,673
1975
750,544
2,545,165
1976
2,311,914
1,420,651
1977
1,953,452
2,059,959
Of these amounts, about one quarter was virgin material, such as dril-
ling dust, and the remainder was reclaimed from meltout and washout of
munitions. Recovered PEP also has been reused by the military. Large
quantities of TNT, for example, have been used to simulate shock waves
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from nuclear bursts. The military also is studying the possibility of
reclaiming PEP for reuse in new munitions, but this poses various
technical problems, including the difficulty of meeting new munitions
specifications, and the question of PEP impurities.
Successful conversion of unwanted PEP into a saleable or useable
non-PEP derivative has been shown to be technically feasible. For
example, red water sulfonated TNT has been converted to plastics inter-
mediate. Tooele Army Depot has started plans to build a pilot plant
converting white phosphorous from unsuitable munitions into saleable
phosphoric acid. Pine Bluff Arsenal has demonstrated the saleability
of white phosphorus already, without prior conversion. Iowa AAP has
been successful in converting surplus lead azide electrolytically to
metallic lead.
A final alternative showing promise is the burning of scrap
PEP for energy recovery. Admixtures to fuel oil would reduce fuel
requirements for incineration. Up to the present, this has been ob-
jectionable due to safety considerations.
5.5.15 Costs For Demil Facilities
A recent meeting of John Brown Associates, Inc. (Brown, 1979) -
with personnel from Hawthorne AAP, Western Demil Facility (WDF) has
resulted in detailed technical and economic information concerning
Hawthorne's demilitarization alternatives. They have proposed an
environmentally sound installation designed to handle a large ammuni-
tion demil inventory. It will be energy-intensive, however, and will
lack adequate control for NO^. The facility, which stockpiles about
2/3 of the Navy's demil inventory, projects a 5-year workload. Little
PEP recovery is planned.
Cost estimates range in the millions: $37M for facilities,
$18M for equipment, and $6M for startup. Total operating manpower
is estimated at 88 for production, 8 for engineering, and 26 for
maintenance at full-scale operation. The burdened hourly costs for
one 8-hour shift/day are $36, $33 and $27 respectively.
The following cost breakdown delineates where some of these
costs are incurred.
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Cost Breakdown	Cost	Manpower
Preparation Building	Not Available
6 cells
control room with remote control consoles
for each cell
Smokeless Powder Accumulation Building	Not Available
(capacity 4700 lb/hr)
vacuum collector
storage
Mechanical Removal Buildings	Not Available
press/puncture
equipment bandsaw
gauged hole saw
major caliber defuzer
large bandsaw
Refining Building (Steam Mel tout)	$2.03M	2
(for TNT, Comp.-B, 2200 rounds/8-hr)
melt kettle
vacuum kettle
flaking belt
Bulk Incinerator Building	51.48M	3
(Radford rotary kiln - capacity
1100 lb $PEP/hr)
explosives grinders
slurry holding tanks with agitator
2 rotary kilns, ceramic lined,
afterburners
fuel oil
Washout/Steamout Building (Hydraulic cleaning)
hot water washout (tower it2)	$2.28M	7*
melt kettle
vacuum kettle
flaking belt
high pressure washout (tower #2)	$1.27M	2
(TNT, Comp-B, ammonium picrate-
capacity 2100/8-hr shift)
*8-hour shift
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Cost Breakdown
Decontamination Buildings
rotary deactivation furnaces
(capacity 8000 lb/furnace/hr)
2 APE 1236 type
feed system
5-section retort
cyclone separators
APE 1276 baghouse filters
large-item flashing chamber
(capacity 6 items/8 hr shift)
35' cylindrical room with tracked
car-bottom system
gas cooler using 121, 8" diameter
steel pipes in two 20' sections
6 baghouses
continuous flashing furnace	$1.68M	6
(capacity 1100 rounds/8 hr shift)
2 cells
conveyor
baghouse filter
Water Treatment Building	$1.29M
conventional municipal type treatment
with flotation/clarifier
3 coal/sand filters
backflash equipment
3 carbon bolumns
heat transfer system
Boiler Plant	Not Available
three 50,000 lb/hr boilers
6 baghouse filters
The following cost breakdown of the NOS Indian Head facility,
Maryland, also resulted from the meetings of John Brown Associates
(Brown and Shapiro, 1979) with facility officials. Indian Head, how-
ever, is ocnstructing a demil site which has no full-scale counterparts
at other sites. The four components are:		
•	Zimpro wet air oxidation unit
•	fluidized bed incinerator
•	high-pressure water washout system
•	wastewater treatment plant.
Cost	Manpower
$1.67M	6
31.27M	4
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Because of this, actual costs are not specified, but rather are best
technical estimates.
Wet air oxidation equipment
Total system including engineering
and construction
$400K
$4. 3M
Fluid bed incinerator unit
Total system including engineering
and construction
Unknown
$6. OM
High pressure washout unit
Total system including engineering
and construction
Unknown
4M/estimate
Water treatment plant
^1.2million
Total Capital Cost
$10+M
5.6 SUMMARY OF EXPLOSIVES INDUSTRY WASTE STUDY
Complying with the proposed EPA hazardous waste regulations of
December 1978 would presently be impossible for most of the commercial
and military explosives industries. Treatment of waste effluents	
gaseous, aqueous, or solid	to minimize pollution problems is currently
less than adequate, and is not practiced in most cases. Because of the
hazardous nature of explosives, producers are usually located in remote,
sparsely populated areas on a large tract of land. Therefore, cases
of leachate contamination of surface or groundwater have not been found,
though they are likely. The increase in NO , particulates, or other
X
gaseous pollutants to the surrounding atmosphere under these circum-
stances, would also be minimal. In isolated locations, ultimate dis-
posal of potentially hazardous solid waste can easily be handled by
open burning or land burial on-site	far removed from any sensitive
geographic/demo graphic areas. Isolated locations are not always the
case, however, especially for military institutions such as Iowa AAP.
Use of large land areas for disposal does not present severe
economic or institutional barriers to most explosives manufacturers.
The cost of hazardous waste treatment and disposal would be compara-
tively lower for these manufacturers.
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Current methods of wastewater treatment are rudimentary, if they
exist at all. Therefore, compliance with new regulations would impose
a severe technical and economic burden on most commercial and military
explosives facilities. This burden might be alleviated if the in-
dustry adopted sound water and waste management practices, such as
good housekeeping practices, improved clean-up of equipment and
buildings, adoptions of environmentally sound and updated processes
for the various manufacturing operations, elimination of obsolete
equipment in favor of automated process, handling and packaging opera-
tions, and substitution of less hazardous fuel or intermediate products.
All these measures would reduce waste volume at the source with an
accompanying reduction in the quantity of potentially hazardous and
toxic constituents. Reuse and recycling of water effluents could also
be achieved to further reduce waste loads.
Adoption of primary treatment methods, in some cases, might be
as simple as pH adjustment, neutralization, filtration, and centrifu-
gation, with subsequent land application of the residue. Where geo-
graphically permissable, open burning of the residue using precaution-
ary safety measures may be the best approach until better alternatives
for treatment and disposal become available. For the military, im-
proved water management programs, reclamation, and reuse of bulk PEP
removed from obsolete munitions, sale to commercial buyers of reclaimed
metal and munitions still in fair condition, or reuse by foreign
governments or within the military for munitions, and other useful
applications, is perhaps the most economical and technically feasible
approach to reducing the large waste PEP inventory.
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6.0 REGULATORY OPTIONS
The final task in this project involved the assessment of alterna-
tives for regulation of ignitable, reactive and volatile wastes. The
following questions are addressed below:
•	Should disposal of IKV wastes be allowed in landfills?
•	Should the wastes be treated prior to disposal to render
them less hazardous?
•	How can resource recovery be encouraged?
•	Would dilution of wastes render them less hazardous
or more easily disposed of?
•	Can dilution serve as a means for complying with
Interim Status Standards?
•	Should long term waste storage be allowed?
•	What are the impacts of regulation on small businesses?
•	Is there a size of operation below which less restrictive
regulations will not seriously impact the environment?
•	For IRV wastes, should industries, waste streams, or
pure substances be regulated?
•	Should wastes be regulated-on the basis of their
volatility?
6.1 LANDFILL DISPOSAL OF IGNITABLE, VOLATILE AND REACTIVE WASTES
The proposed Hazardous Waste Guidelines and Listing Section 250.45
Standards for Treatment and Disposal (December 18, 1978) leaves the bur-
den of proof for environmental safety to the site owner and operator
before disposal of ignitable, volatile and reactive wastes can be allow-
ed in a landfill, surface impoundment, basin or landfarm. From our
investigations, it appears that landfill disposal was the best current-
ly applied technology for only two of the waste streams studied	waste-
water treatment sludges from electroplating and woven fabric dyeing and
finishing	and for these wastes, dewatering, chemical fixation or
encapsulation were recommended prior to final disposal. Because the
6-1
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waste streams studied are representative of a broad range of IRV waste
streams in industry, and because landfill disposal was determined to be
suitable for only two of the thirteen waste streams, it may be that
landfill disposal, in general, does not represent the best available
technology for IRV wastes.
6.2 TREATMENT TECHNIQUES FOR IGNITABLE, REACTIVE AND VOLATILE WASTES
Treatment techniques for ignitable, reactive and volatile wastes
include incineration or other thermal destruction, concentration of the
ignitable, reactive and volatile constituents for reuse, or chemical
conversion of the waste into a salable product. Some form of incinera-
tion was applicable to 11 of the 13 waste streams studied, and was
determined to be best available technology for eight of those waste
streams. Incineration may be used to reduce volume and to destroy the
IRV constituents in the waste stream; the residue can generally be dis-
posed of in a landfill. The disadvantages of incineration include the
need for maintaining high temperatures and long retention times to in-
sure thermal destruction of many IRV wastes, the high capital cost of
equipment, the high operation and maintenance costs for maintaining that
equipment, and,the cost of providing supplemental fuel.
Enforcement of regulations for incineration was considered feasible.
Stack emissions should be monitored at regular intervals, but savings in
monitoring costs may be reduced by measuring, at frequent intervals,
primary and secondary combustion temperature and the feed rate. Stack
emissions may be monitored at longer intervals. The necessary retention
time may be designed into the incinerator. The State of Connecticut has
reported successful monitoring of emissions from incineration of non-
chlorinated solvents by using the above monitoring system (Section 6.9).
The high cost and energy requirements of incineration encourage
the consideration of other methods for removing IRV properties from
waste streams. Recovery of valuable constituents in waste streams was
observed for two of the 13 waste streams studied (Chapter 3). Recovery
and reuse was determined to be the most environmentally sound practice
for several other waste streams. Special circumstances, such as the

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type of process and product quality control requirements, make it diffi-
cult to recommend the application of recovery practices by an exemplary
production facility to all facilities of an entire industry. An example
would be the reuse of spills and spoiled batches in paint production,
described in Chapter 3. Although the recovery of valuable constituents
from waste streams is desirable., it is difficult to encourage from a
regulatory standpoint. Some financial incentives already exist. Raw
materials savings are to be realized, as are savings in disposal costs
due to the decreased volume for disposal and the decreased hazard posed
by the waste, which may allow the use of less expensive handling and
disposal techniques. Therefore, it does not appear that special regu-
lations for recovery of valuable constituents are necessary at this time.
Chemical treatment for conversion of the waste into a salable pro-
duct was not practiced for any of the 13 waste streams studied. Several
chemical treatment processes were recommended as most environmentally
sound methods. More research and development are needed to permit gen-
eral application of these processes to IRV wastes.
In general, it appears that treatment of IRV wastes is feasible,
but expensive. Except for incineration, further research is necessary
in many areas before treatment processes can be applied to an entire
industry. However, isolated plants have been found in many industries
which treat wastes for recovery and reuse of valuable constituents.
6.3 WASTE STORAGE
The December 18, 1978 Draft RCRA 3002 Regulations proposed a 90-
day cutoff period for permanent versus temporary waste storage. The
90-day period appears to be reasonable, considering the following:
•	Containment vessels would probably not be breached
except with poor management practices.
•	Some time allowance is necessary to accumulate a
full load of wastes for off-site disposal.
•	Some time allowance is necessary in case of equip-
ment breakdown, strikes, etc.
6-3
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Certain reactive materials,, such as explosives, should be handled
on a case-by-case basis with no storage allowed unless adequate safety
precautions are taken. Contact with off-site waste disposal facilities
revealed that many do not accept explosives. A general discussion on
storage of ignitable and volatile wastes is given in Section 3.2 and in
Chapter 5. The current practice at industrial plants is to store 1RV
wastes in 55 gallon steel drums. Detailed information on other techni-
ques for storage of wastes was not available. Lagoon storage was prac-
ticed for only two of the 13 waste streams studied.
6.4 MIXING OF WASTES
Mixing of wastes may be performed by either the generator or dis-
poser. Generator practices vary depending on whether treatment, storage
or disposal of wastes is performed on the plant site or by an off-site
waste disposal contractor. If on-site, wastes may be segregated by
their ultimate destinations (incinceration, landfill materials, recovery)
for a large multiproduct manufacturer, while a smaller facility with
only an on-site landfill may not segregate wastes at all.
Off-site disposers must be careful to accept only those wastes
that can be effectively treated by their particular equipment or safely
disposed at their land disposal facility. Therefore, segregation of
wastes becomes more critical, consequently careful segregation by a
generator can result in decreased charges by the disposer. Segregation
of wastes by the generator should be encouraged also because of the
greater potential for recovery of valuable constituents for reuse.
Numerous instances of waste mixing were found in telephone con-
tacts with disposers. The most obvious instances were mixing of acids
and bases for rough neutralization prior to further addition of chemi-
cals. Savings in neutralization chemicals were significant. Careful
mixing of wastes with fuel prior to incineration allowed savings in
supplemental fuel by utilizing heat values of combined wastes. In this
manner, high heat value wastes can be combined with those having little
6-4
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or not heat value; the objective is generally to use supplemental fuel
only for start-up.
Mixing of inert materials such as water with explosives prior to
incineration is common. The result is increased protection to personnel
operating incineration equipment and to the equipment itself by limiting
the potential for severe explosions.
Mixing of inert materials with- other IKV wastes prior to landfill
has been reported, although it is not generally considered by the dis-
posers themselves as a good practice. IRV properties may be reduced,
but the mass disposed and potentially released remains the same. One
disposer commented that even if the practice were acceptable, it would
not be economically feasible due to the large quantities of inert mat-
erials needed to dilute many IRV wastes to acceptable levels. Allowing
the dilution of IRV wastes as part of Interim Status Standards is,
therefore, not recommended.
6.5 TREATMENT, STORAGE OR DISPOSAL OF WASTES OFF THE PLANT SITE
Although general improvement in off-site disposal practices has
been made over the last several years, the off-site disposers performing
best available technology for IRV wastes are not as common as they should
be to ease the transition as regulations are implemented. The question
is, therefore, whether there will be enough complying off-site disposers
to handle the quantity of wastes generated by industry, and whether the
complying waste disposal contractors will be strategically located so
that transportation of IRV wastes over long distances can be avoided.
Conversely, industry may feel that disposal on their plant site
gives them better control over wastes for which they are ultimately
responsible. It is believed that, in general, large plants will tend
to dispose on-site, while smaller plants with smaller technical staffs
and less available capital will use contract disposers. Smaller waste
volumes, particularly those generated by small plants, will necessitate
storage until enough is accumulated to justify a waste pick-up by the
disposer or delivery to the disposal site by the generator.
6-5
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6.6	IMPACT OF REGULATIONS ON SMALL BUSINESSES
Based on the study of industries such as electroplating and paint
manufacturing given in Chapter 3 which are composed of many small
businesses, it would be difficult to set a cutoff point for size of
operation which would allow less restrictive regulation of small busi-
nesses. Although it is recognized that the impact of the regulations
will probably be greatest for smaller businesses, their wastes are no
less hazardous than those of large operations.
Paint industry wastes are good candidates for reuse. Spills and
spoiled batches are already reworked into the process where possible,
and solvents are frequently recovered for reuse. Some solvents, spills
and spoiled batches are more easily recovered than others, however, and
residues remain from recovery processes which require disposal. In the
paint industry, much progress is being made toward reducing waste vol-
umes by more efficient usage of materials, improving housekeeping prac-
tices and decreasing the quantities of hazardous materials such as pig-
ments and solvents used in the process. Small businesses in other in-
dustries must become aware of the potential for reuse of wastes and
the potential for reduction of wastes generated. For wastes which have
uses, but not at the plant generated, a waste exchange between plants
may become feasible. The regulatory aspects of this practice are not
known.
6.7	DEVELOPING REGULATIONS FOR HAZARDOUS WASTES
The alternatives for regulations of hazardous wastes include:
•	developing regulations for classes of hazardous wastes
a basing regulatory decisions on the hazards posed by
pure chemicals or on the hazards posed by a waste stream
•	developing regulations for waste streams on an industry-
by-industry basis
•	developing regulations on a plant-by-plant basis.
6-6
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The above regulatory alternatives were briefly evaluated following the
completed analyses of the thirteen specific waste streams, and in light
of the technical alternatives assessed. Our conclusions follow.
Concerning the development of regulations on pure substances versus
total waste stream composition, the waste streams studied were not pure
substances but were mixtures of many compositions, some of which were
hazardous. If pure substances were used as a basis for regulations,
then a cut-off point would have to be determined (such as the one mg/£
mentioned in the December 18, 1978 draft) below which the waste stream
would not be considered hazardous. When waste streams were considered
as a basis for regulatory process, differences which caused variations
in waste streams became significant. These process differences may need
to be carefully described in regulations based on waste streams. There-
fore, it was found that both the application of a "pure substance ration-
ale" and also the application of a "waste stream rationale" to our thir-
teen waste streams posed different problems and that neither was totally
suitable.
It was also observed that both approaches did not fully consider
other important aspects such as waste form (sludge, liquid, etc.) and
the disposal environment.
When we consider the application of an industry-by-industry approach
to the waste streams studied, it was found that identification and track-
ing of waste streams seemed easier. This was offset by problems posed
by regulating facilities covered by many SIC codes and producing a mixed
waste. In summary, regardless of the regulatory approaches used, it
seemed important to consider the chemical composition, form, hazardous
properties, and disposal environment of waste streams, and to consider
variations in waste streams (both plant-by-plant and within a given
plant). Our further analysis of regulatory approaches was hindered by
the lack of statistically significant information on the composition of
each waste stream and by a lack of Information on spills, process
changes, product changes, equipment changes, in-plant housekeeping and
by the degree of waste stream mixing prior to disposal.
6-7
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6.8	REGULATION OP VOLATILE WASTES
One of Che initial tasks of this project was to develop a definition
of volatility that would be useful in the remainder of the project and
potentially useful for regulations. The definition of volatility pro-
posed in the December 18, 1978 Draft was that substances having a vapor
pressure greater than 78mm of mercury at 25°C would be considered vola-
tile. The definition developed under this project considers volatile
substances with vapor pressures greater than 78mm of mercury at 40°C,
which represents a temperature likely to occur in a disposal site in the
summer. Also considered volatile would be toxic substances with vapor
pressures between 0.1mm Hg at 40°C and 78nm Hg at 40°C.
From studying the thirteen IRV waste streams it has become apparent
that volatility is an important parameter to consider in regulations,
particularly for toxic substances. Volatility covers a physical trans-
port property of wastes not adequately addressed by the concepts of ig-
nitability and reactivity. Appendix A describes incidents where physical
harm resulted from inhaling toxic vapors of previously disposed substances.
The definition of volatility developed in this project needs veri-
fication on actual waste streams and development of a stronger basis
for the cutoff points if eventual use in regulations is anticipated.
Our recommendations for regulation are summarized and presented in
Chapter 2.
6.9	SUMMARY OF CONTACTS WITH STATE AGENCIES AND OFF-SITE WASTE
DISPOSAL CONTRACTORS
Summaries of contacts with selected state agencies and off-site
waste disposal contractors are given in Tables 6.1 and 6.2. It should
be noted that these contacts represent better than average practices and
regulations. Efforts were made to determine better than average waste
disposal contractors through state contacts, the EPA Project Officer,
and in-house knowledge of disposal contractors.
6-8
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From these contacts it was learned that many states have either
very recently passed regulations conforming to expected federal regula-
tions, or are in the process of doing so. It was also learned that many
of the better waste disposal contractors are either already complying
with expected regulations or are making plans to do so. One waste dis-
posal contractor commented that those who expect to modify their sites
quickly as soon as regulations are out will make mistakes and could go
out of business trying to comply. His operation, by gradually modifying
and testing modifications, will need only minor modifications once regu-
lations are implemented.
6-9
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TabLe 6.1 Summary of Contacts with Selected State Agencies

CALIFORNIA
ILLINOIS
NEW JERSEY
CONNECTICUT
MARYLAND
WASTE MANIFEST SYSTEM
X
X
X

X
PROHIBIT IRV WASTES IN
LANDFILLS
Case by
case basis
Case by
case basis
X
Case by
case basis
Case by
case basis
SPECIAL CONTROL OF DIS-
POSAL OF WASTES WITH
HLGU METALS CONTENT
Case by
case basis
X
Case by
case basis
X
Case by
case basis
CHANGE IN REGULATION
IN PROCESS
X


X

COMMENT
Encourage
reuse/recycl-
ing through
waste exchange
and infor-
mation trans-
fer

No secure
landfills
exist in
state
Prohibit
incinera-
tion of
chlori-
nated
organics
Provision for
perpetual care
of disposed
facilities
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Table 6.2 Summary of Telephone Contacts with Selected IRV
Waste Disposers

Wescoo, Inc.
Twin Falls,
Idaho
Waste Hanage-
svnt. Inc.
Eight Facili-
ties. Based
In Illinois
IT Corp.
Hartlnei,
Calif.
BUC Corp.
Wilmington
California
Rollins Eov
Services
Wilmington
Delaware
Solvents
Recovery,
ifw -, Linden
New Jersey
Significant
Chiracterlsclet
Water table
3300 ft deep
Us# abandoned
alsslle silos
and clav lined
t ranches
Located on
natural
clay depoalts
Located In
dry ares,
use solar
evaporation
Located
lo dry
area
Located la
wet srea
Operation set
up to recover
solvents
Inclne ration

X
X

X
X
Blending of fuels

X
X

X
X
Other treatment


X



Storage


X

X

Diaposal
Secure Landfill
X
X

X
X

Encapsulation
X


X
X

Deep Well injectloo



X
X

Land Faro


X

X

Cround Water Honltorlng

X
X
X
X

Uaate Location Records
X
X
X



Solvent Recovery


X


X
Handle Reactive Wastes


X

X

Determination of TSO
Methods
t
Lab Analysis 1
X
X
X
X
X
X
Waste Form
! x
X
X
X
X
Exclusion of
Explosives
1
j
X
X
X
X
Separation of In-
compatible Wastes
X I
1
X
X
X

CGKHENT
i
Excellent
location 1
:
Adjusting
operations
to comply
with antici-
pated regu-
lations
Excellent
location
allows use
of solar
evaporation
Bury
con-
tainers
of IRV
wastes
In cells
of sbeor-
bent ne-
terlal
Incinerate
still
>otteas
Inclnersce
aolvent re-
sovery residues,
Ilspose inclne-
rstlon residue
Ln off—sits
Landfill
6-11
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Tezuka, K. U.S. Patent 3848392, assigned to Tezuka Kosan, K.K.
(November 19, 1974).
Tucker. Progress in Hazardous Chemicals Handling and Disposal:
Institute of Advance Sanitation Research, 1972.
U.S. Environmental Protection Agency. Assessment of Industrial
Hazardous Waste Practices. Storage and Primary Batteries
Industries. 1974c.
U.S. Environmental Protection Agency, 1974. Development Document
for Effluent Limitations Guidelines and New Sources Performance
Standards for the Textile Mills, Point Source Category. EPA-
440/l-74-022a, June 1974.
U.S. Environmental Protection Agency, 1974. Sludge Treatment and
Disposal. Washington, D.C. EPA 625/1-74-006, October 1974.
U.S. Environmental Protection Agency, 1974. Disposal of Hazardous
Wastes, p. 63-64, 1974b.
U.S. Environmental Protection Agency, 1975. State of the Art for
the Inorganic Chemicals Industry: Commercial Explosives,
Atterson & Minear, Washington, D.C. PB 240960, 1975a.
U.S. Environmental Protection Agency, 1976. Assessment of
Hazardous Waste Practices in the Petroleum Refinery Industry.
Jacobs Engineering Co. PB-259-097. June, 1976.
U.S. Environmental Protection Agency, 1976. Preliminary
Examination of Vinyl Chloride, Emissions from. Polymerization
Sludges During Handling and Land Disposal, EPA R-803-11-01-03,
p. 4, February 1976a.
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References (Continued)
U.S. Environmental Protection Agency, 1976b. Assessment of
Industrial Hazardous Waste Practices; Electroplating and Metal
Finishing Industries Job Shops. EPA Contract No. 68-01-2664.
September 1976b.
U.S. Environmental Protection Agency, 1976c. Assessment of
Industrial Hazardous Waste Practices, Paint and Allied Products.
U.S. Environmental Protection Agency, 1976c. Assessment of
Industrial Hazardous Waste Practices, Paint and Allied Products
Industry, Contract Solvent Reclaiming Operations and Factory
Application of Coatings.
U.S. Environmental Protection Agency, June 1976c. Assessment
of Industrial Hazardous Waste Practices, Textile Industry.
Office of Solid Waste Management Programs.
U.S. Environmental Protection Agency, 1976d. Development Document
for Interim Final Effluent Limitations Guidelines and Proposed
New Source Performance Standards for the Explosives Manufacture.
EPA 4401/1-76/060. June 1976.
U.S. Environmental Protection Agency, 1977. Assessment of
Industrial Hazardous Waste Practice, Special Machinery Manufacturing
Industries. Hazardous Waste Management Division, Office of Solid
Wastes.
U.S. Environmental Protection Agency, 1979a. Destroying Chemical
Wastes in Commercial Scale Incinerators. Chapter 4. SW-112, 1977.
U.S. Environmental Protection Agency, 1977b. Alternatives for
Hazardous Waste Management in the Organic Chemical Pesticide and
Explosives Industry. PB-278 059, September 1977b.
U.S. Environmental Protection Agency, 1977. Assessment of Industrial
Hazardous Waste Practices; Special Machinery Manufacturing Industries.
EPA Contract 68-01-3193, March 1977.
U.S. Environmental Protection Agency, 1977c. Control of Volatile
Organic Emissions from Solvent Metal Cleaning. EPA 450/L-77-022
November 1977c.
U.S. Environmental Protection Agency, 1977. Industrial Process
Profiles for Environmental Research, Chapter 12: The Explosives
Industry. Hudak & Parsons, Cincinnati, Ohio.
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References (Continued)
U.S. Environmental Protection Agency, 1977e. Assessment of
Industrial Hazardous Waste Practices: Electronic Components
Manufacturing Industry. Wapora. January 1977.
U.S. Environmental Protection Agency, 1978a. Development
Document for Proposed Existing Source Pretreatment Standards
for Electroplating Point Source Category. EPA-440/1078/085.
February 1978a.
U.S. Environmental Protection Agency - Land Disposal of Solid
Waste, Proposed guidelines 18138-18148. March 26, 1979.
U.S. Environmental Protection Agency (Federal Register):
Proposed Guidelines and Regulations and Proposal on Identification
and Listing (Part IV) December 18, 1979.
U.S. Environmental Protection Agency, 1978c. Vinyl Chloride,
Ambient Water Quality and Criteria.
U.S. Environmental Protection Agency (Federal Register): EPA
3001 Draft; 43 (243) December 18, 1978a.
Vaux, W.G., Weeks, S.A., and Walukas, D.J. Oil Spill Treatment
with Composted Domestic Refuse. In Proceedings of the Joint
Conference on Prevention and Control of Oil Spills. 1971.
Viola, P.L., Bigotti, A., and Caputo, A. Organic Response of
Rat Skin, Lungs, and Bones to Vinyl Chloride. Cancer Research,
31: 516-522; 1971.
Weismantel, G.E. Chem. Eng. 82 (22). 1975.
Wiles, C.C. and Lubowitz, H.R. A polymer—cementing and
encapsulating process for managing hazardous wastes in Residual
Management by Land Disposal. Proceeding of the Hazardous Waste
Research Symposium, Arizona University. July 1976.
Witt, Philip A. Solid Waste Disposal. Chem. Eng. May 8, 1972.
Zofell, C.E. Microbial Degradation of Oil: Present Status,
Problems and Perspectives. The Microbial Degradation of Oil
Pollutants. Center for"Wetland Resources, LSU-SG-73-01, 1973.
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Cudahy, J.J. and Standifer, R.L. Emissions Control Options For The
Synthetic Organic Chemicals Manufacturing Industry. Hydroscience,
EPA Contract No. 68-02-2577, October, 1979.
Easterbrook, G. These Reactors Are Designed For Meltdown; Waste Age.
May 1979. pp. 18-24.
Henriksen, P. One Private Plant Treats Oil, Chemical Residues in
Denmark. Solid Wastes Management. May 1974.
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APPENDIX A
WORKING DEFINITION
OF VOLATILITY
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WORKING DEFINITION OF VOLATILITY
Volatility is a chemical contact word used to describe the physical
characteristics of a substance, as a result it has been used as a means
of describing the potential hazard of a substance. Numerous damage in-
cident reports exist which ascribe the volatility of a waste material as
the cause of damage. Some of these are given in Table A.l.
Of the approximately 400 damage incidents in EPA's file of hazard-
ous waste disposal damage reports, eight incidents were identified which
were caused by air pollution from volatile substances (EPA, 1978). The
remaining cases were related primarily to water pollution problems.
Additional cases of incidents involving volatile waste disposal were
also identified from a cumulative annual study of damages from hazard-
ous wastes (Abbey, 1978).
One of the initial tasks of this project was to develop a working
definition of volatility to correlate this property of wastes with
damages that could result from Improper disposal. This definition was
developed and used to help determine whether or not waste streams
should be considered volatile. Definitions for ignitability and
reactivity, which had been included in draft regulations for RCRA
Section 3001 (Federal Register, 1978), were used to determine whether
waste streams fell into these categories. These three definitions are
given in Table A-2.
The original intent of the definition development effort was
solely to further the goals of this project. However, while the
definition was being developed, the EPA Office of Solid Waste was also
in the midst of considering definitions of volatility for the purpose
of regulating volatile wastes. Because of this, some effort was ex-
pended to assist EPA by assessing how the developed definition could be
used for regulating volatile wastes. The approach taken for developing
this definition was considered for use in regulations and rejected by
EPA. For the sake of completeness we have included some information
gathered for regulatory efforts even though data gaps exist in some
A-l
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Table A.1 Damage Incidents Involving Land Disposal of Volatile Wastes
Inj urv
Cause
Serious complaints of illness by 53
residents living in valley near
Elkton, Maryland
100 homes in Niagara Falls, N.Y.
abandoned with toxic fumes in
basements, leaching of chemical
waste in the backyards, and
basements. Local residents were
found to have health problems in
areas such as liver function and
success of pregnancy
Brain abnormalities found in
workers in Rocky Mountain Arsenal,
CO
Air pollution. Exposures to
mixtures of solvents due to a
nearby chemical plant that
recovered solvents from discarded
chemical materials (butyl alcohol;
amyl alcohol, ethyl acetate,
toluene, trichloroethylene, benzene,
methyl ethyl ketone, acetone, carbon
tetrachloride, chlorobenzenes,
butanol, ethyl ether, o-, m-, and
p-xylene.
Homes built on the old canal which
had been used as industrial dump
for 25 years. 82 different com-
pounds, 11 of them suspected
carcinogins, had been disposed there
(aliphatics, aromatics and chlorinated
compounds)
Inadvertant exposure to nerve gas
(organophosphate)
Several homes abandoned with
fumes and danger of fire in
Conell Hts., PA
Paints and solvent dumped in sewer
lines
17 workers sick m Louisville,
KY
Spill of organic hydrocarbons into
sewer
Compactor operator killed and
compacter destroyed in Calumet,
ILL
Explosion on compaction at landfill
of illegally dumped solvents
(ethyl acetate)
Bulldozer operator became
nauseated
People suffered nose bleedings,
nausea m Smithfield, RI
Persons suffered eye and throat
irritation in Lake City, GA
Fumes from benzene hexachloride manu-
facturing • wastes uncovered during
site preparation for a oaseball
field (lindane, BHC)
Landowner with unlicensed pit (PCB's;
phenols, methyl chloride)
Drums in landfill erupced sending
fumes into air (cyanide and organic
compounds)
A-2
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Table A.l (continued)
Imurv
Loss of bulldozer in Genessee
Co., MI
Some workers in the building
downwind became nauseated
resulting from air pollution
from the evaporation of volatile
liquid wastes from pond surface
in Contra Costa County, CA
Corrosive damage to homes in San
Francisco Bay Area. Residents
experienced noxious odors, eye
and throat irritation
Compacting bulldozer destroyed,
fish killed. Contamination of
air, and surface and groundwater
down gradient from the landfill
Alkyl lead intoxication at lead
recovery facility in San
Francisco, CA. 2 collectors
on a bridge became ill from
vapors escaping from trucks
hauling organic lead wastes
Cause
Bulldozer operator became dizzy
and eyes irritated, left oulidozer
and returned to find it in flames
(Volatile substances)
Volatile wastes evaporated from
the surface of a disposal pond,
(crotyl chloride, amines, and
Cj-Cg hydrocarbons)
Fumes (organic vapors, acidic vapors
etc.) from the surface of industrial
liquid waste evaporation ponds
(volatile industrial liquid)
Drums containing oily wastes and
nickel exploded during compacttion
(unidentified chemical wastes)
Evaporation of organic leaa vapors
from disposal sites, recovery
facilities, and from transporting
vehicles.
A-3
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Table A.2 Definitions of Volatility, Ignitability
and Reactivity Used in This Report
Developed Definition of Volatility
Volatile Substances are those with vapor pressures of 78 mm Hg
and higher at 40°C and those with vapor pressures between
0.1 and 78 mm Hg at 40°C that have Sax toxicities of 2 or
greater.
Substances that are not volatile
below 0.1 mm Hg at	40 C and
between 0.1 and 78 mm Hg at
of less than 2.
are those with vapor pressures
those with vapor pressures
40°C that have Sax toxicities
Existing Definition of Ignitability
Ignitable substances are those with flash points of 60°C (140°F)
or lower.
Existing Defintion of Reactivity
Reactive substances are those which are normally unstable and
readily undergo violent chemical change, or form toxic
fumes or explode when exposed to moisture. Additionally,
forbidden explosives as defined in 49CFR173.51, Class A
explosive as defined in 49CFR173.53, and class B
explosives as defined in 49CFR173.58 are included.
A-4
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areas. This information is by no means conclusive and does not reflect
current EPA thinking for regulating volatile wastes.
The developed definition was useful in determining whether waste
streams were volatile. However, the major problem for regulating
volatility using this definition, is the fact that a means of measuring
volatility of an entire waste stream was needed. Vapor pressures and
toxicities of waste streams are not widely available in literature.
Therefore, a major data development effort would have been necessary to
incorporate this definition in regulations.
A.l RELATION OF STUDY TO THE APPROACH CHOSEN
The primary purpose of developing the working definition was to
provide a relatively easy means for evaluating whether a waste stream
was volatile by using existing information in the literature. The
definition, in order to be useful to the study, had to incorporate the
assessment of major waste stream constituents. This approach is
illustrated by the list of substances, vapor pressures and toxicities
in Table A.3 and also the application of information such as that in
the table to the actual waste streams in Appendix B.
The purpose of this analysis was to evaluate the use of vapor
pressure and toxicity as a means of using volatility to indicate the
relative hazard of a substance. Vapor pressures are usually expressed
in the literature for each chemical at 25°C temperature. One approach
was to determine vapor pressure at 40°C, since it was believed that
this temperature more nearly described the temperatures that may be
encountered in land disposal facilities.
The developed definition was applied for specific pure substances.
The substances were listed with 60th volatility indices and their
toxicity ratings according to Sax.
A-5
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Volatility for 40°C was calculated using the following formula
which is the Clausius-Clapyron equation:
,	AH 1 + constant
log P " O03R ~
Where AH can be evaluated from the slope of the line and value of
2.303R
log p at a point on the line.
Table A.# illustrates the volatility at 25°C and 40°C for example
chemical substances, also listed are their toxicity ratings according
to Sax.
A. 2 VOLATILITY OF PURE SUBSTANCES
A list of ignitable, volatile and reactive waste streams was
assembled from the literature and is included as Appendix B. The
definitions given in Table A.l were used in determining whether waste
streams belong in the list. Additionally, since most waste streams
are made up of many components and some may be Ignitable, volatile and
reactive, while some may not, a waste's inclusion in the list was
determined by considering known major constituents. Therefore, the
definition developed for this study was applied to a number of pure
substances to determine whether or not they would be considered
volatile. A discussion of some of the findings follows.
There are many compounds that have vapor pressures above the
78 mm Hg level in the developed working definition. Among these is
carbon tetrachloride, which at A0°C has a vapor pressure of 216 mm Hg
and whose inhalation toxicity has a rating of 3 for both chronic and
acute systemic effects. Acetonitrile, a major component of the waste
stream generated in its production, also presents a hazard. At 40°C
it has a vapor pressure of 140 mm Hg and an acute systemic inhalation
toxicity rating of 3. Both of these compounds would be volatile
according to the developed definition and the EPA proposed definition.
A_£
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TABLE A.3 Comparison of Vapor Pressures and Toxicities of Selected Chemicals
Toxic Hazard Rating by Inhalation	N10SH* Standards
Chemical
Vapor Pressure
at 40°C nun Mr
Vapor Pressure
at 25°C ram lift
Acute
Local
Acute
Systemic
2
Chronic
Local
Clironlc
Systemic
2

Ethyl ether,
C«"lO°
921.00
532.45
12
U

Methylene Chlorido,
(ntchtoramethene), CII^Cl^
784.28
425.07
12
3
|i
1
7 5 ppm TUA
261 mg/m
Dioxone,
W2
79.68
40.08
2
3
V
3
1 ppm 3
3.6 mg/m
Acotone,
W
421.00
228.80
2
2
11
1

cie - 1,2 - Dielilorocthylone,
W:,2
387.77
202.50
2
2
11
I

Tlilornf oral,
oici1
362.21
190.6ft
11
3
11
u
2 ppm
9.78 fflg/n
Qirlmn tetrachloride,
cc:i4
210.00
117.9*
0
3
11
3
2 ppm j
1T.ft mg/m
Methyl cthvl kctony,
W
185.5(1
95.82
1
2
11
|i

F.tliyl nccrntc,
Wl
178.50
67.6ft
11
2
II
1

Dciircnr,
170.48
80.2?
1
2
0
3
1 p|im
'Nntlonnl Institute for Occupational Safety nnd Health
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TABLE A.3 Comparison of Vapor Pressures and Toxicities of Selected Chemicals (continued)
Clicro lea 1
Aceton1trIle,
W
Tr tcliloroet hy lene»
CjMClj
Vapor Pressure
at 40° C mm llg
170.18
141.04
Vapor Pressure
at 25 C mm llg
R7.78
71.98
To»lc llatard Rating by Inhalation
Acute	Clironte Chronic
Acute
Local
11
II
Systemic
3
Local
12
U
Systemic
1
1
N10SII Standards
<_ 4 ppm
8.7 rog/a
>
I
00
Ethyl Alcohol,
CjlljOll
1,2 - Dlcliloropropane,
C3n6C,2
1,4 - Dloxnne,
W2
Water,
"2°
Toluene,
C7M8
Tet rachloroethylene,
C2C,4
n-<>ctnnc,
C8"l8
Benzyl Chloride,
Wl
F.tliyl benzene,
V'.O
135.00
99.57
79.97
55.32
55.57
37.56
31.00
24.28
20.43
58.76
50.30
40.08
23.76
26.68
17.78" —
13.77
11.20
9.30
II
12
12
II
12
. 0
11
II
II
12
II
1 ppm 3
3.6 mg/ro
100 ppm .
375 mg/n
50 ppm -
339 mg/m
5 mg/m
12
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TABLE A.3 Comparison of Vapor Pressures and Toxicities of Selected Chemicals (continued)
Tonic llaiard Rating by Inhalotlon
H10SII Stundurds
Clicml cjnl
UiiCriiiol ,
V.o0
Styrunc,
V'«
1,1,2,2 - lutrachoroutliaue,
wu
CyL lolioxunone,
Cb",0°
Pentucliloroetltuiie,
C2IIC,5
I,A - biclilorobunieeite,
W2
Ulnicione illcolio 1
Ch".202
Phono I ,
W
HI trobtiitzenu,
C6"SM°2
Vapor Pressure
at 40°C mn Hit
IS.21
15.75
14.04
10.26
10.10
4.69
). J2
1.00
0.8)
Vapor Pressure
nt 25°C mn lln
7.00
7.22
6.29
4.55
4.44
1.99
1.29
0.40
0.31
Acute
Local
11
12
Acn
Sys
12
12
e
eralc
Clironl c
Local
II
12
Clironlc
Systemic
1
2
5.2 ppm3
20 mg/m TWA
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TABLE A.3 Comparison of Vapor Pressures and Toxicities of Selected Chemicals (continued)
Toxic llatard Rating by Inhalotlon	N10SII Standards
Chemical
1,1,4 - Tr Ichlorobenzene,
W»J
2,A,5 - TrIchloroplienol ,
Wi°
Vopor Pressure
at 40°C nra IIR
1.13
0.14
Vapor Pressure
at 25°C ran IIr
0.4}
0.05
Acute
Local
12
Acute
Systemic
Chronic
Local
loss liair
Clironic
Systemic
>
I
1 - Chloronuphtlialene,
c,ni.7ci
0.10
T - llcxachlorocyclohexnne,	< 0.14
Wb
o.oj
II
A1,I1
1}
A2
Diethyl phthalate,
C|2".«°A
0.012
0.003
Mercury, metallic
l*CH • a
0.007
< 0.1
0.002
11
12
I2.A3
13
I mg/u' IVA
U:	not harmful, unless unusual conditions or overwhelming dosage
1:	slightly harmful, effects readily reversible after exposure period
it modur.iloly harmful, Irreversible and reversible effects noc enough to cause death or permanent Injury
3: highly tuxlc, can cause death and permanent injury
I
\i: unknown effects
It Irritant	A: Allergen
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A.2.1. Excluded Wastes
PCB's are an example of wastes known to have a significant inhala-
tion toxicity (a rating of 3 for ecute systemic and chronic local and
systemic), but they are not volatile according to the definition. This
class of compounds has a vapor pressure slightly below the 0.1 mm Hg
level. Most organic compounds having 16 to 18 carbon atoms or more have
vapor pressures below 0.1 mm Hg, and so would not be defined as volatile.
The definition would exclude metallic mercury, an element known to be
toxic. It has an inhalation toxicity index of 3 for both acute and
chronic exposure. It also has a vapor pressure of 0.09 mm Hg at 40°C,
which is below the minimum vapor pressure of compounds to be included
by our definition. Despite this low vapor pressure it has significant
toxic effects in its vapor phase and over time can saturate the air of
a room with a high enough concentration of mercury vapors to have
noticeable toxic effects.
A.2.2 Included Wastes
There are a large number of compounds that have vapor pressures
between 78 mm Hg and 0.1 mm Hg. Examples include phenol and trichloro-
benzene. Phenol, a constituent of the waste stream generated in the
production of phenolic resins, has a vapor pressure of 1.57 mm Hg at
40°C and an inhalation toxicity rating of 3 for acute exposure and 2
for chronic exposure. Trichlorobenzene isomers are a major constituent
of the waste stream generated by polyester manufacture. 1,2,3-trichloro-
benzene has a vapor pressure of 1.0 at A0°C and an inhalation toxicity
rating of 2 for both acute and chronic systemic effects. When present
in sufficient concentrations in the waste stream, both of these com-
pounds pose a potential hazard due to their vapors.
Heavy metals and organometallics are typically present in very
small concentrations in waste streams, yet are hazardous due to their
volatility and inhalation toxicity. Examples are tetraethyl lead and
organo arsenic compounds. Tetraethyl lead is a constituent of the
waste stream generated when it is produced. It has a vapor pressure
A-ll
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of 1 mm Hg at 38.4°C and an inhalation toxicity of 3 for chronic and
acute exposure. Organo arsenic compounds are constituents of waste
waters of pharmaceutical manufacturing. They have inhalation toxicities
of 3 for both acute and chronic exposure. Both compounds, though they
appear as minor constituents of waste streams and have fairly low vapor
pressures, pose a hazard due to their Inhalation toxicity.
Comparison of JRB's list of components of potentially hazardous
waste streams (Appendix B) with the OSHA (1979) and NIOSH (1979) lists
of Threshold Limit Values (TLV) guidelines for industrial exposure, we
have found that with the exception of kerosene and crotyl chloride,
which is not widely used, JRB's list of key components is contained
within the OSHA and NIOSH lists. A more exhaustive search of waste
streams may reveal more compounds not on the OSHA and NIOSH lists. How-
ever, our list of waste streams is aimed at waste disposal problems as
opposed to exposure to hazards in the work place dealt with by the OSHA
and NIOSH lists. Vaste steams by their nature are mixtures of many
components that do not behave in the same way as pure compounds and
must be handled differently.
A.3 VOLATILITY IN LANDFILLS, IMPOUNDMENTS AND LAND TREATMENT FACILITIES
Volatility would apply to a waste regardless of its disposal in a
landfill, an impoundment or a land treatment facility (land farm)
operation. Volatility as defined previously describes a property of a
substance at 40°C, which is more conservative than the 25°C at which
vapor pressures are normally given.
In a landfill, the presence of soils of low permeability may allow
the build-up of pressure from volatile substances. The compacted soil
may develop fissures through which vapors can escape. Ambient tempera-
tures at the surface may approach 40°C in summer months, while tempera-
tures below the surface will be somewhat less and will decrease with
depth to roughly the mean annual temperature for the landfill site.
Exceptions are where decomposition and other reactions are taking
place, which may increase temperatures to as much as 60°C.
A-12
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Impoundments will contain combinations of substances such as
liquids and sludges which would flow if unrestrained. Volatile compo-
nents in impoundments then tend to be released to the atmosphere con-
tinuously from the surface unless impeded by a top layer of another
substance of relatively low specific gravity. Pressure will not build
to the degree that may occue in a landfill.
Land treatment is a waste management practice that includes the
application of waste onto the soil and/or incorporation into the soil
surface. The soil serves as a physical-chemical filter medium to
immobilize inorganic waste constituents, and as a substance for bacte-
rial degradation of organic waste constituents. Compaction of the soil
is not necessary. Volatile substances in a land farm can be released
to the atmosphere more easily than in a landfill, although pressures
may temporarily build in the deeper portions of disturbed soils.
Temperatures may approach 40°C at the surface, but would normally
decrease below the level at which wastes are disposed.
A.4 VOLATILITY OF IMPURE SUBSTANCES
Very few waste streams are pure substances. Therefore, the vola-
tility of impure substances also must be considered to make the
definition useful for evaluating mixed wastes. Advantages and dis-
advantages of various approaches to the issue of concentration, partic-
ularly low concentrations of highly volatile substances in an impure
waste stream, are presented below.
A.4.1 Concentration Cutoff Point of 1 Percent
Consideration was given to establishing a low limit below which
concentrations of volatile substances in a waste stream could be dis-
regarded. A 1 percent value has been suggested because this concentra-
tion could be easily determined by a waste generator or disposer. A
waste stream containing 99 percent or more nonvolatile substances and
1 percent or less volatile substances would be considered nonvolatile.
This approach has the advantage of simplicity since it would apply
A-13
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under all conditions. The disadvantages are the possibility of allowing
improper disposal of a highly volatile, highly toxic substance which
remains hazardous at a concentration of less than 1 percent.
A.4.2 Sliding Scale of Volatility Weighted by Potential Hazard
Use of a sliding scale utilizing potential hazard for determination
of volatility of impure substances was considered. Substances would be
ranked according to volatility so that the more volatile a substance,
the lower its acceptable concentration in a waste stream. Highly vola-
tile substances at low concentrations would be weighted by their
potenital hazard, although computaitons would be difficult for a waste
stream containing many volatile substances. A methodology would have
to be developed for implementing this method, if chosen.
A.4.3 Application of NIOSH Environmental Standards to Waste Streams
One method suggested for determining a concentration at which
volatile materials could be present in a waste stream without the entire
waste being classified as volatile involved the use of NIOSH environ-
mental standards (NIOSH, 1979). This concept would apply NIOSH envi-
ronmental standards for a constituent directly to a waste stream.
Thus, if the NIOSH standard for a substance is 3 ppm and the volatile
constituent is present at a concentration below 3 ppm, the waste would
not be classed as volatile. On the other hand, if the constituent were
present at 4 ppm the entire waste Stream would be considered volatile.
The rationale for this method is that if the concentration of a vola-
tile constituent does not exceed the environmental standard, even under
the most favorable meteorological conditions, the environmental stan-
dard would not be exceeded.
Detailed studies of each constituent and a thorough analysis of
its effects on human health covered by the OSHA regulations have been
made in a series of documents issued by NIOSH called Criteria Documents.
However, limiting waste stream concentrations to these standards would
result in unnecessarily restrictive concentrations. Also, the list of
A-14
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some 400 constituents does not necessarily cover all hazardous waste
streams, nor does it cover the properties of the waste stream when it
contains two or more constituents. EPA has proposed a formula for
adding the contribution of two or more constituents that are toxic.
A.4.4 Utilization of Partial Pressures
Partial pressures of individual constituents of a given waste
stream must be determined to apply this methodology to the developed
definition of volatility. According to this definition the waste
stream would be volatile if one or more of its constituents are vola-
tile and the sum of the contributions to the total pressure exceeded
the limits of the definition.
Additional work is necessary to determine the validity of this
method for actual waste streams and techniques for measurement of par-
tial pressures of waste stream constituents must be chosen. Utiliza-
tion of partial pressures would achieve the goal of assigning lower
allowable concentrations to constituents with higher volatilities,
while remaining consistent with the developed defintion.
A.5 SUMMARY
Many alternatives exist with which volatility can be applied to
impure substances. The greatest problems with applying volatility to
impure substances is that for many waste streams, the exact composition
is not known.
Secondly, the synergistic effects of the impure substances are not
known and without laboratory tests on each substance, the volatility is
not known. None of the alternatives given is complete in itself, and
more work is necessary to further develop them.
A.5.1 Chosen Alternatives
The approach used in this study for applying the definition of
volatility to waste streams is to use the volatility of the pure
A-15
-------
substance in the stream which is of the largest concentration. This
provided the ability to identify volatile waste streams without actually
performing the research necessary before alternatives could be put into
practice. For example, while the concentration cutoff at 1 percent is
the simplest approach, and would have been used in this study, insuffi-
cient information on composition of wastes was available to justify its
use.
A.5.2 How the Definition May Be Used
Using the developed working definition of volatility for applica-
tions beyond this study may be feasible. Although not actually a part
of this study it may provide some possible approaches for future
regulatory activities. The approach for using the definition for this
study involved identifying major constituents of wastes and determining
whether the constituents were volatile and then extrapolating this
information to the parent waste streams. While this approach was
necessary for this study due to a lack of analytical data on waste
stream compositions, the approach does not appear satisfactory for
regulating volatile wastes. If a regulatory approach required the
identification and use of individual waste stream constituents, then
the approaches described in Section A.4 should be considered. If waste
stream constituents are not required, then approaches such as using
vapor pressures and toxicities of entire waste stream to determine
volatility should be considered.
A.5.3 Measurement in Wastes
Further research and experimentation needs to be performed on the
subject of volatility of hazardous waste streams. Volatility is a
property of wastes that has caused damage to human health and the en-
vironment. Some of the other ideas proposed for measuring volatility
have included use of such things as molecular weights of chemical
constituents and solubility in water as well as vapor pressure. These
ideas present problems similar to those experienced for the working
definition in this report. Molecular weights of numerous chemicals
A-16
-------
may have to be synthesized to determine how volatilization may occur in
a disposal facility. Additionally, solubility in water is not likely to
accurately describe volatilization from leachate or watery wastes.
Measurement of vapor pressures of entire waste streams is feasible,
however and some laboratory experimentation has been performed at Utah
State University to measure vapor pressures of mixed wastes. Toxicity
of wastes will be determined as EPA extraction procedures are implement-
ed. Therefore, we feel that coupling vapor pressures and toxicities of
mixed wastes should not be abandoned as an approach for regulating
volatility.
A-17
-------
APPENDIX B
DATA BASE LIST OF IGNITABLE,
REACTIVE AND VOLATILE WASTE STREAMS
-------
In the following list:
•	Annual Production (waste generation) is given
in metric tons per year.
•	Toxicities are taken from Sax, Dangerous
Properties of Industrial Materials, 4th
edition. Blanks indicate the substance
was not listed in Sax.
•	Toxicities are given for major components
of the waste stream.
•	References cited in list are given at end
of the Appendix. Numbers are those given in
list of references. Page numbers are given
where applicable.
B-l
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-------
REFERENCES CITED IN APPENDIX B
1.	U.S. Environmental Protection Agency. 1978. Hazardous Waste-
Proposed Guidelines and Regulations and Proposal on Identifica-
tion and Listing. Federal Register 40CFR Part 250 p.58946
Vol. 43, No. 243, December 18, 1978.
2.	U.S. Environmental Protection Agency. 1977. Alternatives for
Hazardous Waste Management in Two Organic Chemical Pesticides
and Explosives Industries. Contract No. 68-9-4127, Report
No. SW-151c. 1977.
3.	U.S. Environmental Protection Agency. 1978. Assessment of
Industrial Waste Practices, Rubber and Plastics Industry.
Contract No. 68-01-3194. March, 1978.
4.	U.S. Environmental Protection Agency. 1977. Assessment of
Industrial Hazardous Waste Practices—Electroplating and
Metal Finishing Industries—Job Shops. Contract No. 68-01-2664,
Report No. SW-136c. 1977.
5.	U.S. Environmental Protection Agency. 1977. Assessment of
Industrial Hazardous Waste Practices—Electronic Components
Manufacturing Industry. Contract No. 68-01-3193, Report
No. SW-140c. 1977.
6.	U.S. Environmental Protection Agency. 1977. Assessment of
Industrial Hazardous Waste Practice—Special Machinery Indus-
tries. Contract No. 68-01-3193, Report No. SW 141c, p.15. 1977.
7.	U.S. Environmental Protection Agency. 1976. Assessment of
Industrial Hazardous Waste Practices, Textile Industry.
Contract No. 68-01-3178, Report No. SW 125c, pages 3-25,
3-38, 3-40, 3-53, 3-65, and 3-77. 1976.
8.	U.S. Environmental Protection Agency. 1975. Survey of Methods
Used to Control Wastes Containing Hexachlorobenzene. Contract
No. 68-01-2956, Task Order No. 68-01-3203. November, 1975.
9.	Gruber; G.I. and Chassemi, M. 1975. Draft Final Report
Assessment of Industrial Hazardous Waste Practices, Organic
Chemicals, Pesticides and Explosives Industries. Contract
No. 68-01-2919, Report No. 25666-6010-TO-00. April, 1975.
10.	U.S. Environmental Protection Agency. 1977. Alternatives
for Hazardous Waste Management in the Inorganic Chemicals
Industry. Contract No. 68-01-4190, Report No. SW 149c. 1977.
11.	Ottenger, R.S., et.al. 1973. Profile Report—Sodium Alloy and
Sodium Potassium Alloy, Recommended Methods for Reduction Neu-
tralization, Recovery or Disposal of Hazardous Wastes. Vol. 13
August, 1973.
B-19
-------
12.	State of Maryland. Prepared by Division of Solid Waste,
Department of Health and Mental Hygiene, Maryland
Environmental Service. Report on Hazardous Waste Practices-
State of Maryland.
13.	U.S. Environmental Protection Agency. 1978. Draft Background
Document, Resource Conservation and Recovery Act, Subtitle C -
Hazardous Waste Management, Section 3001 - Identification and
Listing of Hazardous Waste, Section 250.14 - Hazardous Waste
Lists. December 15, 1978.
14.	U.S. Environmental Protection Agency. 1976. Assessment of
Industrial Hazardous Waste Practices - Leather Tanning and
Finishing Industry. Contract No. 68-01-3261. November, 1976.
15.	Midwest Research Institute. 1976. A Study of Waste Generation,
Treatment and Disposal in the Metals Mining Industry. SPA -
pp. 261.052. October, 1976.
16.	Varsar, Inc. for the EPA. 1975. Assessment of Industrial
Hazardous Waste Practices - Storage and Primary Batteries
Industry. 1975.
17.	L. Schalit, et.al., Acurex Corporation. Hazardous Solid Waste
Streams from Organic Chemicals Manufacturing and Related Indus-
tries. EPA Contract No. 68-03-2567.
18.	Booz-Allen and Applied Research. Hazardous Waste Materials:
Hazardous Effects and Disposal Methods, Vol. II. EPA Contract
No. 68-03-0032. 1973.
19.	Noyes Data Corporation. 1976. Environmental Technology
Handbook, No. 4, How to Dispose of Toxic Substances and
Industrial Wastes. 1976.
20.	U.S. Environmental Protection Agency. 1976. Pharmaceutical
Industry. Hazardous Waste Generation, Treatment and Disposal.
EPA Contract No. 68-01-2684. 1976.
21.	J. Patterson, N. Shapita, J. Brown, W. Duchert, S. Poison. 1976.
State of the Arts: Military Explosives and Propellant Production
Industry, Vol. II; Wastewater Characterization. PB26918/8ST.
August, 1976.
22.	NATO Committee On The Challenges of Modem Society. 1976
Report No. NAT0/CCMS-55. October, 1976.
23.	California Department of Health. 1978. California Character-
ization and Assessment System for Hazardous and Extremely
Hazardous Wastes. March, 1978.
24.	Sax, N.I. Van Nostrand Reinhold Co., New York. 1975.
Dangerous Properties of Industrial Materials, 4th edition.
1975.
B-20
-------
APPENDIX C
SELECTION OF IGNITABLE,
REACTIVE AND VOLATILE
WASTE STREAMS
-------
C. SELECTION OF IGNITABLE, REACTIVE AND VOLATILE WASTE STREAMS
Nearly 300 waste streams were identified from literature and roughly
characterized by industry; whether the waste was ignitable, volatile or
reactive; key component of the waste stream; toxicity of the key compo-
nent; form for disposal, and disposal methods identified in literature.
The list was made as a starting point for choosing the 13 waste
streams to be studied further. The initial list of waste streams, along
with references and comments on each are included in Appendix B.
C.1 METHOD FOR SELECTION OF WASTE STREAMS
The methodology used for choosing waste streams from the list of
approximately 300 is shown in Figure C.l. Ignitability, reactivity and
volatility, and their possible combinations, were prime considerations
and were the basis for initial grouping of the waste streams. A pri-
oritized listing of selection criteria follows each heading. Repre-
sentation of each group in the list of 13 waste streams was not a se-
lection criteria.
Ignitable waste streams were evaluated based on the industry gen-
erating the waste, the quantity of waste stream generated, concentra-
tion of ignitable constituents, toxicity of the waste stream and its
form for disposal. Efforts were made to minimize the number of waste
streams from a particular industry and eliminate from consideration
waste streams generated in very low quantities, and those with very low
concentrations of ignitable constituents, or low toxicity. Efforts were
also made to choose a variety of waste stream forms such as sludge, tar,
liquid or solid. None of the 13 chosen waste streams were just ignit-
able. Criteria for ignitability were used to evaluate waste streams
that are ignitable and volatile, ignitable and reactive, and ignitable,
volatile and reactive.
Volatile waste streams, as defined in an earlier section, were
evaluated based on their degree of volatility. Those with vapor pres-
sures from 78 to 0.1 mm Hg at 40°C were given a set of criteria
-------
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— Methodology
for Selection of 13 Waste Streams
for Further Study
-------
differing from those used to evaluate waste streams having vapor
pressures greater than 78 mm Hg at 40°C.
Waste streams with volatilities from 78 to 0.1 mm Hg were evaluated
for toxicity, industrial category, quantity of waste generated, concen-
tration of volatile constituents in the waste stream, vapor pressure
near 0.1 mm Hg at 40°C, vapor pressure near 78 mm Hg at AO^C and form
for disposal. A toxicity rating of moderate or high qualified the waste
stream as volatile in this vapor pressure range, according to the defi-
nition given in an earlier section. As before, duplicated industrial
category, and generation of a very low quantity and low concentration of
volatile constituents were reasons for eliminating waste streams from
further consideration. Choosing waste streams with vapor pressures near
0.1 and near 78 mm Hg at 40°C will help verify these values as cutoff
points. Form for disposal was the final criteria.
Waste streams with volatilities greater than 78 mm Hg at 40°C were
evaluated for industrial category, quantity generated, concentration of
volatile constituents, toxicity, vapor pressure near 78 mm Hg at 40°C
and form for disposal. Choice of waste streams with vapor pressures
near the cutoff point of 78 mm Hg at A0°C aided in evaluating the
criteria.
Reactive waste streams were evaluated for industrial category,
quantity generated, concentration of reactive constituents, toxicity and
form for disposal.
Combinations of ignitable, reactive and volatile characteristics in
a waste stream required use of criteria for each characteristic. Consid-
erable judgment was necessary for conflicting priorities in the criteria.
C.2 WASTE STREAMS FOR FURTHER STUDY
Thirteen waste streams (Table C.l) were chosen for further study
from an initial list of approximately 300, using the methodology de-
scribed previously. A discussion of each waste stream follows.
C-3
-------
TABLE C.l Waste Streams Chosen for Study
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i
i
3
Ignltabla, g«*ctlv*,
Toalc, Volatile, Tar
Ignttabla, Volatll*,
Toalc
Volatile, Tailc
fvliuitu* lUftnlng
(•tiolw*
frodut. (i
Dla*o1vad Air Flotation
Italt SklMlnii
Hadlua
tow
Hcdlua
J
) 1
1
ItolI.bU. Kol.t |U,
Toalc










Hvltl
(total ProdtKta
and Mnln had
Mulal Product*
Slwdgea







ruil lla
KmuLklut Ing
Tail|l«t*
Slodgaa Ircm Dyvlng
and Flulslitng
Hadlua
Low
Nrdlia
1
i i
1
Tab lc
HjouIjeiurlng
Solvent-Thinned
PiiKki* llqwld Uaataa
High
Low
nigb
1
i •
J
Igaltabla, toliilU,
Toslr Liquid
Binary
LI tbliw~Sul fur
OIhrMo Call*
Scrap l«lla
Low
Ulgh
Hadliw»
J
i »
/
aoactiv*, Volatll*,
Toalc) Lltblva vaaclt
violently wllb sola-
tar* producing hydro*
g«n gaa

TWT
KiJ tfattf
Ml|b
Hlgb
Mlgb
m
w w
u
Igaltabla, gaaetlv*,
Volat ll* Ll>|uld
Military
ftulh m Munition*
IAF tyeral (una
|m 1 m>1 Ing
loo A
lull ppp
Pink Uatwr
nigb
Rlgb
Blgh
low
nigh
nigh
m
«
tt •
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a
«*
Ignltabl*, Irvllva,
VolillbU Ll9old
Ignltabla, Volatile
1 (quid
-------
C.2.1 Organic Chemicals and Plastics Manufacturing
Sulfur sludge from the chlorination step in parathion manufacture is
generated in combination with organophosphate compounds. The vapor pres-
sure is between 0.1 and 78 mm Hg, but, being toxic, is volatile by our
definition. Sulfur has a flashpoint of 66°C. Disposal in landfills,
ocean dumping, and incineration have been mentioned in the literature.
Polyvinyl chloride wastewater treatment sludges are one of several
waste streams from polyvinyl chloride production. This waste stream is
approximately 70 percent water and 30 percent vinyl chloride monomer,
polyvinyl chloride, intermediate products and process additives. The
waste is a sludge and is ignitable, volatile and toxic.
Tars from aniline manufacture contain as key components aniline and
nitrobenzene. The waste is ignitable, reactive, volatile and toxic.
Distillation residues from chlorobenzene manufacture are ignitable,
volatile and toxic, and are typically disposed on land. They are gener-
ated at the rate of 13,000 kkg/yr. See Appendix B.)
Nitrobenzene column bottoms are volatile and toxic and are pro-
duced at an estimated 350 kkg of waste/per yr. (Appendix B) The compo-
sition od the waste streams is not known, although nitrobenzene, benzene,
various sulfates and nitro-substituted aromatics are believed to be
present.
C.2.2 Petroleum Refining
Top surface skimmings from dissolved air flotation (DAF) units are
ignitable and volatile. Their estimated average oil content is 12.5
percent. The waste stream is considered toxic because of the trace
metals and toxic organics present. An estimated 952,560 kkg of DAF
skimmings were disposed in 1979 (Appendix B).
C.2.3 Electroplating and Metal Finishing
Wastewater treatment sludges from electroplating and metal finish-
ing contain cyanide, alkalies, acids, chromium and heavy metals in
C-5
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significant quantities. The generation rate estimated for 1979 is 56,398
kkg dry weight, and the waste is volatile and toxic.
C.2.4 Textile Manufacturing
Wastewater treatment sludges from woven fabric dyeing and finishing
operations in the textile industry contain heavy metals, chlorinated
organics and dyes in significant quantities. The sludge was generated at
an estimated 13,700 kkg dry weight for 1977 (Appendix B) and is ignit-'
able, volatile and toxic. Constituents and disposal methods for this
waste stream are currently being investigated by the industry, but
results were not available in time for inclusion in this study.
C.2.5 Paint Manufacturing
Liquid wastes from solvent-thinned trade sales paint production
are generated at 101,366 kkg/yr (Appendix B). The waste stream is
ignitable, volatile and toxic and is generally disposed on land. The
waste stream contains pigments and solvents and may contain heavy metals
such as cadmium, selenium, mercury, lead and chromium depending on type
and color of paint produced.
C.2.6 Primary Batteries
Although a relatively new battery, the lithium-sulfur dioxide cell
will present challenging treatment, storage and disposal problems as
production increases. The quality control rejection rate for this bat-
tery is estimated at 1-3 percent by weight of plant production. Pro-
duced in steel containers, battery components include lithium metal
(reactive with moisture) and volatile organic solvents. Some of the
components are toxic.
C.2.7 Commercial Explosives
Red waterfrom TNT manufacture is ignitable, reactive and volatile.
A key component of this waste is TNT, which has a high inhalation tox-
icity. The waste is normally disposed as a liquid.
C-6
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C.2.8 Military Explosives
Bulk propellants, explosives and pyrotechnic munitions exhibit
high volatility, reactivity and ignitability. The waste stream is a
liquid.
Pink water from LAP operations, including manufacture of Composi-
tion A, is ignitable and volatile. The key components are nitro com-
pounds. Toxicity is not known. The literature cites carbon absorption
and subsequent incineration or regeneration of the carbon for treatment
of the waste stream as methods of disposal.
In summary, the steps followed in choosing waste streams for fur-
ther study included developing a data base list of approximately 300
waste streams, developing a selection methodology and using the method-
ology to select 13 waste streams for study. Detailed study of waste
streams provided information on treatment, storage and disposal techni-
ques and allowed further evaluation of the cost and environmental im-
pact of implementing these techniques.
C-7
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APPENDIX D
UPDATING COSTS
I
-------
D. UPDATING COSTS
Cost information reported in literature varied in age from 1973
dollars to 1978 dollars. A means of converting cost is given in the
accompanying chart. To obtain 1978 costs, a multiplier for the costs
given in the report is obtained by first dividing the 1978 annual
index by the index for the year given in the text. The multiplier is
then applied to costs given in the text to update costs to 1978.
D-l
-------
5
AnnuJ)n«Wi
1970-125.7
1871 ¦ 1322
1872- 137.2
1973-144.1 '
1874 ° 19&4
1976- 1824
1976-192.1
1977 - 204.1
1978- 21&&
A*-**'
&K3UW? *T
> -1
fapt *79 Auf. 79 Wv 79 bpL "79
1970 - 303J
1971» 321J
1972 - 332.0
1973-344.1
1974-39M
1975 ° 444J
1978 ° 472.1
1977 ° 60&A
1978-64&3
ct pwm cost maex
praUn.
rav.
find
fori
11967-60- 100)

a*»j
ZH3
ai4
Element, maehmerv, tupoora
.... SUA
2B8.S
268.0

Construction l^or	

1MJB
19«7
188.3
BuiMnfi 	-
.... 331J
230.0
338.0
3144
EfHiiwtm ft nowttiQA	

180.2
187 j6
182j>
hfenottd•qwprrwm

"awj
2B2jB
30J

.... 2S4.7
28U
281.6

npa, vetow ft fltOnqi	
... 30O
302.6
301.1
373.1
^QOM MMTUMMti
— 2ns
3334
913
318J
^npiAconottMn	
... 2884
au
asia
3884
Oemic** epuipmwt	
.... 1864
IBtJ
ra.8
1883
Structural wppora ft mi*. .
.... 278.0
774*
2734
263.8
NOTf Onvtomdawocomeommof 1
(tw«0M«r*dH
3M«a
IWI^ |flM
¦WMp,
N» * IMS. *D 14Q«m
*•
N» t3Q «n aw ««m
t irtr
I.
M&S equipment cost index
(irae- iow
CtanM... .
Oaf ^retfaen
MiiWr% mUinf
«





Ma
2nd a
in a
M79
1879
1979
teu<

677 JD
«84
0013
888.9
690.6
608.6
601 a
mjo
593.0
6703

687.6
673.7
879.1
0S&0
860.1
817.2
903J
806.7
nu
S7Sj0
B80J
643j6
038.1
614.1
•42J
6774
6103
IBM
57®.7
S60.7
62B.7
6134
SMJ
710J
603J
6784
60L7
SOU
873.7
»mm anw*> M*. a.
Figure D.l Curves for Updating Costs for Treatment, Storage and Disposal
D-2
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