Waste Management Plant Design

SECTION 6
PLANNING AND DESIGN OF

HAZARDOUS WASTE TREATMENT CENTERS
Planning and designing a hazardous waste treatment center (HWTC) is a necessary
complement to construction of common effluent treatment plants (CETPs) (see Section 5). The
purpose of an HWTC is to provide a safe alternative to uncontrolled disposal of hazardous
industrial liquid and solid wastes. A related purpose is to direct toxic discharges from industry
away from CETPs to prevent impairment of their plants' treatment processes. An HWTC is a
single centralized facility that serves a relatively large geographic area including many
individual SMSEs to take advantage of economies of scale that allow the use of hazardous
waste treatment options, such as incineration, that are beyond the technical and financial
capabilities of individual SMSEs. Although this chapter focuses on centralized treatment, the
possibility of installing treatment processes for specific types of wastes at the industrial facility
should not be overlooked. For example, relatively small distillation units for solvent recovery
are available, and some SMSEs might be able to take advantage of this waste minimization
option.
This section focuses on the planning and engineering design of HWTCs and includes
information on the major types of hazardous waste treatment alternatives available. Volume II
includes an exercise to estimate waste generation from an industry producing lacquered
wooden utensils and to analyze the appropriate treatment technologies.
6.1
DESIGN BASIS
A centralized HWTC is actually only part of a larger system that can include: (1) a
collection system (road, rail, or a combination of the two) for obtaining wastes from individual
SMSEs (and larger enterprises), (2) transfer centers where wastes with similar characteristics
can be identified and combined, (3) a system for transport of bulk wastes from transfer centers
to the centralized treatment plant, (4) an HWTC designed to handle a wide range of hazardous
wastes, and (5) a secure landfill for disposal of solidified wastes and other treatment residuals
(e.g., incinerator ash, residual sludges).
The major differences involved in designing an HWTC compared with a CETP are (1)
HWTCs only use mobile collection systems are never sewer systems, and (2) treatment
systems at HWTCs need to be flexible enough to handle wastes with varying characteristics
because of the diversity of waste sources.
6-1
6.1.1 Solid and Liquid Waste Characteristics and Volume

Section 3 provides basic information on the types of wastes that an HWTC is likely to
handle. Because a large number of SMSEs might be involved, obtaining detailed information
on the waste characteristics and volumes for each enterprise may not be feasible. Detailed
audits of randomly selected enterprises in a particular industrial category can provide a basis
for estimating the overall waste characteristics and volume for that category, provided an
inventory of all existing enterprises is available. Efforts should concentrate on identifying the
volume of wastes in the major categories identified in Table A-2 of Worksheet A in Volume II
(e.g., cyanide wastes, heavy metal sludges and solutions, halogenated solvents, nonhalogenated
solvents). For the purpose of treatment method selection and the design of operating
parameters, it is important to have some idea of the range of concentrations of the major waste
streams (i.e., percent organics and the maximum concentrations of metals in wastewater, etc.).
6.1.2 Collection and Transportation
For the following reasons, mobile rather than pipe systems are most cost-effective in
transporting wastes from SMSEs to an HWTC:
n
n
n
Both solid and liquid wastes must be collected, so mobile pickup is still required
even if a pipe system is in place.
When multiple liquid waste streams (spent solvents, contaminated wastewaters)
have to be handled separately, multiple pipe collection systems are prohibitively
expensive.
Outlying SMSEs can be more easily served by mobile systems than a pipe network.
More expensive construction materials are generally required for pipe systems
handling hazardous wastes.
Just as pretreatment before discharge to a sewer is essential for effective functioning of

a CETP, segregation of hazardous waste streams at the SMSE is essential for effective
operation of an HWTC. Segregation maximizes opportunities for recovery and recycling of
wastes such as solvents and metals, and minimizes potential hazards from mixing of
incompatible wastes. Liquid wastes at the SMSE are generally stored in holding tanks that can
be pumped into portable tanks for transport to an HWTC, while solid wastes can be stored in
drums or other containers that can be transported or possibly reused.
Large quantities of liquid wastewaters and dilute sludge slurries are most economically
transported using vacuum inductor tank trucks. Tank trucks are manufactured in a variety of
capacities ranging from 1,000 to 6,000 gallons. Small volumes of waste (less than 500 gallons)
are most economically stored in drums and transported on flatbed trucks. A standard industrial
drum holds 55 gallons. Drums are especially applicable in situations where several small
volumes of different, incompatible wastes are generated at a single facility.
6-2
During the design of an HWTC, transportation maps are developed showing locations
of individual SMSEs in relation to roads, rail lines, and navigable waterways. Specific design
elements of a collection and transportation system include: 1) the selection of container
materials suitable for the types of wastes to be transported; 2) choosing types and sizes of
vehicles compatible with available transport routes; 3) choosing the number of vehicles to
ensure a waste pickup that is commensurate with the volume of waste generated with a safety
margin for delays and maintenance; and 4) the development of safe operating procedures for
tracking, handling, and transporting the hazardous materials.
6.1.3 Transfer Centers or Stations
An HWTC capable of handling the full range of hazardous wastes generated in a region
might be too far from many SMSEs to allow efficient transportation directly to the center.
Transfer centers allow preliminary classification and mixing of compatible wastes, thus
facilitating processing and treatment upon arrival at the HWTC. Waste storage at transfer
centers also facilitates equalization of the volumes of different waste types to further enhance
the efficient operation of the HWTC.
Location is a key consideration in the design of transfer centers. Centers should be near
major transportation corridors (rail lines, highways) to facilitate transporting large volumes of
waste from the transfer center to the HWTC. A transfer center should have enough land area
available to provide temporary storage of containerized waste and possibly larger volume
storage of several types of liquid wastes. Other important design elements for these centers
include: (1) designing facilities for chemical analysis of wastes for classification and
compatibility testing (see Section 6.1.4), and (2) designing containment systems to protect
onsite workers and nearby populations from exposure to hazardous materials.
6.1.4 Characterization and Classification of Received Wastes
Wastes received at an HWTC must be accurately characterized and classified to avoid
hazards from mixing of incompatible wastes and to ensure that waste volumes do not exceed
the design limits of treatment processes. Potential hazards from mixing incompatible hazardous
wastes include:
n
n
n
n
n
n
Explosions
Fire
Generation of flammable gas
Generation of toxic gas
Generation of heat
Solubilization of toxins
6-3
Figure 6-1 identifies potentially incompatible combinations of 12 types of hazardous

waste. Compatibility is primarily a concern when different wastes are mixed to create larger
batches for treatment by a particular process. Compatibility might also be of concern in
designing waste storage facilities. These should be designed to minimize the possibility of
accidental releases being incompatible.
Screening tests that do not require sophisticated and expensive laboratory equipment are
usually used for compatibility testing. These tests are normally used during collection if liquid
wastes are mixed in the transport container, or at transfer centers. An HWTC should have a
laboratory capable of performing accurate analyses of a wide range of organic and inorganic
substances. Laboratory analyses allow identification of wastes that exceed specifications for
continuous treatment processes. Off-specification wastes must either be treated using an
alternative method or modified by mixing them with other wastes until they fall within
specifications. Laboratory analyses are also used to characterize wastes that are treated using
batch chemical processes for the purpose of determining required chemical inputs to complete
reactions.
The U.S. Environmental Protection Agency (EPA) (1984a) provides detailed guidance
of development of waste analysis plans. Appendix A contains several checklists that may be
useful in the development of waste analysis plans and a list of simple American Society for
Testing and Material (ASTM) test methods for screening waste characteristics. Appendix E
also includes a bibliography of major references on methods for chemical analysis of wastes
and wastewaters.
Figure 6-1. Compatibility of selected hazardous wastes (Batstone et al., 1989)
6-4
6.2
HAZARDOUS WASTEWATER TREATMENT PROCESS ALTERNATIVES
As with CETPs, methods for treating hazardous industrial wastewater can be broadly
classified as physical, chemical, and biological. Physical methods for component separation
(e.g., gravity, filtration) discussed in Section 5.2 for CETPs are equally applicable to
hazardous wastewaters and are generally used for the same purposes, including: (1)
preliminary (see Section 5.2.1) and primary treatment (see Section 5.2.2) to remove settleable
solids, and (2) clarification systems (see Section 5.2.2) to remove flocculated impurities and
precipitates following chemical treatment processes that generate suspended solids.
Figure 6-2 identifies the operational size ranges of different methods for physical
treatment of industrial wastewater. Physical treatment methods can be classified as component
separation methods that use size or density as the primary separation factor and phase
separation methods that generally operate on the ionic and molecular level to separate
contaminants from the liquid matrix. As shown in Figure 6-2, however, some phase separation
methods also operate within the molecular size range.
This section focuses on physical phase separation and chemical treatment methods that
are commonly used for treating hazardous industrial wastewaters. Most of the chemical
processes discussed in this section also are suitable for pretreatment of wastewater on site at an
SMSE prior to discharging to a CETP. When used on site, it is mainly the residuals
(concentrated liquid wastes and sludges) generated by these processes that would be collected
for treatment at a HWTC. In the absence of pretreatment and discharge to a CETP, toxic
wastewater should be collected and transported to an HWTC where the same or similar
treatment processes would be used. The advantage of pretreatment of industrial wastewater on
site is that a much smaller volume of more concentrated waste can be sent to the HWTC.
Physical phase separation methods covered in this section include:
n
n
n
n
n
Air stripping (Section 6.2.1)

Carbon adsorption (Section 6.2.2)
Reverse osmosis (Section 6.2.3)
Ultrafiltration (Section 6.2.3)
Liquid carbon dioxide extraction (Section 6.2.3)
Chemical treatment methods covered in this section include:

n
n
n
n
n
n
Neutralization (Section 6.2.4)

Chemical precipitation (Section 6.2.5)
Cyanide destruction (Section 6.2.6)
Chromium reduction (Section 6.2.7)
Electrolytic recovery (Section 6.2.8)
Ion exchange (Section 6.2.9)
6-5
Figure 6-2. Operational size ranges of methods for treating industrial wastewaters
(Fresenius et al., 1989)
The descriptions of these materials are drawn largely from EPA's Development
Document for Proposed Effluent Limitations Guidelines and Standards for the Centralized
Waste Treatment Industry (EPA). This report contains much useful performance data on
treatment methods used in the centralized waste treatment industry.
Biological treatment methods applicable to toxic wastewaters are discussed briefly in
Section 6.2.10. Appendix B identifies references that include more detailed information on
engineering design for specific processes.
6.2.1 Air Stripping
Air stripping is an effective treatment method for removing dissolved volatile organic
compounds from wastewater. The removal is accomplished by passing high volumes of air
through the agitated wastewater stream. The process results in a contaminated off-gas stream
that, depending upon air emissions standards, usually requires treatment in air pollution control
equipment.
Stripping can be performed in tanks or in spray or packed towers. Treatment in packed
towers is the most efficient application. The packing typically consists of plastic rings or
saddles. Two commonly used types of towers, cross-flow and countercurrent, differ in design
only in the location of air inlets. Cross-flow towers draw air through the sides for the total
6-6
height of the packing. The countercurrent tower draws the entire air flow from the bottom. The
cross-flow towers are more susceptible to scaling problems and are less efficient than the
countercurrent towers. A countercurrent air stripper is shown in Figure 6-3.
Figure 6-3. Air stripping system diagram (U.S. EPA, 1995)

Figure 6-3a shows a variance of the countercurrent air stripper system.
Figure 6-3a. Compact bed scrubber

Source: Productos qumicos. Planes de accin para mejoramiento ambiental. Manual para
empresarios de la PYME. Santaf de Bogot: Sir Speedy. Impresiones Daza Aragn Ltda.
6-7
The driving force of the air stripping mass-transfer operation is the difference in
concentrations between the air and liquid streams. Pollutants are transferred from the more
concentrated wastewater stream to the less concentrated air stream until equilibrium is reached;
this equilibrium relationship is known as Henry's Law. The strippability of a pollutant is
expressed as its Henry's Law Constant, which is a function of both its volatility and solubility.
Air strippers are designed according to the characteristics of the pollutants to be
removed. Organic pollutants can be divided into three general strippability ranges (low,
medium, and high) according to their Henry's Law Constants. The low strippability group,
with Henry's Law Constants of 10-3 (mg/m3 air)/(mg/m3 water) and lower, are not effectively
removed by air stripping. Pollutants in the medium (10-1 to 10-3) and high (greater than 10-1)
groups are effectively stripped. Pollutants with lower Henry's law constants require greater
column height, more trays or packing material, greater pressure and temperature, and more
frequent cleaning than pollutants with a higher strippability.
Low temperatures adversely affect the air stripping process. Air strippers experience
lower efficiencies at lower temperatures, with the possibility of freezing occurring within the
tower. For this reason, depending on the location of the tower, it may be necessary to preheat
the wastewater and the air feed streams. The column and packing materials must be cleaned
regularly to ensure that low effluent levels are attained.
Air stripping has proved to be an effective process in the removal of volatile pollutants
from wastewater. It is generally limited to influent concentrations of less than 100 mg/L
organics. Well-designed and operated systems can achieve over 99 percent removals.
6.2.2 Carbon Adsorption
Activated carbon adsorption is a demonstrated treatment technology for the removal of
organic pollutants from wastewater. Most applications use granular activated carbon (GAC) in
column reactors. Sometimes powdered activated carbon (PAC) is used alone or in conjunction
with another process, such as biological treatment. GAC is the more commonly used method;
however, a diagram of a downflow fixed-bed GAC system is presented in Figure 6-4.
6-8
Figure 6-4. Carbon adsorption system diagram (U.S. EPA, 1995)

The mechanism of adsorption is a combination of physical, chemical, and electrostatic
interactions between the activated carbon and the adsorbate, although the attraction is primarily
physical. Activated carbon can be made from many carbonaceous sources including coal, coke,
peat, wood, and coconut shells.
The key design parameter is adsorption capacity, a measurement of the mass of
contaminant adsorbed per unit mass of carbon, which is a function of the compound being
adsorbed, the type of carbon used, and the process design and operating conditions. In general,
the adsorption capacity is inversely proportional to the adsorbate solubility. Nonpolar, highmolecular-weight organics, with low solubility, are readily adsorbed. Polar, low-molecularweight organics, with high solubilities, are more poorly adsorbed. Competitive adsorption of
other compounds affects adsorption. The carbon may preferentially adsorb one compound over
another with the competition resulting in an adsorbed compound being desorbed from the
carbon.
In a fixed-bed system, pollutants are removed in increasing amounts as wastewater
flows through the bed. In the upper area of the bed, pollutants are rapidly adsorbed. As more
wastewater passes through the bed, this rapid adsorption zone increases until it reaches the
bottom of the bed. At this point, all available adsorption sites are filled and the carbon is said
6-9
to be exhausted. This condition can be detected by an increase in the pollutant concentration of

the effluent from the bed and is called breakthrough.
GAC systems usually comprise several beds operated in series. This design allows the
first bed to go to exhaustion, while the other beds still have the capacity to treat to an
acceptable effluent quality. The carbon in the first bed is replaced, and the second bed then
becomes the lead bed. The GAC system piping is designed to allow switching of bed order.
After the carbon is exhausted, it can be removed and regenerated. Usually, heat or
steam is used to reverse the adsorption process. The light organic compounds are volatilized,
and the heavy organic compounds are pyrolyzed. Spent carbon can also be regenerated by
contacting it with a solvent that dissolves the adsorbed pollutants. Depending on system size
and economics, some facilities may choose to dispose of the spent carbon instead of
regenerating it. For very large applications, as may occur at an HWTC, construction of an
on-site regeneration facility may be justified. For smaller applications, it is generally
cost-effective to use a vendor service to deliver regenerated carbon and remove the spent
carbon. These vendors transport the spent carbon to their centralized facilities for regeneration.
GAC adsorption is a widely used wastewater treatment technology. Generally, the
chemical oxygen demand (COD) of the waste stream can be reduced to less than 10 mg/L and
the biological oxygen demand (BOD) to less than 2 mg/L. Removal efficiencies typically are in
the range of 30 to 90 percent.
Poor GAC system performance sometimes results from competitive adsorption between
compounds in the waste stream. The pollutant methylene chloride is often used as a measure of
adsorption competition in a GAC system because it is readily adsorbed and also desorbed by
competitive compounds. Thus, low methylene chloride removals indicate competitive
adsorption effects. Oil and grease can adversely affect GAC performance by coating the carbon
particles, thereby inhibiting the adsorption process. A commonly applied limit on oil and
grease loading to a GAC system is 10 mg/L. Suspended solids also adversely affect GAC
performance by plugging the bed, resulting in excessive head loss. A commonly used total
suspended solids (TSS) loading limit to a GAC system is 50 mg/L. Poor performance of GAC
units used at centralized waste treatment plants in the United States of America has been
observed and attributed to the inherent difficulty of operating carbon adsorption units for
variable waste streams (EPA, 1995).
6.2.3 Other Physical Treatment Technologies
Other less commonly used physical treatment technologies used in the U.S. centralized
waste treatment industry include:
n
n
n
Reverse osmosis
Ultrafiltration
Carbon dioxide liquid extraction
6-10
Reverse osmosis (RO) is a process for separating dissolved solids from water. It is
commonly used to treat oily or metal-bearing wastewater. RO is applicable when the solute
molecules are approximately the same size as the solvent molecules. A semipermeable,
microporous membrane and pressure are used to perform the separation. RO systems are
typically used as end-of-pipe polishing processes, prior to final discharge of the treated
wastewater.
Osmosis is the diffusion of a solvent (such as water) across a semipermeable membrane
from a less concentrated solution into a more concentrated solution. In the reverse osmosis
process, pressure greater than the normal osmotic pressure is applied to the more concentrated
solution (the waste stream being treated), forcing the purified water through the membrane and
into the less concentrated stream, which is called the permeate. Low-molecular-weight solutes
(for example, salts and some surfactants) do not pass through the membrane. They are referred
to as concentrate. The concentrate is recirculated through the membrane unit until the permeate
flow drops. The permeate can either be discharged or passed along to another treatment unit.
The concentrate is contained and held for further treatment or disposal. An RO system is
shown in Figure 6-5a.
Figure 6-5. Other physical treatment technologies: (a) reverse osmosis, (b) liquid carbon
dioxide extraction (EPA, 1995)
Performance of an RO system is dependent upon the dissolved solids concentration and
temperature of the feed stream, the applied pressure, and the type of membrane selected. The
key RO membrane properties to be considered are selectivity for water over ions, permeation
rate, and durability. RO modules are available in various membrane configurations, such as
spiral-wound, tubular, hollow-fiber, and plate and frame. In addition to the membrane
6-11
modules, other capital items needed for an RO installation include pumps, piping,
instrumentation, and storage tanks. The major operating cost is attributed to membrane
replacement.
EPA (1995) presents performance data for a single unit with an average reduction in the
concentration of oil and grease by 87.4 percent. Aluminum, barium, calcium, chromium,
cobalt, iron, magnesium, manganese, nickel, and titanium were all reduced in this unit by
more than 98 percent.
Ultrafiltration (UF) is used for the treatment of metal-finishing wastewater and oily
wastes. It can remove substances with molecular weights greater than 500, including suspended
solids, oil and grease, large organic molecules, and complex heavy metals. UF is used when
the solute molecules are greater than 10 times the size of the solvent molecules and are less
than one-half micron. The centralized waste treatment industry applies UF to treat oil/water
emulsions. Oil/water emulsions contain both soluble and insoluble oil. Typically, the insoluble
oil is removed from the emulsion by gravity separation assisted by chemical addition. The
soluble oil is then removed through UF. Oily wastewater containing 0.1 to 10 percent oil can
be effectively treated using UF. A UF system is typically used as an in-plant treatment
technology, treating the oil/water emulsion prior to mixing with other wastewater. A schematic
UF system is similar to reverse osmosis (see Figure 6-5a), with the difference being in the
characteristics of the membrane.
In UF, a semipermeable, microporous membrane performs the separation. Wastewater
is sent through membrane modules under pressure. Water and low-molecular-weight solutes
(e.g., salts, some surfactants) pass through the membrane and are removed as permeate. The
membrane rejects emulsified oil and suspended solids, which are removed as concentrate. The
concentrate is recirculated through the membrane unit until the permeate flow drops. The
permeate can either be discharged or passed along to another treatment unit. The concentrate is
contained and held for further treatment or disposal.
The primary design consideration in UF is membrane selection. Membrane pore size is
chosen based on the size of the contaminant particles targeted for removal. Other design
parameters to be considered are solids concentration, viscosity, and temperature of the feed
stream, and membrane permeability and thickness.
U.S. EPA (1995) presents performance data for a UF system that treats oily
wastewater. The system removed 87.5 percent of the influent oil and grease and 99.9 percent
of the TSS. Removal of several organic and metal pollutants exceeded 90 percent.
Liquid carbon dioxide (CO2) extraction is used to extract and recover organic
contaminants from aqueous waste streams. A licensed, commercial application of this
technology, the "Clean Extraction System (CES)," is used in the centralized waste treatment
industry. The process can be effective in removing organic substances such as hydrocarbons,
aldehydes and ketones, nitriles, halogenated compounds, phenols, esters, and heterocyclics. It
6-12
is not effective in removing some compounds that are very water-soluble, such as ethylene
glycol, and low-molecular-weight alcohols. It can provide an alternative in the treatment of
waste streams that historically have been incinerated.
The waste stream is fed into the top of a pressurized extraction tower containing
perforated plates, where it is contacted with a countercurrent stream of liquefied CO2. The
organic contaminants in the waste stream are dissolved in the CO2; this extract is then sent to a
separator, which redistills the CO2. The distilled CO2 vapor is compressed and reused. The
concentrated organics bottoms from the separator can then be disposed or recovered. The
treated wastewater stream that exits the extractor (raffinate) is pressure-reduced and may be
further treated for residual organics removal if necessary to meet discharge standards. A
diagram of the CES is presented in Figure 6-5b.
Pilot-scale operational data for a commercial CES unit show high removals for the
organic compounds chloroform, 1,2-dichloroethane, ethylbenzene, methylene chloride, and
toluene, with rates generally exceeding 99 percent (phenol removal was poorest with 83
percent). EPA sampled a CES operating unit and found significantly lower removal rates,
ranging from 48 to 88 percent.
6.2.4 Neutralization
Acidic corrosive wastes (pH less than 2) and alkaline corrosive wastes (pH greater than
12.5) typically require neutralization prior to use of subsequent treatment processes to limit
corrosion of processing equipment and to improve treatment efficiency. Neutralization or pH
adjustment is often required for wastes that do not classify as corrosive in order to optimize
chemical treatment such as precipitation (see Section 6.2.5) and biological treatment.
Major neutralization processes include (1) mixing of acid and alkali waste streams, (2)
use of alkaline materials to neutralize acids (limestone, lime, and caustic soda), and (3) used of
acidic reagents to neutralize alkaline wastes (sulfuric acid, hydrochloric acid, carbonic acids
and liquid carbon dioxide). Table 6-1 provides summary information on these processes,
including:
n
n
n
n
n
Applicable waste streams

Stage of development
Performance
Residuals generated
Cost
Mixing acid and alkali waste streams is the simplest and least expensive method,
provided the wastes are compatible. Cyanide-containing wastes generally require treatment to
destroy cyanides (see Section 6.2.6) before neutralization. Typically, a tradeoff exists between
the cost of neutralization reagents and length of time required for neutralization and the volume
6-13
of sludge the process creates. Cheaper methods generally take a longer time to complete
neutralization due to more dilute concentrations of reagents. Cheaper reagents, such as
limestone and lime, and sulfuric acid also tend to produce larger volumes of sludges.
Selection of a neutralization method requires evaluation of the compatibility of waste
streams with each other and available reagents. Selection of a method also required weighing
the tradeoffs of the reagent cost versus the speed of neutralization and the sludge disposal cost.
Section 6.4.2 discusses further options for treatment and use of corrosive wastes.
6.2.5 Chemical Precipitation
Chemical precipitation is used to remove metal compounds from wastewater. In the
chemical precipitation process, soluble metallic ions and certain anions are converted to
insoluble forms, which precipitate from the solution. The precipitated metals are subsequently
removed from the wastewater stream by liquid filtration or clarification. The performance of
the process is affected by chemical interactions, temperature, pH, solubility, and mixing
effects.
Various chemicals can be used as precipitants, including sodium hydroxide (NaOH),
lime (Ca(OH)2), soda ash, sulfide, ferrous sulfate, and acid. Hydroxide precipitation is
effective in removing such metals as antimony, arsenic, chromium, copper, lead, mercury,
nickel, and zinc. Sulfide precipitation primarily removes mercury, lead, and silver.
Hydroxide precipitation using lime or caustic is the most commonly used means of
chemical precipitation, and of these, lime is used more often than caustic. The chief advantage
of lime over caustic is its lower cost. Lime is more difficult to handle and feed, however, as it
must be slaked, slurried, and mixed, and can plug the feed system lines. Lime also produces a
larger volume of sludge, and the sludge is generally not suitable for reclamation due to its
homogeneous nature. Also, dewatered metal sludge is typically sold to smelters for reuse, and
the calcium compounds in lime precipitation sludge interfere with smelting. The metals from
caustic precipitation sludge can often be recovered. The reaction mechanism for precipitation
of a divalent metal using lime is shown below:
M++ + Ca(OH)2 _ M(OH)2 + Ca++
And, the reaction mechanism for precipitation of a divalent metal using caustic is:
M++ + 2NaOH _ M(OH)2 + 2Na++
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Table 6-1. Summary of neutralization technologies (Wilk et al., 1988)

Process
Applicable Waste
Streams
All acid/alkali
compatible waste
streams except
cyanide
Stage of
Development
Well developed
Limestone
Dilute acid waste

streams of less than
5,000 mg/l mineral
acid strength and
containing low
concentration of acid
salts
Lime
Acid/alkali
mutual
neutralization
Performance
Residuals Generated
Cost
Generally slower than

comparable technologies
due to dilute concentration
of reagents. May evolve
hazardous constituents if
incompatible wastes are
mixed
Variable, dependent on
quantity of insolubles and
products contained in each
waste stream
Least expensive of
all neutralization
technologies
Well developed
Requires stone sizes of

0.074 mm or less. Requires
45 minutes or more of
retention time. Can only
neutralize acidic wastes to
pH 6.0. Must be aerated to
remove evolved CO2
Will generate voluminous

sludge product when
reacted with sulfatecontaining wastes. Stones
over 200 mesh will
sulfonate, be rendered
inactive, and add to sludge
product
Most cost-effective
in treating
concentrated wastes.
May be cost-effective
in treating dilute
acidic wastes
All acid wastes
Well developed
Requires 15 to 30 minutes
of retention time. Must be
slurried to a concentration
of 10 to 35% solids prior to
use. Can under-(below pH
7) or over- (above pH 7)
neutralize
Will generate voluminous

sludge similar to limestone
More expensive than

crushed limestone
(200 mesh)
Caustic soda
All acid wastes
Well developed
Requires 3 to 15 minutes of
retention time. In liquid
form, easy to handle and
apply. Can under- or overneutralize including pH 13
or higher
Reaction products are

generally soluble, however,
sludges do not dewater as
readily or as easily as lime
or limestone
Most expensive of all

widely used alkaline
reagents (five times
the cost of lime)
Sulfuric acid
All alkaline wastes

except cyanide
Well developed
Requires 15 to 30 minutes
of retention time. In liquid
form, but presents burn
hazard. Highly reactive and
widely available
Will generate large

quantities of gypsum sludge
when reacted with calciumbased alkaline wastes
Least expensive of
all widely used acidic
reagents
Hydrochloric
acid
All alkaline wastes
Well developed,
but rarely
applied due to
high reagent cost
Requires 5 to 20 minutes of
retention time. Liquid form
present burn and fume
hazard. More reactive than
sulfuric
Reaction products are

generally soluble
Approximately twice
as expensive as
sulfuric on a
neutralization
equivalent basis
Carbonic acids,
liquid carbon
dioxide
All alkaline wastes

except cyanide
Emerging
technology
Retention time 1 to 11/2

minutes. In liquid form,
must be vaporized prior to
use. Can only neutralize
alkaline wastes to pH 8.3
and point
Will form calcium

carbonate precipitate when
reacted with calcium-based
alkaline wastes
Approximately 3 to 4
times as expensive as
sulfuric. Therefore,
limited to
applications using
more than 200 tons
of reagents per year
or with flow rate
greater than 100,000
gpd
In addition to the type of treatment chemical chosen, another important design factor in
the chemical precipitation operation is pH. Metal hydroxides are amphoteric, meaning that they
6-15
can react chemically as acids or bases. As such, their solubilities increase toward both lower
and higher pH levels. Therefore, each metal has an optimum pH for precipitation that
corresponds to its point of minimum solubility. Another key consideration in a chemical
precipitation application is the detention time, which is specific to the wastewater being treated
and the desired effluent quality. It may take from less than an hour to several days to achieve
adequate precipitation of the dissolved metal compounds.
Chemical precipitation is a two-step process. It is typically performed in batch
operations where the wastewater is first mixed with the treatment chemical in a tank. The
mixing is typically achieved by mechanical means such as mixers or recirculation pumping.
Then, the wastewater undergoes a separation/dewatering process such as clarification or
filtration, where the precipitated metals are removed from solution. In a clarification system, a
flocculent is sometimes added to aid in the settling process. The resulting sludge from the
clarifier or filter must be further treated, disposed, or recycled. A typical chemical
precipitation system is shown in Figure 6-6.
Figure 6-6. Chemical precipitation system diagram (U.S. EPA, 1995)

The batch operation aspect of chemical precipitation makes it an easily adapted process
for treatment at HWTCs, where the waste receipts can be highly variable. A facility can hold
its wastes and segregate them by pollutant content for treatment. This type of waste treatment
6-16
management, called selective metals precipitation, can be implemented to concentrate on one

or two major pollutants of concern. This application of chemical precipitation uses several
tanks to allow the facility to segregate its wastes into smaller batches, thereby avoiding
interference with other incoming waste receipts and increasing treatment efficiency. These
specific operations also produce specific sludges containing only the target metals, making
them suitable for reclamation.
The effluent quality achievable with chemical precipitation depends upon the metals
present in the wastewater and the process operating conditions. This technology is widely used
with possible removal efficiencies greater than 99 percent, and it often removes metal
pollutants down to levels of 1 g/L or less.
6.2.6 Cyanide Destruction
Cyanide is a very toxic pollutant and, therefore, wastes containing cyanide are an
important environmental concern. Electroplating and metal finishing operations produce most
cyanide-bearing wastes. At least a dozen cyanide destruction technologies are available, but
only six are used commonly: alkaline chlorination, ozonation, ozonation with irradiation,
electrolytic hydrolysis, hydrogen peroxide oxidation, and precipitation processes (Weathington,
1988). The most commonly used method is alkaline chlorination with either gaseous chlorine
or sodium hypochlorite.
A diagram of an alkaline chlorination system is presented in Figure 2-9. Alkaline
chlorination can destroy free dissolved hydrogen cyanide and can oxidize all simple and some
complex inorganic cyanides; however, it cannot effectively oxidize stable iron, copper, and
nickel cyanide complexes. The addition of heat to the alkaline chlorination process can
facilitate the more complete destruction of total cyanides.
In alkaline chlorination using gaseous chlorine, the oxidation process is accomplished
by direct addition of chlorine (Cl2) as the oxidizer and sodium hydroxide (NaOH) to maintain
pH levels (see Figure 2-9). The reaction mechanism is:
NaCN + Cl2 + 2NaOH
2NaCNO + 3Cl2 + 6NaOH
NaCNO + 2NaCl + H20

2NaHCO3 + N2 + 6NaCl + 2H20
Destruction of the cyanide takes place in two stages. The primary reaction is partial
oxidation of the cyanide to cyanate at a pH above 9. In the second stage, the pH is lowered to
the 8 to 8.5 range for the oxidation of the cyanate to nitrogen and carbon dioxide (as sodium
bicarbonate). Each part of cyanide requires 2.73 parts of chlorine to convert it to cyanate and
an additional 4.1 parts of chlorine to oxidize the cyanate to nitrogen and carbon dioxide. At
least 1.125 parts of sodium hydroxide are required to control the pH with each stage.
6-17
Alkaline chlorination can also be conducted with sodium hypochlorite (NaOCl) as the
oxidizer. The oxidation of cyanide waste using sodium hypochlorite is similar to the gaseous
chlorine process. The reaction mechanism is:
NaCN + NaOCl
2NaCNO + 3NaOCl + H20
NaCNO + NaCl
2NaHCO3 + N2 + 3NaCl
Cyanide destruction efficiencies of greater than 99 percent are possible with this
technology but can vary greatly depending on the forms of cyanide present.
6.2.7 Chromium Reduction
Reduction is a chemical reaction in which electrons are transferred from one chemical
to another. The main application of chemical reduction in wastewater treatment is the reduction
of hexavalent chromium to trivalent chromium. This is a commonly used pretreatment process
in the leather tanning industry (see Section 2.3.3) and the electroplating industry (see Section
2.3.5). The reduction enables the trivalent chromium to be precipitated from solution in
conjunction with other metallic salts. Sulfur dioxide, sodium bisulfite, sodium metabisulfite,
and ferrous sulfate are strong reducing agents commonly used in industrial wastewater
treatment applications. Two types of chromium reduction are discussed here:
n
n
Reduction through the use of sodium metabisulfite or sodium bisulfite

Reduction through the use of gaseous sulfur dioxide
A diagram of a chromium reduction system using gaseous sulfur dioxide is presented in

Figure 2-9.
These chromium reduction reactions are favored by a low pH of 2 to 3. At pH levels
above 5, the reduction rate is slow. Oxidizing agents such as dissolved oxygen and ferric iron
interfere with the reduction process by consuming the reducing agent. After the reduction
process, the trivalent chromium is removed by chemical precipitation.
Chromium reduction using sodium metabisulfite (Na2S205) and sodium bisulfite
(NaHSO3) are essentially similar. The mechanism for the reaction using sodium bisulfite as the
reducing agent is:
3NaHSO3 + 3H2S04 + 2H2CrO4
Cr2(S04)3 + 3NaHSO4 + 5H20
The hexavalent chromium is reduced to trivalent chromium using sodium metabisulfite,

with sulfuric acid used to lower the pH of the solution. The amount of sodium metabisulfite
needed to reduce the hexavalent chromium is reported as 3 parts of sodium bisulfite per part of
6-18
chromium, while the amount of sulfuric acid is 1 part per part of chromium. The theoretical
retention time is about 30 to 60 minutes.
A second process uses sulfur dioxide (SO2) as the reducing agent. The reaction
mechanism is:
3SO2 + 3H20
3H2SO3 + 2H2CrO4
3H2SO3
Cr2(S04)3 + 5H20
The hexavalent chromium is reduced to trivalent chromium using sulfur dioxide, with
sulfuric acid used to lower the pH of the solution. The amount of sulfur dioxide needed to
reduce the hexavalent chromium is reported as 1.9 parts of sulfur dioxide per part of
chromium, while the amount of sulfuric acid is 1 part per part of chromium. At a pH of 3, the
theoretical retention time is approximately 30 to 45 minutes.
U.S. EPA (1995) reported hexavalent chromium reduction efficiency of 99.99 percent
for the sulfur dioxide process based on one centralized waste treatment plant. Another plant
using the chromium reduction process with sodium metabisulfite actually showed an increase in
hexavalent concentration, indicating the importance of careful process control to achieve
treatment objectives.
6.2.8 Electrolytic Recovery
Electrolytic recovery is used for the reclamation of metals from wastewater. It is a
common technology in the electroplating, mining, and electronic industries and is used for the
recovery of copper, zinc, silver, cadmium, gold, and other heavy metals. Nickel is poorly
recovered due to its low standard potential.
The electrolytic recovery process uses an oxidation and reduction reaction. Conductive
electrodes (anodes and cathodes) are immersed in the metal-bearing wastewater, with electrical
energy applied to them. At the cathode, a metal ion is reduced to its elemental form
(electron-consuming reaction). At the same time, gases such as oxygen, hydrogen, or nitrogen
form at the anode (electron-producing reaction). After the metal coating on the cathode reaches
a desired thickness, it may be removed and recovered. The metal-plated cathode can then be
used as the anode.
The equipment consists of an electrochemical reactor with electrodes, a gas venting
system, recirculation pumps, and a power supply. A diagram of an electrolytic recovery
system is presented in Figure 6-7. Electrochemical reactors are typically designed to produce
high flow rates to increase the process efficiency.
A conventional electrolytic recovery system is effective for the recovery of metals from
relatively high-concentration wastewater. A specialized adaptation of electrolytic recovery,
6-19
called extended surface electrolysis (ESE), operates effectively at lower concentration levels.
The ESE system uses a spiral cell containing a flow-through cathode that has a very open
structure and therefore a lower resistance to fluid flow. This also provides a larger electrode
surface. ESE systems are often used for the recovery of copper, lead, mercury, silver, and
gold.
6.2.9 Ion Exchange
Ion exchange is commonly used for the removal of heavy metals from relatively
low-concentration waste streams, such as electroplating wastewater. A key advantage of the
ion exchange process is that it allows for the recovery and reuse of the metal contaminants. Ion
exchange can also be designed to be selective to certain metals and can provide effective
removal from wastewater that has high background contaminant levels. A disadvantage is that
some organic substances can foul the resins.
In an ion exchange system, the wastewater stream is passed through a bed of resin. The
resin contains bound groups of ionic charge on its surface, which are exchanged for ions of the
same charge in the wastewater. Resins are classified by type, either cationic or anionic; the
selection is dependent upon the wastewater contaminant to be removed. A commonly used
resin is polystyrene copolymerized with divinylbenzene.
The ion exchange process involves four steps: treatment, backwash, regeneration, and
rinse. During the treatment step, wastewater is passed through the resin bed. The ion exchange
process continues until pollutant breakthrough occurs. The resin is then backwashed to
reclassify the bed and to remove suspended solids. During the regeneration step, the resin is
contacted with either an acidic or alkaline solution containing the ion originally present in the
resin. This "reverses" the ion exchange process and removes the metal ions from the resin.
The bed is then rinsed to remove residual regenerating solution. The resulting contaminated
regenerating solution must be further processed for reuse or disposal. Depending upon system
size and economics, some facilities choose to remove the spent resin and replace it with resin
regenerated off site instead of regenerating the resin in-place.
Ion exchange equipment ranges from simple, inexpensive systems such as domestic
water softeners, to large, continuous industrial applications. The most commonly encountered
industrial setup is a fixed-bed resin in a vertical column, where the resin is regenerated
in-place. A diagram of this type of system is presented in Figure 6-8. These systems can be
designed so that the regenerant flow is concurrent or countercurrent to the treatment flow. A
countercurrent design, although more complex to operate, provides a higher treatment
efficiency. The beds can contain a single type of resin for selective treatment, or the beds can
be mixed to provide for more complete deionization of the waste stream. Often, individual
beds containing different resins are arranged in series, which makes regeneration easier than in
the mixed bed system.
6-20
Figure 6-7. Electrolytic recovery system diagram (U.S. EPA, 1995)

Ion exchange is very effective in the treatment of low-concentration, metal-bearing
wastewater. A common application, chromic acid recovery, has a demonstrated performance
of 99.5 percent. Copper removal from metal finishing rinsewaters can also exceed 99 percent,
and nickel removals range from 82 to 96 percent.
6.2.10 Ozonization
Ozone (O3) is a blue gas generated by the passage of air through a high potential
electric field (10,000 to 20,000 v). Ozone is used to disinfect wastewater because of its
oxidizing properties.
In industrial wastewater treatment, several contact units or chambers with ozone must
be available to guarantee oxidation of pollutants, virus and bacteria. If wastewater contains
flocculated material and an ozone disinfection is desired, it is appropriate to use a turbine
contact system. Indeed, bubbles produced by a porous diffuser system cannot create sufficient
turbulence to disintegrate the agglomerated matter or completely oxidize bacteria and virus.
The estimation of ozone dosage often requires a previous laboratory test.
6-21
Figure 6-8. Ion exchange system diagram (U.S. EPA, 1995)

6.2.10 Biological Treatment
Conventional biological treatment processes for wastewater are discussed in Section
5.3. These processes generally require pretreatment of industrial wastewater to reduce
concentrations of heavy metals and toxic organics to levels that will not impair the performance
of the biological treatment system.
If CETPs or conventional sewage treatment plants are able to treat the bulk of
nonhazardous organics in industrial wastewaters, biological treatment methods are not likely to
be a major component in an HWTC. If the HWTC does receive a significant volume of
nonhazardous industrial wastewater with organics, the treatment options would be similar to
those discussed for CETPs in Section 5.3. Biological treatment process choices might well be
different for an HWTC compared with a CETP because the need for maintenance is less of a
constraint.
Rotating biological contactor systems (RBCs) (see Section 5.3.4) are the conventional
biological treatment process that is most suitable for specific treatment of industrial
wastewaters containing up to 1 percent soluble organics, including solvents, halogenated
organics, acetone, alcohols, phenols, phthalates, ammonia, and petroleum products. RBCs also
can treat inorganic cyanides (EPA, 1992).
6-22
Slurry biodegradation is a treatment process where an aqueous slurry is created by

combining sludge with water and biodegraded aerobically using a self-contained reactor or a
lined aerated lagoon. The process is similar to the conventional activated sludge process or an
aerated lagoon, except that the system can handle highly contaminated soils or sludges that
have contaminant concentrations ranging from 2,500 mg/kg to 250,000 mg/kg. The main
applications of this technology are treating coal tars, refinery wastes, hydrocarbons, woodpreserving wastes, and organic and chlorinated organic sludges. The required operational
parameters of the process are similar to the activated sludge process. As with activated sludge,
the presence of heavy metals may inhibit microbial metabolism of the slurry.
A promising innovative technology, the anaerobic, expanded-bed, GAC bioreactor,
currently being developed by EPA's Risk Reduction Engineering Laboratory in Cincinnati,
Ohio, uses both GAC biological treatment to overcome the problems created by wastewaters
that contain both biodegradable organics and toxic organics. Figure 6-9 shows a schematic of
the system. The GAC sorbs the toxic organics, and the expanded bed configuration enhances
biomass attachment to the GAC, allowing decomposition of the wastewater's readily
biodegradable constituents and providing regeneration of more slowly degraded substances that
are sorbed on to the GAC. This design, combined with heating to optimize microbial activity
rates, allows hydraulic retention times of 3 to 12 hours, representing a significant reduction in
bioreactor volume compared with conventional technologies. Table C-3 in Worksheet C in
Volume II provides additional information about suitable wastes for this technology.
Figure 6-9. Schematic of anaerobic, expanded-bed GAC bioreactor
6-23
6.3
OTHER HAZARDOUS WASTE TREATMENT PROCESS ALTERNATIVES

Alternative treatment methods for hazardous wastes can be broadly classified as:
n
n
Solidification/stabilization technologies (see Section 6.3.1)

Thermal treatment technologies
Incineration (see Section 6.3.2) is the most commonly used thermal treatment method,
but other thermal treatments are available (see Section 6.3.3). Use of both
solidification/stabilization and thermal treatment (most likely incineration) is an integral part of
an HWTC.
6.3.1 Solidification/Stabilization (S/S)
Solidification or fixation refers to techniques that incorporate hazardous waste into a
solid material of high structural integrity. Encapsulation involves either fine waste particles
(microencapsulation) or a large block or container of wastes (macroencapsulation).
Stabilization refers to techniques that treat hazardous waste by converting it into a less soluble,
mobile, or toxic form. Solidification/stabilization (S/S) processes use one or both of these
techniques.
In situ S/S processes are applied to in place wastes or contaminated soils, and ex situ
S/S processes involve in-tank treatment. Ex situ S/S processes are most likely to be used at an
HWTC. Figure 6-10 shows generic elements of an in-tank treatment system. The key elements
of this system include separating and crushing large particles, and the mixing stage where
binding agents and water are added. At an HWTC, S/S technologies are most likely to be used
for two types of waste streams: (1) as-received solid wastes (e.g., plastics, resins, tars and
sludges that are not suitable for treatment using other processes, and (2) as a final treatment
step for residual solids and sludges generated from other treatment processes on site. The final
step in handling S/S treated wastes usually involve disposal in a secure landfill.
Table C-4 in Worksheet C (Volume II) provides summary information on major S/S
processes. Solidification through the addition of cement, lime, or other pozzolanic materials
such as flyash are the most commonly used and are suitable for the large majority of inorganic
wastes. Other S/S processes, such as embedding waste in thermoplastic materials such as
bitumen, paraffin or polyethylene, and microencapsulation are more expensive and are usually
used only for problem-causing wastes such as those with a high organic content. Physical
stabilization involves blending sludge or semiliquid wastes with a bulking agent such as
pulverized fly ash to produce a soil-like consistency that can be readily transported by truck,
conveyor, or rail car to a disposal site.
A key consideration in evaluating the suitability of S/S technologies is whether the
waste to be treated has physical or chemical properties that would interfere with the
6-24
stabilization or solidification process. Table 6-2 identifies factors that might interfere with
these processes.
S/S binding agents
Excavation
Classification
Mixing
(1)
(2)
(3)
Off-gas
treatment
(optional)
Residuals
(4)
Water
Oversize rejects
Stabilized and solidified

media
VOC
capture and
treatment
Crusher
Figure 6-10. Elements of a typical ex situ solidification/stabilization process (U.S. EPA,

1993)
6-25
Table 6-2. Summary of factors that may interfere with stabilization and solidification
processes (U.S. EPA)
Potential Interference
Characteristics Affecting Processing Feasibility

VOCs
Volatiles not effectively immobilized; driven off by heat

of reaction. Sludges and soils containing volatile
organics can be treated using a heated extruder
evaporator or other means to evaporate free water and
VOCs prior to mixing with stabilizing agents.
Use of acidic sorbent with metal hydroxide wastes
Solubilizes metal.
Use of acidic sorbent with cyanide wastes
Releases hydrogen cyanide
Use of acidic sorbent with waste containing

ammonium compounds
Use of acidic sorbent with sulfide wastes
Releases ammonia gas
Use of alkaline sorbent (containing carbonates such

as calcite or dolomite) with acid waste
Use of siliceous sorbent (soil, fly ash) with
hydrofluoric acid waste
Presence of anions in acidic solutions that form
soluble calcium salts (e.g., calcium chloride acetate,
and bicarbonate)
May create pyrophoric waste.
Presence of halides
Easily leached from cement and lime.
Organic compounds
Organics may interfere with bonding of waste materials

with organic binders
Semivolatile organics or polyaromatic hydrocarbons

(PAHs)
Organics may interfere with bonding of waste materials.
Oil and grease
Weaken bonds between waste particles and cement by

coating the particles. Decrease in unconfined
compressive strength with increased concentrations of oil
and grease.
Fine particle size
Insoluble material passing through a No. 200 mesh sieve

can delay setting and curing. Small particles can also
coat larger particles, weakening bonds between particles
and cement or other reagents. Particle size > inch in
diameter not suitable.
Halides
Reduced physical setting, easily leached for cement and

pozzolan S/S. May dehydrate thermoplastic
solidification.
Releases hydrogen sulfide
May produce soluble fluorosilicates

Cation exchange reactions leach calcium from S/S
product increases permeability of concrete, increases rate
of exchange reactions.
Soluble salts of manganese, tin, zinc, copper and lead Reduced physical strength of final product caused by
large variations in setting time and reduced dimensional
stability of the cured matrix, thereby increasing
leachability potential.
Cyanides
Cyanides interfere with bonding of waste materials.
6-26

Sodium arsenate, borates, phosphates
Retard setting and curing and weaken strength of final

product.
Sulfate
Retard setting and cause swelling and spalling in cement

S/S. With thermoplastic solidification may dehydrate and
rehydrate, causing splitting.
Phenols
Marked decreases in compressive strength for high

phenol levels.
Presence of coal or lignite
Coals and lignites can cause problems with setting,

curing, and strength of the end product.
Sodium borate, calcium sulfate, potassium

dichromate, and carbohydrates.
Interferes with pozzolanic reactions that depend on

formation of calcium silicate and aluminate hydrates.
Nonpolar organics (oil, grease, aromatic

hydrocarbons, PCBs)
May impede setting of cement, pozzolan, or organicpolymer S/S. May decrease long-term durability and
allow escape of volatiles during mixing. With
thermoplastic S/S, organics may vaporize from heat.
With cement or pozzolan S/S, high concentrations of
phenol may retard setting and may decrease short-term
durability; all may decrease long-term durability; all may
decrease long-term durability. With thermoplastic S/S,
organics may vaporize. Alcohols may retard setting of
pozzolans.
Polar organics (alcohols, phenols, organic acids,

glycols)
Solid organics (plastics, tars, resin)
Ineffective with urea formaldehyde polymers; may retard

setting of other polymer S/S.
Oxidizers (sodium hypochlorite, potassium

permanganate, nitric acid, or potassium dichromate)
May cause matrix breakdown or fire with thermoplastic

or organic polymer S/S.
Metals (lead, chromium, cadmium, arsenic, mercury) May increase setting time of cements if concentration is
high.
Nitrates, cyanides
Increase setting time, decrease durability for cementbased S/S.
Soluble salts of magnesium, tin, zinc, copper and

lead
May cause swelling and cracking within inorganic matrix

exposing more surface area to leaching.
Environmental/waste conditions that lower the pH of

matrix
Eventual matrix deterioration.
Flocculants (e.g. ferric chloride)
Interference with setting of cements and pozzolans.
Soluble sulfates > 0.01% in soil or 150 mg/L in

water
Endangerment of cement products due to sulfur attack.
Soluble sulfates > 0.5% in soil or 2000 mg/L in

water
Serious effects on cement products from sulfur attacks.
Oil, grease, lead, copper, zinc and phenol
Deleterious to strength and durability of cement, lime/fly

ash, fly ash/cement binders.
Aliphatic and aromatic hydrocarbons
Increase set time for cement.
6-27

Chlorinated organics
May increase set time and decrease durability of cement

if concentration is high.
Metal salts and complexes
Increase set time and decrease durability for cement or

clay/cement.
Inorganic acids
Decrease durability for cement (Portland Type I) or

clay/cement.
Inorganic bases
Decrease durability for clay/cement; KOH and NaOH

decrease durability for Portland cement Type III and IV.
6.3.2 Incineration
Incineration is the most commonly used method for thermal treatment of organic
liquids, and solids and sludges contaminated with toxic organics. Figure 6-11 shows a flow
diagram with the following key elements of an incinerator system: (1) waste processing, which
includes screening, size reduction, and waste mixing, (2) a waste feed system, (3) a
combustion unit, (4) air pollution control equipment to collect/treat products of incomplete
combustion, particulate emissions, and acid gases, and (5) facilities for handling and disposing
residual ash from the combustion unit, and particulates and residual wastewater from the air
pollution control system.
Incinerators are usually classified by the type of combustion unit, with rotary kiln,
liquid injection, fluidized bed, and infrared units being those most commonly used for
hazardous wastes. Existing industrial boilers and kilns, especially cement kilns, are also
sometimes used for thermal treatment of hazardous wastes. Table 6-3 identifies major waste
properties that affect the performance of an incinerator. Table C-5 in Worksheet C (Volume II)
provides additional information about qualifying factors relevant to different types of
incinerator units. Appendix B identifies major references that provide more detailed
information about the selection and design of incinerators.
Incineration is a relatively expensive treatment option, but the economies of scale
created by a large HWTC mean an incinerator is likely to be a key element in the design of a
facility capable of treating a wide range of hazardous wastes. Incineration is also sometimes
used to treat sludge from conventional wastewater treatment plants serving large cities. As
discussed in Section 6.5, sludge from CETPs normally is put to beneficial use; however, it
might be necessary to transport highly contaminated sludges to an HWTC for further
treatment, and possibly incineration.
6-28
Exhaust to Atmosphere
Acid Gas
Control
Waste
Processing
Auxiliary
Fuel
Combustion
Air
Particulate
Removal
Waste
Feeding
Gas
Conditioning
Combustion
Unit
Ash
Residual
Treatment
Removal
Wastewater
To Disposal
Figure 6-11. Incineration system concept flow diagram (U.S. EPA, 1991)
Table 6-3. Waste properties affecting incineration system performance (U.S. EPA, 1991)
Property
Hardware Affected
Heating value
Rotary kiln
Density
Rotary kiln
Halogen and
sulfur content
Quench system, air

pollution control
equipment design and
operation.
Feed system
Moisture
Particle size
distribution
H:Cl ratio of
POHCs.
Any fusion
characteristics
(determined by
chemical
characteristics,
e.g., alkalis).
Operating Parameter
Affected
Rotary kiln temperature,
flue gas residence time.
Weight of material held by
kiln.
Pump cavitation, pH
control, blowdown rate,
particulate emissions.
Cyclone, SCC, ducts,

wet electrostatic
precipitation (WEP),
instrumentation.
_____
Kiln draft, particulate

emissions excess oxygen
control, temperature
control.
Incinerators ability to
thermally destroy
POHCs/PICs.
Rotary kiln, cyclone,

ducts, quench elbow,
instrumentation
Kiln draft, temperature,

excess O2 control.
6-29
Effect of Performance
Feed capacity, fuel usage.
Feed capacity.
Feed capacity, caustic
usage.
Increased fuel usage to
maintain temperature.
Fouling of duct, cyclone,
SCC, process water system,
and instruments.
As H:Cl ratio decreases,
thermal stability of POHCs
increases and oxidation of
PICs is reduced. Under
oxygen starved conditions,
the tendency to form PICs
increases as the N:Cl ratio
decreases.
Slagging of kiln, plugging of
instruments and downstream
equipment.
Example Feeds of
Concern
Plastics, trash.
Brominated sludge (high
density sludge).
Trial burn mixture,
brominated sludge.
Soils, brominated
sludge, vermiculite.
C2Cl6C6l6, C2HCl and
similar compounds.
Plastic, trash,
brominated sludge.
6.3.3
Other Thermal Treatment Technologies
Other thermal treatment technologies include a variety of methods that use heat (but not
primarily oxidation by direct air combustion as with incineration) to remove or destroy organic
contaminants. Available technologies include:
n
n
n
Pyrolysis
Wet air oxidation
Thermal desorption
Supercritical water oxidation is an emerging thermal treatment technology that has

received considerable bench-scale and pilot-scale testing.
Pyrolysis is a thermal process that transforms hazardous organic materials in an oxygenpoor atmosphere into gaseous components and a solid residue (coke) containing fixed carbon
and ash. Upon cooling, the gaseous components condense, leaving an oil/tar residue. Pyrolysis
is applicable to a wide range of organic wastes in soil and sludge, including polychlorinated
biphenyls (PCBs) and dioxins/furans.
Wet air oxidation uses elevated temperature and pressure to oxidize dissolved or finely
divided organics. Its main application is to treat waste streams that are too dilute (less than 5
percent organics) to treat economically by incineration and that have contaminant levels above
those considered ideal for biological treatment. This technology can also be used to treat
wastewaters with pesticides, phenolics, organic sulfur, and cyanide. It is not suitable for
halogenated aromatic organics or for treating large volumes of waste.
Thermal desorption is used to physically separate volatile and some semivolatile
contaminants from soil, sediments, sludges, and filter cakes by heating them at temperatures
high enough to volatilize the organic contaminants. Desorbed organics in the gas stream are
then treated by being burned in an afterburner, condensed in a single- or multistage condenser,
or captured by carbon adsorption beds. Thermal desorption systems are usually classified as
low temperature (200 to 600oF/93 to 215oC) or high temperature (600 to 1,000oF/315 to
538oC) systems.
The main difference between the two is that low-temperature systems target volatile
organic compounds, whereas high-temperature systems target semivolatile organics.
Supercritical water oxidation (SCWO) uses oxidants (air, oxygen, or hydrogen
peroxide) to decompose organics in an aqueous waste stream that is above the critical point of
water (364oC/221 atmospheres). Supplemental fuel may be required at startup and for dilute
wastes, but waste streams with a COD greater than 15,000 mg/L generally are self-sustaining.
SCWO can be used for liquid wastes, sludges, and slurried solid wastes.
6-30
Table C-5 in Worksheet C (Volume II) provides additional information about the above
thermal treatment methods and a number of innovative thermal treatment technologies (electric
reactor, molten glass, molten salt, and radiofrequency thermal heating), and also identifies
references where more detailed information can be obtained.
6.4
SELECTION OF TREATMENT PROCESSES
Major considerations in the selection of hazardous waste treatment processes at HWTCs

include:
n
Waste medium. Wastewater, organic liquids, sludge, and solids containing the same
type of contaminants may often require different treatment processes (see Section
6.4.1).
Contaminant type. The physical and chemical properties of contaminants in a waste
affect the suitability of available treatment processes. For example, precipitation is a
chemical treatment method that applies mainly to inorganics such as metals and
cyanides. Air stripping and thermal treatment methods, on the other hand, are more
suited for treatment of wastewaters and solids contaminated with volatile and
semivolatile organics. Whether organic contaminated wastes are halogenated or
nonhalogenated also may influence the suitability of a particular treatment option.
Mixed organic and inorganic wastes are often the most difficult to treat, frequently
requiring a series of different treatment steps. Contaminant-specific waste treatment
options are covered further for corrosive wastes in Section 6.4.2, solvent wastes in
Section 6.4.3, and other contaminants in Section 6.4.4.
Contaminant concentration. The successful operation of some treatment processes
depend on the concentration of contaminants in the waste stream. Section 6.4.1
provides information on the range of applicability of treatment techniques as a
function of the organic concentration in liquid waste streams.
Waste volume. Some treatment methods, such as incineration, require large volumes
of waste to be cost-effective. Other methods, such as wet air oxidation (see Section
6.3.3), are better suited for small volumes of waste. Process efficiency requires a
reasonably good match between the volume of waste at which a process works
efficiently and the volume of waste to be treated.
Waste variability. Continuous treatment processes generally operate more efficiently
if the waste stream does not vary greatly in flow rate and chemical composition.
Equalization tanks (see Section 5.2.1) are often used to control variability for
continuous wastewater treatment processes. Batch treatment processes are well
suited for wastes that vary in chemical composition.
6-31
Availability. The importance of reliable performance of treatment technologies

generally restricts technology choices to those that are commercially developed.
Testing and development of innovative and emerging technologies may be possible
but probably not as a central feature of any treatment train that handles large
volumes of waste.
Cost. Cost will probably be the major factor for choosing between two or more
treatment options that satisfy all the other criteria. As discussed in Section 5.4.2,
evaluating treatment costs requires considering the overall cost and the relative
significance of capital, and operation and maintenance costs.
Residuals. Most treatment processes produce residuals that may require further
treatment (e.g., off gases) or disposal (e.g., ash, sludges). The type and volume of
residuals generated should be considered when selecting a treatment technology.
The types of wastes received at an HWTC depend on the specific industrial processes
used by the industries sending wastes to the facility. Numerous treatment options could be
suitable for a particular batch or stream of waste. Worksheet A in Volume II describes a
procedure for identifying waste characteristics and treatment options for specific industrial
categories.
The screening procedure described in Worksheet A is applicable for selecting potential
treatment options for CETPs and HWTCs. Criteria for selecting onsite pretreatment options for
SMSEs prior to discharging wastes is more similar to the criteria for CETPs discussed in
Section 5.4.1. An HWTC generally mixes similar wastes from many individual sources. An
important step in the process of selecting treatment options for an HWTC is to determine the
major types of waste streams that will be handled by the facility through combining these
wastes.
6.4.1 Media-Specific Options
Table 6-4 identifies potential treatment alternatives for various types of liquid and solid
hazardous wastes for (1) waste minimization, (2) pretreatment, and (3) treatment and disposal.
Table 6-4 indicates that treatment options are often dependent on the concentration of the waste
stream. Thus, options identified for recycling of concentrated inorganic liquids differ from
those for treating dilute inorganic liquids, except for electrodialysis. Figure 6-12 identifies the
approximate ranges of applicability of commercially available treatment techniques (solid bar)
as a function of organic concentration in liquid waste streams. The dashed lines indicate
potential extensions of available technologies and the emerging technology of supercritical
water oxidation.
6-32
The pretreatment options for various waste media identified in Table 6-4 are mostly
physical methods, many of which are discussed in Sections 5.2.1, 5.2.2, and 5.5.2. Major
chemical pretreatment methods include neutralization, cyanide destruction, and chromium
reduction. Treatment and disposal methods identified in Table 6-4 are discussed in Sections 6.2
and 6.3.
Table 6-5 is a matrix showing the potential applicability of 17 treatment technologies
for general types of contaminants in three media: (1) aqueous wastes, (2) organic liquids, and
(3) sludges and soils. Although this table was developed for screening technologies for onsite
remediation of contaminated sites, all of the treatment categories could be used in HWTCs.
6.4.2 Corrosive Wastes
Neutralization of corrosive wastes was discussed in Section 6.2.4. Table 6-6 provides
the following information on eight treatment technologies for recovery and reuse of corrosive
wastes:
n
n
n
n
n
Applicable waste streams

Performance
Residuals generated
Cost
Because of the problems involved in transporting corrosive wastes to an HWTC, these

technologies would generally be best applied at the industrial facility where they are generated.
Unfortunately, financial constraints would probably limit the use of such technologies by
SMSEs.
6-33
Table 6-4. Hazardous waste management alternatives (Wilk et al., 1988)

Waste Management
Objective
Applicable Waste
Type(s)
Potential Waste Management/Treatment Alternative
Waste minimization
Source reduction
All
Raw material substitution

Product reformulation
Process redesign
Waste segregation
Recycling
Concentrated inorganic
liquids (e.g. plating,
etching solutions)
Dilute inorganic liquids
(e.g. plating rinses)
Concentrated organic
liquids (e.g. solvents with
acid/alkali)
Crystallization
Ion exchange
Evaporation/distillation
Electrodialysis
Solvent extraction
Thermal decomposition
Ion exchange
Reverse osmosis
Donna dialysis/coupled
Electrodialysis
transport
Neutralization followed by recovery such as distillation, evaporation, stream
stripping, or use as a fuel.
Reuse in process with

lower raw material
specifications
Mutual neutralization
Screening
Distillation
Centrifugation
Decanting
Extraction
Cyanide destruction
through chlorination
Chromium reduction
Sedimentation
Flotation
Equalization
Flotation
Distillation
Filtration
Setting
Centrifugation
Equalization
Filter press
Centrifugation
Bulky solids
Vacuum filtration
Other dewatering
Shredders
Hammermills
Crushers
Neutralization
Acidic waste
Alkaline waste
All
Limestone
Sulfuric acid
Lime
Hydrochloric acid
Caustic soda
Carbonic acid (CO2)
Treatment and disposal
Metal-containing liquid
Precipitation and
clarification
Adsorption
Biological treatment
Air stripping
Distillation
Extraction
Incineration
Solidification
Chemical oxidation
Incineration
Steam stripping
Supercritical fluids
Use as a fuel
Encapsulation
Ozonation
Incineration
Wet air oxidation
Waste exchange
Pretreatment
Concentrated liquids
Recycling
Dilute organic liquids
Liquid with solids
Liquid-two-phase
Liquid or sludge with
cyanide
Liquid or sludge with
hexavalent chromium
Sludge
Trace organic-containing
liquids
Dilute organic-containing
liquid
Concentrated organic
liquid
Inorganic sludges and
solids
Organic sludges and solids
6-34
Evaporation
Wet air oxidation
Landfill
Figure 6-12.
Approximate ranges of applicability of treatment techniques as a function

of organic concentration in liquid waste streams (Breton et al., 1987)
6-35
Table 6-5. Onsite waste treatment technology matrix (U.S. EPA, 1991)
6-36
Table 6-6.
Process
Evaporation/
Distillation
Crystallization
Summary of recovery/reuse technologies for corrosive wastes (Wilk et al., 1988)

Applicable Waste
Stage of
Performance
Streams
Development
Plating solution
Well-established
Metal plating
for treating plating recovered for
rinses; acid
reuse in plating
rinses
pickling liquors
bath. Rinse water
can be reused
H2SO4 pickling
liquors;
HNO3/HF;
pickling liquors;
caustic aluminum
etch solutions
20 to 25 systems
currently in
operation (fewer
applications for
caustic recovery)
97-98% recovery
for H2SO4 (8095% metal
removal)
Residuals
Generated
Impurities will be
concentrated,
therefore,
crystallization/
filtration system
may be required
Ferrous sulfate
heptahydeate
crystals (can be
traded or sold)
Cost
Can be costeffective for
recovering
corrosive plating
solutions from
rinse waters
Cost-effective if
treating large
quantities of waste
99% HNO3 and

50% HF
recovered
Ion exchange
Electrodialysis
Metal fluoride
crystals (can recover
additional HF by
thermal
decomposition)
80% recovery
Aluminum
NaOH
hydroxide crystals
(can be traded or
sold)
Plating rinses:
Several RFIE units Cocurrent systems Cocurrent process
RFIE and APU
acid pickling
in operation for
not technically
generates spent
are cost-effective
baths; aluminum
treatment of
feasible for direct regenerant, which is
etching solutions; corrosives
treatment of
also corrosive
H2SO4; anodizing
corrosives; can be
solutions; rackused in
stripping solutions
conjunction with
(HF/HNO3)
neutralization
technologies to
lower overall costs
Units for direct
RFIE units show
Recovered metals
treatment of acid
good results.
which can be
bath only available Conventional
reused, treated,
from ECO-TEC
RFIE performs
disposed, or
Ltd.
best with dilute
marketed
solutions. APU
performs best with
high metal
concentration (30
to 100 g/L)
Units currently
85% recovery of
Metals which can be Cost-effective for
Recovery of
etching solution.
treated, disposed, or specific
chromic/sulfuric
being sold, but
regenerated for
applications
acid etching
limited area of
45% copper
(chromic/sulfate
application. 5 in
removal; 30%
reuse
solutions
zinc removal
acid etchants)
operation
Recovery of
Several in
plating rinses
operation
(particularly
chromic acid rinse
Works best when

copper
concentrations are
in the 2 to 4 oz/gal
6-37
Chromic acid can be

returned to plating
bath; rinse water
can be reused
Low capital
investment; cost
effective for
specific
Process
Applicable Waste
Streams
waster)
Stage of
Development
Performance
Residuals
Generated
usage
Marketed, none in
Recovery of
HNO3/HF pickling operation to date
liquors
3 M HF/HNO3
recorded
2M KOH Soln
which can be
recycled back to the
pretreatment step
for this ED
application
Recovered plating
solution returned to
plating bath (after
being concentrated
by an evaporator).
Rinsewater reused
Reverse osmosis Plating rinses
Corrosive waste
membranes
marketed by four
companies. RD
module systems
applicable to
corrosives
available from two
companies
90% conversion
achieved with
cyanide plating
rinses
Donna
dialysis/coupled
transport
Donnan analysis
only lab-scale
tested
Data not available Data not available

for Donna analysis for Donnan analysis
(further testing
required)
Coupled transport
lab and field
tested. Coupled
transport system is
currently being
marketed
Coupled transport
has demonstrated
99% recovery for
chromate from
plating rinses.
Other plating
rinses should be
applicable, but not
fully tested
Plating rinses;
potentially
applicable to acid
baths
Solvent
extraction
HNO3/HF pickling Commercial-scale 95% recovery of

liquors
systems installed
HNO3; 70%
for development
recovery of HF
purposes in
Europe and Japan.
No commercialscale installations
in U.S.
Thermal
decomposition
Acid wastes
Well-established
for recovering
spent pickle
liquors generated
by steel industry.
Pilot-scale stage
for organic wastes
99% regeneration
efficiency for
pickling liquors
(1) RFIEL Reverse flow ion exchange
6.4.3 Solvent Wastes
6-38
Cost
application
(chromic acid
rinses)
Cost-effective for
large quantity
generator
Cost-effective for
limited
applications.
Development of a
more chemically
resistant
membrane would
make it very costeffective for a
wider area of
application
No cost data
available for
Donna analysis
For chromate
plating rinse
applications, sodium
chromate is
generated: can be
used elsewhere in
plant or subjected to
ion exchange to
recover chromic
acid for recycle to
plating solution
Metal sludge (95%
iron can be
recovered by
thermal
decomposition)
Average capital
cost for plating
shop is $20,000.
Can be costeffective for
specific
applications
98-99% purity iron

oxide which can be
reused, traded, or
marketed
Expensive capital
investment. Only
cost-effective for
large quantity
waste acid
generators
Not available
Many industries generate solvent wastes through cleaning equipment. Solvents are used
extensively in the metals treatment/finishing industries and the electronics industries. Fresh
solvents are organic liquids and can be either halogenated (such as tetrachloroethylene) or
nonhalogenated (such as methanol and toluene). Solvent wastes can be either, single- or multi
component waste streams (i.e., mixed with water, solids, or both).
Table 6-7 provides an overview of solvent waste minimization and treatment options,
and Table 6-8 provides the following information on more than two dozen specific
recovery/treatment options: (1) applicable waste streams, (2) stage of development of the
process, (3) performance, and (4) residuals generated.
Solvent reclamation technologies, such as distillation, evaporation, and steam stripping,
are applied to spent solvents to remove water and other liquid contaminants before they are
reused. If a solvent is only contaminated with solids, reclamation can be accomplished by
filtration or other physical component separation methods. Sometimes, contaminated solvents
can be reused without treatment by shifting use to applications with lower purity requirements.
Organic liquid solvents also have potential for use as a supplemental fuel in industrial kilns and
high-temperature industrial boilers. Special care is required when using halogenated solvents as
a fuel to ensure that concentrations of chlorine in the fuel blend do not exceed levels that will
corrode the system.
The main treatment option for concentrated waste solvents for which reclamation is not
feasible is thermal treatment. Table 6-8 identifies four incineration options and seven other
thermal technologies; of these seven technologies, only pyrolysis (see Section 6.3.3) is
commercially available. Most of the physical and chemical treatment options identified in
Table 6-9 are for aqueous waste streams contaminated by relatively low concentrations of
solvents. Figure 6-12 can be used as a guide for identification of potential technologies based
on the concentration of solvents and other organics in wastewater.
6-39
Table 6-7. Solvent waste management alternatives to land disposal (Breton et al., 1987)
Waste
management
objective
Waste
Minimization
Applicable waste
type(s)
Potential waste management alternative

Raw material
substitution
Product
reformulation
Reclamation
Process redesign
Waste segregation
Screening
Floatation
Decanting
Distillation
Vacuum filtration
Sedimentation
Settling
Floatation
Filtration
Centrifugation
Centrifugation
Distillation
Filter press
Centrifugation
Other
dewatering
Bulky solids
Low Btu/High
Viscosity
Shredders
Blending
Hammermills
Crushers
Treatment
Physical
Liquid
Distillation
Steam stripping
Evaporation
Air stripping
Chemical
Liquid
Biological
Liquid
Wet air oxidation

Other chemical
oxidations
Activated sludge
Aerated lagoon
Incineration
All
Liquid inyection
Rotary kiln
All
Pyrolysis
processes
Plasma systems
Molten glass
Electric reactor
Organic liquid
Decanting
Dehydrating
Solid/sludge
Solidification
Encapsulation
Aqueous Liquid
Carbon adsorption
Ozonation
Resin adsorption
Other oxidations
Recycling
All
All
Reuse (e.g., as a fuel or process solvent)
Pretreatment
Liquid with solids
Liquid Two Phase
Sludge
Other
thermal
Fractionation
Carbon
adsorption
Supercritical water oxidation
Chlorinolysis
Trickling
filter
Fluidizedbed
Circulating
fluid bed
Molten salt
Extraction
Extraction
Resin
adsorption
Ozonation
Starved air
Post-treatment
6-40
Fractionatio Thermal
n
destruction
Thermal
destruction
Air stripping Biological
Treatment
Table 6-8. Summary of solvent treatment processes (Breton et al., 1987)

Process
Applicable waste
streams
Performance
Residuals generated
Incineration
Liquid injection
incineration
Rotary kiln incineration
Fluidized bed incineration
Fixed/multiple hearths
All pumpable liquids

provided wastes can be
blended to Btu level of
6500 Btu/lb. Some solids
removal may be
necessary to avoid
plugging nozzles
All wastes provided Btu
level is maintained
Estimated that over 219

units are in use. Most
widely used
incineration technology
Over 40 units in
service; most versatile
for waste destruction
Liquids or nonbulky solids Nine units reportedly in
operation-recirculating
bed units under
development
Can handle a wide variety Approximately 70 units
of wastes
in use. Old technology
for municipal waste
combustion
Excellent destruction
efficiency (>99.99%).
Blending can avoid
problems associated with
residuals, e.g., HCl
TSP, possibly some PICs and

HCl if halogenated organics
are fired. Only minor ash if
solids removed in
pretreatment processes
efficiency (>99.99%)
Requires APCDs. Residuals

should be acceptable if
charged properly
As above
efficiency (>99.99%)
Performance may be
marginal for hazardous
wastes, particularly
halogenated wastes
As above
Only a few units now

burning hazardous
waste
Usually excellent
destruction efficiency
(>99.99%) because of long
residence times and high
temperatures
Requires APCDs. Residuals

should be acceptable
Several units in use
Most units tested have

demonstrated high DRE
(>99.99%)
Waste must be blended to

meet emission standards for
TSP and HCl unless boilers
equipped with APCDs
Manufacturer reports high

efficiencies (>99.99%)
Bed material additives can

reduce HCl emissions.
Residuals should be
acceptable
Will need APC device for
HCl and possibly PICs; solid
retained (encapsulated) in
molten glass
Use as a Fuel
Industrial kilns
High temperature
industrial boilers
Generally all wastes, but

Btu level, chlorine
content, and other
impurity content may
require blending to
control charge
characteristics and
product quality
All pumpable fluids, but
should blend halogenated
organics. Solids removal
particularly important to
ensure stable burner
operation
ther Thermal Technologies

Circulating bed combustor Liquids or nonbulky solids Only one U.S.
manufacturer. No units
treating hazardous
waste
Molten glass incineration Almost all wastes,
Technology developed
provided moisture and
for glass
metal impurity levels are manufacturing. Not
within limitations
available yet as a
hazardous waste unit
Molten salt destruction
Not suitable for high
Technology under
(>20%) ash content
development since
wastes
1969, but further
development on hold
Furnace pyrolysis units
Most designs suitable for One pyrolysis unit
all wastes
RCRA permitted.
Certain designs
available commercially
6-41
No performance data
available, but DREs should
be high (>99.99%)
Very high destruction

Needs some APC devices to
efficiencies for organics (six collect material not retained in
nines for PCBs)
salt. Ash disposal may be a
problem
Very high destruction
TSP emissions lowers than
efficiencies possible
those from conventional will
(>99.99%). Possibility of
need APC devices for HCl
PIC formation
Process
Plasma arc pyrolysis
Applicable waste
streams
Present design suitable
only for liquids
Commercial design
appears imminent, with
future modifications
planned for treatment of
sludges or solids
Fluid wall advanced
Suitable for all wastes if
Ready for commercial
electric reactor
solids pretreated to ensure development. Test unit
free flow
permitted under RCRA
In situ vitrification
Technique for treating
Not commercial,
contaminated soils, could further work planned
possibly be extended to
slurries. Also use as
solidification process
Physical Treatment Methods
Technology well
Distillation
This is a process used to
developed and
recover and separate
equipment available
solvents. Fractional
from many suppliers;
distillation will required
widely practiced
solids removal to avoid
technology
plugging columns
Technology is well
Evaporation
Agitated thin film units
can tolerate higher levels developed and
equipment is available
of solids and higher
from several suppliers;
viscosities than other
widely practiced
types of stills
technology
Technology well
Stream Stripping
A simple distillation
process to remove volatile developed and
available.
organics from aqueous
solutions. Preferred for
low concentrations and
solvents with low
solubilities
Technology well
Air Stripping
Generally used to treat
low concentration aqueous developed and available
streams
Liquid-liquid extraction
Carbon adsorption
Resin Adsorption
Performance
Efficiencies exceeded six
nines in tests with solvents
Requires APC devices for

HCP and TSP, needs flare for
H2 and CO destruction
Efficiencies have exceeded

six nines in tests with
solvents
No date available, but
DREs of over six nines
reported
Requires APC devices for

HCP and TSP, needs flare for
H2 and CO destruction
Off gas system needed to
control emissions to air. Ash
contained in vitrified soil
Separation depends upon

reflux (99 + percent
achievable). This is a
recovery process
Bottoms will usually contain

levels of solvent in excess of
1,000 ppm; condensate may
require further treatment
This is a solvent recovery

process. Typical recovery
of 60 to 70 percent
Bottoms will contain

appreciable solvent. Generally
suitable for incineration
Not generally considered a

final treatment, but can
achieve low residual solvent
levels
Aqueous treated stream will

probably require polishing.
Further concentration of
overhead steam generally
required
Not generally considered a

final treatment, but may be
effective for highly volatile
wastes
Can achieve high efficiency
separations for certain
solvents/waste combinations
Can achieve low levels of
residual solvent in effluent.
Air emissions may require

treatment
Generally suitable only

for liquids of low solid
content
Suitable for low solid,
low concentration aqueous
waste streams
Technology well
developed for industrial
processing
Technology well
developed; used as
polishing treatment
Suitable for low solid

waste streams. Consider
for recovery of valuable
solvent
Technology well
Can achieve low levels of
developed in industry
residual solvent in effluent.
for special resin/solvent
combinations.
Applicability to waste
streams not
demonstrated
6-42
Residuals generated
Solvent solubility in aqueous

phase should be monitored
Adsorbate must be processed
during regeneration. Spent
carbon and wastewater may
also need treatment.
Adsorbate must be processed
during regeneration.
Applicable waste
streams
Process
Performance
Residuals generated
Chemical Treatment Processes

Wet air oxidation
Suitable for aqueous

liquids, also possible for
slurries. Solvent
concentrations up to 15%
High
temperature/pressure
technology, widely used
as pretreatment for
municipal sludges, only
one manufacturer
Supercritical water
For liquids and slurries
Supercritical conditions
oxidation
containing optimal
may impose demands
concentrations of about
on system reliability.
10% solvent
Commercially available
in 1987
Ozonation
Oxidation with ozone
Now used as a
(possibly assisted by [UV] polishing step for
suitable for low solid,
wastewaters
dilute aqueous solutions
Oxidation technology
Other chemical oxidation Oxidizing agents may be
well developed for
processes
highly reactive for
cyanides and other
specific constituents in
species (phenols), not
aqueous solution
yet established for
general utility
Chlorinolysis
Suitable for any liquid
Process produces a
chlorinated wastes
product (e.g., carbon
tetrachloride). Not
likely to be available
Dechlorination
Dry soils and solids
Not fully developed
Biological Treatment
Methods
Aerobic technology
suitable for dilute wastes
although some
constituents will be
resistant
Pretreatment for biological

Some residues likely which
treatment. Some compounds need further treatment
resist oxidation
Supercritical conditions
achieve high destruction
efficiencies (>99.99%) for
all constituents
Not likely to achieve

Residual contamination likely;
residual solvent levels in the will require additional
low ppm range for most
processing of off gases
wastes
Not likely to achieve
residual solvent levels in the will require additional
processing
low ppm range for most
wastes
Not available
Destruction efficiency of
over 99% reported for
dioxin
Conventional treatments May be used as final
treatment for specific
have been used for
wastes, may be
years
pretreatment for resistant
species
6-43
Residuals not likely to be a

problem. Halogens can be
neutralized in process
Air and wastewater emissions

were estimated as not
significant
Residual contamination seems
likely
will usually require additional
processing
Figure 6-9. Industrial wastewater process applicability matrix (McArdle et al., 1987)
6-44
6.4.4 Other Contaminant-Specific Options

Table 6-9 is a matrix identifying the applicability of 19 physical, chemical, and
biological technologies for treating the following wastewater characteristics: (1) suspended
solids, (2) oil, grease, and immiscible liquids, (3) pH, (4) total dissolved solids, (5) metals,
(6) cyanides, (7) volatile organics, (8) semivolatile organics, (9) pesticides and PCBs, and (10)
pathogens.
Table 6-10 is a similar matrix rating the potential effectiveness of 16 thermal,
chemical, physical, and biological treatment technologies for eight types of organic
contaminants and eight types of inorganic contaminants in soils and sludge. This matrix was
developed for screening technologies at contaminated sites, but all the ex-situ technologies (11
of the 16) are equally applicable to treatment of hazardous waste at HWTCs.
Table 6-11 is a matrix rating the effectiveness of six technologies for treating
contaminated solids for 11 major types of hazardous contaminants. These 11 groups were
developed for the EPA Superfund program to facilitate tests for the treatability of materials at
uncontrolled hazardous waste sites. The nine categories for organic contaminants represent a
more detailed breakdown than shown in other tables in this guide. A more complete list of
applicable treatment technologies for these treatability groups as they relate to pesticide
chemical waste groups is contained in Table B-5 in Worksheet B (Volume II).
Finally, Table C-8 in Worksheet C (in Volume III) provides a screening matrix for
more than 50 treatment technologies in relation to the following five major groups of
contaminants: (1) volatile organic compounds (VOCs), (2) semivolatile organic compounds
(SVOCs), (3) fuels (petroleum hydrocarbons), (4) inorganics, and (5) explosives. Information
on how to use this matrix is presented in Worksheet C.
Although the matrices in Tables 6-5, 6-9, 6-10, 6-11, and C-9 overlap somewhat, each
contains significant information that is not covered elsewhere.
6-45
Table 6-10. Treatment technology screening guide contaminants in soil and sludges
(U.S. EPA, 1988)
6-46
Table 6-11. Predicted treatment effectiveness for contaminated solids

(Offut and Knapp, 1990)
6-47
6.4.5 Industry-Specific Options

Table 6-12 is a matrix that identifies the applicability of 27 candidate treatment and
control technologies for 34 industries. This table provides a somewhat quicker way to prepare
a preliminary list of candidate treatment technologies for a particular industry than the
procedure described in Worksheet A (Volume II), but should not be used as a substitute for a
more detailed screening process.
6.4.6 Most Commonly Used Treatment Processes
Typically, HWTCs need to have the ability to treat the full range of hazardous wastes
that are produced by industrial processes, unless industrial production in a region is so
specialized that certain categories of hazardous waste are not generated. Compared with
CETPs, treatment processes at HWTCs need to handle concentrated liquid, sludge, and solid
wastes, which mainly require physical, chemical, and thermal treatment, and also use of S/S
technologies. If an HWTC also receives large amounts of industrial wastewater, then
biological treatment processes are also likely to be significant, and the HWTC would also
function as a CETP.
Table 6-13 summarizes the results of a survey that EPA conducted in 1994 of 85
centralized waste treatment facilities in the United States to identify the types of treatment
technologies in actual use. All of these facilities mainly treat liquid wastes received from
industries. The 22 technologies in Table 6-13 are classified as (1) physical pretreatment, (2)
physical phase separation, (3) chemical, (4) biological, and (5) sludge dewatering.
Equalization is the most commonly used pretreatment method (81 facilities) with
clarification/flocculation (35 facilities) and gravity separation (18 facilities) also commonly
used. Granular media filtration (equally divided between sand filters and multimedia filters)
and carbon adsorption are the most commonly used physical treatment methods.
Precipitation is by far the most commonly used chemical treatment method, and
multiple applications at a single facility are typical. Cyanide destruction and chromium
reduction were performed at a little less than half the facilities.
Activated sludge was the most commonly used biological treatment process and was
usually used only at facilities with onsite manufacturing operations that produced a relatively
constant waste stream that could support a continuous biological treatment system.
Plate and frame press filtration was the most commonly used sludge dewatering method
(34 facilities), followed by vacuum filtration (10 facilities) and belt pressure filtration (6
facilities).
Chapter 8 includes a case study of an existing HWTC that outlines the mix of
technologies likely to be required at HWTCs.
6-48
Table 6-12. Candidate treatment and control technology for 34 industries (Saltzberg
and Cushnie, 1985)
6-49
Table 6-13. Frequency of use of treatment technologies at industrial centralized waste

treatment facilities
Technology
Number (Out of 85)

Physical Pretreatment
Gravity separation
18
Clarification/flocculation
35
Dissolved air flotation
Emulsion breaking
Most oils subcategory facilities
Equalization
81 (36 unstirred, 45 stirred or aerated)

Physical (Phase Separation)
Air stripping
Granular media filtration
10 sand filters, 9 multimedia filters
Carbon adsorption
11
Reverse osmosis
Ultrafiltration
Liquid carbon dioxide extraction
1
Chemical
Precipitation
184 individual applications (more than one per

facility)
Cyanide destruction
30
Chromium reduction
38 (4 sulfur dioxide, 21 sodium bisulfite, 2 sodium

metabisulfite, 11 other reagents)
Electrolytic recovery
Ion exchange
1
Biological
Sequencing batch reactors
Biotowers
Activated sludge
12
Sludge Dewatering
Plate and frame pressure filtration
34
Belt pressure filtration
Vacuum filtration
10
Source: EPA (1995) WTI Survey
6-50
6.5
RESIDUALS MANAGEMENT AND DISPOSAL
Several types of residuals (i.e., waste products) are generated from the treatment
processes employed at CETPs and HWTCs including: sludges, solids, incinerator ash, air
emissions, and concentrated liquid waste streams.
Table 6-14 provides an overview of the major types of residuals associated with
wastewater treatment processes. Table 6-1 identifies residuals associated with specific
neutralization processes, and Table 6-8 identifies residuals associated with solvent treatment
processes. Treatment and disposal options for the major types of residuals produced by CETPs
and HWTCs are discussed below.
Table 6-14.
Residual generated by various wastewater treatment processes (McArdle et

al., 1987)
Residuals
Treatment process
Sludges
Pretreatment operations
Sedimentation
Granular media filtration
Oil/water separation
Physical/chemical treatment operations
Neutralization
Precipitation flocculation/sedimentation
Oxidation/reduction
Carbon adsorption
Air stripping
Steam stripping
Reverse osmosis
Ultrafiltration
Ion exchange
Wet-air oxidation
Biological treatment operations
Activated sludge
Sequencing batch reactor
Powdered activated carbon treatment (PACT)
Rotating biological contactor
Trickling filter
Air
emissions
Concentrated
liquid waste stream
Spent
carbon
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
6.5.1 Overview of Sludge Treatment Options

The treatment processes described in Sections 5 and 6 concentrate solids from liquid
wastes into sludges that must be treated (e.g., stabilized and dewatered) before being finally
disposed. The following discussion addresses sludge treatment processes relevant to both
CETPs and HWTCs.
6-51
Figure 6-13 shows a general schematic for handling sludge at municipal wastewater
treatment plants. Most processes shown in this figure are intended to remove water, reduce
volume, or reduce the mass of solids in the initial sludge, which is typically only a few percent
solids and the rest water. Many of these processes, such as aerobic and anaerobic digestion,
lime stabilization, and composting, also reduce pathogens in municipal wastewater sludges.
Table 6-15 describes the effect of major sludge treatment processes on sludge and their
significance for sludge use and disposal options. If CETPs are likely to receive human as well
as industrial wastewaters, reduction of pathogens should be a significant design consideration,
especially if land application for agricultural purposes is desired. In HWTCs, pathogen
reduction generally is not a concern unless the facility processes medical wastes.
Sludge thickening methods typically increase sludge solids from a few percent solids to
as much as 10 percent solids. Raw primary sludges that have not received biological treatment
also require stabilization to control odors and pathogens. WPCF/WEF (1980) provides more
detailed information on sludge thickening.
Sludge stabilization involves digestion or oxidation of sludge to reduce the mass of
solids and pathogens. Lime stabilization, during which lime (hydrated lime, Ca(OH)2;
quicklime, CaO; or lime-containing kiln dust or fly ash) is added in sufficient amounts to raise
the pH above 12, is a method for pathogen reduction. Major references for additional
information on sludge stabilization include EPA (1977) and WPCF/WEF (1985, 1987b).
THICKENING
PRIMARY
SLUDGE
TREATMENT
* Compost
* Incineration
* Drying
* Source thickening in the

primary clarifier
* Gravity
STABILIZATION
*
*
*
*
THICKENING
SECONDARY
SLUDGE
Anaerobic digestion
Aerobic digestion
Wet air oxidation
Anaerobic -aerobic
digestion
* Chlorine oxidation
* Lime stabilization
CONDITIONING
* Ferric chloride
* Lime
* Lime and ferric
chloride
* Polymer
* Heat treatment
* Elutriation
* Freeze-thaw
DEWATERING
*
*
*
*
*
*
*
Solid-bowl centrifuge
Belt filter-press
Vacuum filter
Filter press
Drying beds
Sludge lagoons
Gravity/low pressure
devices
ULTIMATE
DISPOSAL
* Land spread
* Landfill
* Land injection
* Dissolved air flotation

* Solid-bowl centrifuge
* Belt or drum thickener
Figure 6-13. General schematic for solids handling showing most commonly used
methods of treatment and disposal (U.S. EPA, 1987)
6-52
Table 6.15.
Effects of pretreatment and sludge treatment processes on sludge and

sludge use/disposal options
Treatment process and definition
Effect on sludge
Pretreatment: Reduction in
contaminant levels in industrial
wastewater discharge
Reduces levels of heavy metals and

organics in industrial wastewater
discharge, thereby lowering the
concentration of these constituents in
the sludge
Heat drying: Application of heat to

kill pathogens and eliminate most of
the water content
Disinfects sludge. Slightly lowers

potential for odors and biological
activity
Effect on use/disposal options
Increases the viability of land

application, distribution and marketing,
and ocean disposal. Reduces need for
pollution control devices during
incineration, and prevents problems
with incinerator ash disposal
Thickening: Low-force separation of
Increases solids concentration of sludge Lowers sludge transportation costs for
all options
water and solids by gravity or flotation by removing water, thereby lowering
sludge volume
Digestion (Aerobic and Anaerobic):
Reduces the volatile and biodegradable Reduces sludge quantity. Preferred
Biological stabilization of sludge
organic content of sludge by converting stabilization method prior to landfilling
through conversion of some of the
it to soluble material and gas. Reduces and land application. Reduces heat
organic matter to water, carbon
pathogen levels and controls
value for incineration, but anaerobic
dioxide, and methane.
putrescibility
digestion produces recoverable
methane
Lime Stabilization: Stabilization of
Raises sludge pH. Temporarily
Increases the amount of auxiliary fuel
sludge through the addition of lime
decreases biological activity. Reduces
required in incineration if the amount
pathogen levels and controls
of inert material in the sludge is
putrescibility. Increases the dry solids
increased
mass of the sludge
Conditioning: Alteration of sludge
Improves sludge dewatering
Increases the amount of auxiliary fuel
properties to facilitate the separation of characteristics. Conditioning may
required in incineration if the amount
water from sludge. Conditioning can
increase the mass of dry solids to be
of inert material in the sludge is
be performed in many ways, e.g.,
handled and disposed of without
increased
adding inorganic chemicals such as
increasing the organic content of the
lime and ferric chloride; adding
sludge
organic chemicals such as polymers; or
briefly raising sludge temperature and
pressure. Thermal conditioning also
causes disinfection
Dewatering: High-force separation of Increases solids concentration of sludge Reduces fuel costs for incineration.
water and solids
by removing much of the entrained
Reduces land requirements and bulking
water, thereby lowering sludge volume. soil requirements for landfilling.
Some nitrogen and other soluble
Lowers sludge transportation costs for
materials are removed with the water
all options. Dewatering may be
undesirable during land application in
regions where the water itself is a
valuable agricultural resource.
Reduction of nitrogen levels may or
may not be an advantage
Composting: Aerobic process
Lowers biological activity. Can destroy Useful prior to land application and
distribution and marketing. Often not
involving the biological stabilization of all pathogens. Degrades sludge to a
appropriate for other use or disposal
sludge in a windrow, in an aerated
humus-like material. Increases sludge
static pile, or in a vessel
mass due to addition of bulking agent
options due to cost
6-53
Generally used only prior to

distribution and marketing
Sludge conditioning involves physical (heat, freeze-thaw) or chemical treatment to

reduce moisture content and modify sludge characteristics to increase the rate of subsequent
dewatering processes. WPCF/WEF (1988) provides more detailed information on sludge
conditioning.
Sludge dewatering increases solids content to the point where sludge can be more or
less handled as a solid for use or disposal (see Section 6.5.1.1). The solids content of
dewatered sludges varies greatly depending on the characteristics of the sludge and the
dewatering method used but typically ranges from 20 to 50 percent. Table 6-16 outlines
operational selection criteria for sludge dewatering processes based on plant size. Major
references for additional information on municipal sludge dewatering include EPA (1987) and
WPCF/WEF (1983, 1987a). The next section provides additional information on commonly
used dewatering methods at hazardous waste treatment facilities.
6.5.1.1 Sludge Dewatering at HWTCs
Hazardous waste treatment processes such as sedimentation, neutralization,
precipitation, and oxidation/reduction produce sludges that often must be dewatered before
further treatment or disposal. This section describes three dewatering systems that are
commonly used at industrial waste treatment facilities in the United States (see Table 6-13):
n
n
n
Plate and frame pressure filtration

Vacuum filtration
Belt pressure filtration
Plate and Frame Pressure Filtration

A plate and frame filter press consists of a number of filter plates or trays connected to
a frame and pressed together between a fixed end and a moving end (Figure 6-14a). Filter
cloth is mounted on the face of each plate. The sludge is pumped into the unit under pressure
while the plates are pressed together. The solids are retained in the cavities of the filter press
and begin to attach to the filter cloth until a cake is formed. The water or filtrate passes
through the filter cloth and is discharged from a drainage port in the bottom of the press. The
sludge influent is pumped into the system until the cavities are filled. Pressure is applied to the
plates until the flow of filtrate stops. At the end of the cycle, the pressure is released and the
plates are separated. The filter cake drops into a hopper below the press. The filter cake can
then be disposed of in a landfill. The filter cloth is washed before the next cycle begins. The
key advantage of plate and frame pressure filtration is that it can produce a drier filter cake
than other methods of sludge dewatering can, and the fact that it is a batch process is an
advantage when sludges from different waste streams need to be handled separately. Because
of the batch operation, however, a plate and frame filter press is more labor intensive.
6-54
Table 6-16. Operational Selection Criteria for Sludge Dewatering Processes (U.S. EPA,
1987)
Plant Size
Small
< 0.08 m3/s
(< 2 mgd)
Medium
0.08 0.44 m3/s
(2 10 mgd)
Large
> 0.44 m3 /s
Key Criteria
Minimum Mechanical Complexity
Local Repairs and Parts
Minimum operator attendance
Reliable without skilled service
Unaffected by climatic factors
Large excess capacity
Handleable cake
Low operator attendance
Local repair and parts
Transportable cake without nuisance
Mechanical reliability
Competitive O&M costs
Drier cake
Lowest O&M costs/ton dry solids
Lowest capital costs/ton dry solids
Drier cake
High output/unit
Mechanical reliability
Transportable cake without nuisance
General Considerations
Compatibility with existing equipment with long-term sludge disposal.

Long-term serviceability/utility
Acceptable environmental factors
Good experience at other operating installations.
Competence and quality of local operator and service personnel
Compatibility with plant size
Acceptance by user and regulatory agency.
Availability and need of manufacturers services.
Rotary Vacuum Filtration

Rotary vacuum filters come in drum, coil, and belt configurations. The filter medium
can be made of cloth, coil springs, or wire-mesh fabric. A typical application is a rotary
vacuum belt filter (see Figure 6-14b). A continuous belt of filter fabric is wound around a
horizontal rotating drum and rollers. The drum is perforated and is connected to a vacuum.
The drum is partially immersed in a shallow tank containing the sludge. As the drum rotates,
the vacuum that is applied to the inside of the drum draws the sludge onto the filter fabric. The
water from the sludge passes through the filter and into the drum, where it exits via a
discharge port. As the fabric leaves the drum and passes over the roller, the vacuum is
released. The filter cake drops off the belt as it turns around the roller. The filter cake can then
be disposed of. Because vacuum filtration systems are relatively expensive to operate, they are
6-55
usually preceded by a thickening step that reduces the volume of sludge to be dewatered. It is a
continuous process and therefore requires less operator attention.
Belt Pressure Filtration
Belt pressure filtration uses gravity followed by mechanical compression and shear
force to produce a sludge filter cake. Belt filter presses are continuous systems that are
commonly used to dewater biological treatment sludge. Most belt filter installations are
preceded by a flocculation step, where polymer is added to create a sludge that has the strength
to withstand being compressed between the belts without being squeezed out. A typical belt
filter press is illustrated in Figure 6-14c. During the press operation, the sludge stream is fed
onto the first of two moving cloth filter belts. The sludge is gravity-thickened as the water
drains through the belt. As the belt holding the sludge advances, it approaches a second
moving belt. As the first and second belts move closer together, the sludge is compressed
between them. The pressure is increased as the two belts travel together over and under a
series of rollers. The turning of the belts around the rollers shears the cake, which furthers the
dewatering process. At the end of the roller pass, the belts move apart and the cake drops off.
The feed belt is washed before the sludge feed point. The dropped filter cake can then be
disposed of. The advantages of a belt filtration system are its lower labor requirements and
lower power consumption. One disadvantage is that belt filter presses produce a poorer quality
filtrate and require a relatively large volume of belt wash water.
6.5.2 Final Use and Disposal Options for Sludge
Residual sludges that remain after any recyclable constituents have been removed are
dewatered as much as possible before being ultimately disposed. Further stabilization, such as
adding a bulking agent (see Section 6.3.1), may be required to create a sludge consistency that
is easier to handle for transport to the location of ultimate disposal. Final disposal options for
sludge include beneficial uses such as (1) land application and (2) distribution and marketing of
composted sludge, or non-beneficial uses such as (1) landfilling, (2) incineration (see Section
6.3.2), and (3) ocean disposal.
The main difference between CETPs and HWTCs is that if SMSE pretreatment
programs are successful for a CETP, it should be possible to put sludge to a beneficial use by
land application for agricultural production, forestry, or land reclamation, whereas sludges
generated at HWTCs generally are unsuitable for beneficial uses. The general approach to
residuals management at an HWTC it is to treat them on site to minimize volume and toxicity,
and dispose of the remainder in a secure landfill. Figure 6-15 rates the relative importance of
sludge constituents, major sludge characteristics, and costs for the five use/disposal options.
Solids created using solidification processes, and incinerator ash, also require
placement in a final disposal area. The main disposal options for such residuals are landfilling
and ocean disposal.
6-56
Major general references for additional information on sludge treatment, use, and
disposal include HMCRI (1974-1989), EPA (1979, 1984b, 1985b), and WPCF/WEF (1989).
Figure 6-14. Selected sludge dewatering systems: (a) plate and press pressure filtration,
(b) vacuum filtration, and (c) belt pressure filtration (U.S. EPA, 1995)
6.5.2.1 Land Application
Where land is available, and sludges are uncontaminated or contaminants exist in
concentrations that are within acceptable limits, land application is the method of choice.
Timing and rates of application may differ depending on whether the land is used for
agricultural crops, pasture, or forestry. Sludge is especially valuable for reclamation of
severely disturbed or degraded lands. Some capital costs for sludge treatment are showed in
Section 7.3.2 Table 6-16 presents pollutant concentration limits for land application of sludges.
6-57
Table 6-17. Pollution limit for land application of sludge
Pollutant
Arsenic
Cadmium
Chrome
Copper
Lead
Mercury
Molibdene
Nickel
Selenium
Zinc
Maximum concentration
limit (**)
(mg/kg)
75
85
3000
4300
840
57
75
420
100
7500
Description (*)
Permissible
Pollutant accumulation
concentration limit (***)
rate
(mg/kg)
(kg/ha)
41
41
39
39
3000
1200
1500
1500
300
300
17
17
18
18
420
420
100
36
2800
2800
Annual pollutant
accumulation rate
(kg/ha/year)
2.0
1.9
150
75
15
0.85
0.90
21
5.0
140
(*) All limits in a dry basis; (**) absolute values; (***) monthly averages.
USEPA. 40 CFR Part 503, Standards for the use or disposal of sewage sludge. 1993.
Major references for additional information on land application of sewage sludge include
HMCRI (1974-1989), EPA (1983, 1994), and WCPF/WEF (1989).
6.5.2.2 Distribution and Marketing
Composting of sludge produces a stable product that can be bagged and marketed.
Composting requires mixing of dewatered sludge with a bulking agent such as wood chips,
bark, rice hulls, or straw, and further aerobic decomposition. Major references for additional
information on sludge composting include Benedict et al. (1987), HMCRI (1974-1989), and
EPA (1985a).
6-58
Figure 6-15. Importance factors affecting sludge use/disposal options: (a) sludge
constituents, (b) sludge characteristics, and (c) cost factors
6-59
6.5.2.3 Landfilling
Modern landfills are coming under increased regulatory scrutiny, and as a result, will
be more protective of the environment in the future. A variety of specific technologies are
associated with a state-of-the-art landfill including: liner systems, leachate collection systems,
leachate treatment, landfill gas control and recovery, improved closure techniques, provisions
for post-closure care, and monitoring systems, all of which are discussed below. If landfills
are properly planned and operated, a completed landfill site can ultimately be used by the
owner for recreational or other purposes, such as open space. Batstone et al. (1989) address
technical requirements for safe disposal of hazardous waste in landfills. Table B-1, in
Appendix B, identifies major references on the design of secure landfills.
Siting a Landfill
Siting a hazardous waste landfill involves analyzing a number of factors associated with
location alternatives. Because of environmental concerns, careful scientific and engineering
analysis must take place during potential site evaluations. Surface and subsurface geology,
hydrogeology, and the environmental nature of surrounding areas must be evaluated for
potential impacts. Ground water resources must be protected, and the integrity of soils must be
preserved. A substantial hydrogeological investigation and prediction of leachate quantities are
usually performed early in the planning stages. When siting a new landfill, decision makers
also will have to consider logistical factors such as access roads, travel distance, and travel
time.
Hazardous Waste Landfill Components
Cells are the basic building blocks of landfills. During daily operations, waste is
confined to defined areas where it is spread and compacted throughout the day. At the end of
the day (or several times a day), the waste is covered by a thin layer of soil, which also is
compacted. This unit of compacted and covered waste is called the cell. Several adjacent cells
(all the same height) are referred to as a lift. A landfill consists of a series of lifts.
The components of a hazardous waste landfill include:
n
n
n
Foundations
Dikes
Liner Systems
- Low-permeability soil liners
- Flexible membrane liners (FMLs)
- Leachate collection systems
Final cover systems
6-60
Foundations
The foundations for hazardous waste landfills should provide structurally stable
subgrades for the overlying landfill components. The foundations also should provide
satisfactory contact with the overlying liner or other system components. In addition, the
foundations should resist settlement, compression, and uplift resulting from internal or external
pressures, thereby preventing distortion or rupture of the landfill components.
Dikes
The purpose of a dike in a hazardous waste landfill is to function as a retaining wall,
resisting the lateral forces of the stored wastes. A dike is the aboveground extension of the
foundation and provide support to the overlying landfill components. Dikes therefore must be
designed, constructed, and maintained with sufficient structural stability to prevent their
failure. Dikes also may be used to separate cells for different wastes within a large landfill.
Dikes may be constructed of soil material that is compacted as necessary to a specified
strength. Materials other than soil may be used to construct dikes, as long as the design of the
dike accommodates the particular properties of the selected materials and proper installation
procedures are followed. Drainage layers and structures may be included in the dike design if
conditions warrant control of seepage. Although seepage through a dike should be prevented
by a liner system, a dike must be designed to maintain its integrity if the liner fails and
seepage occurs.
Liner Systems
The primary function of a liner system is to minimize and control the flow of leachate
from the site to the environment, particularly towards ground water. Liners are made of lowpermeability soils (typically clays) or synthetic materials (e.g., plastic). Landfills can be
designed with more than one liner, and a mix of liner types may be used (these are referred to
as composite liners).
There are two types of liner systems currently used in land disposal facilities in the
U.S. A single liner system consists of one liner and one leachate collection system as shown in
Figure 6-16. A double liner system includes two liners (primary and secondary), with a
primary leachate collection system above the primary (top) liner and a secondary leak
detection/leachate collection system between the two liners, as shown in Figure 6-17.
6-61
Figure 6-16. Schematic of a single clay liner system for a landfill (U.S. EPA, 1988)
Figure 6-17. Schematic of a double liner and leak detection system for a landfill
(U.S. EPA, 1988)
6-62
The term "liner system" includes the liner(s), leachate collection system(s), and any
special additional structural components such as filter layers or reinforcement. The major
components of both single and double liner systems are the following:
n
n
n
Low-permeability soil liners

Flexible membrane liners (FML)
Leachate collection and removal systems (LCRS)
Low-Permeability Soil Liners. The purpose of a low-permeability soil liner depends

on the overall liner system design. In the cases of single liners constructed of soil or double
liner systems with soil secondary liners, the purpose of the soil liner is to prevent constituent
migration through the soil liner. In the case of soil liners used as the lower component of a
composite liner, the soil component serves as a protective bedding material for the FML upper
component and minimizes the rate of leakage through any breaches in the FML upper
component. An objective shared by all low-permeability soil liners is to serve as long-term,
structurally stable bases for all overlying materials.
Low-permeability soil liner design is site- and material-specific. Prior to design, many
fundamental yet important criteria should be considered such as: in-place permeability of the
liner; liner stability against slope failure, settlement, and bottom heave; and the long-term
integrity of the liner. Natural and manmade soil amendments (e.g., soil-cement, bentonite,
lime) may be specified in a soil liner design to enhance the performance of natural soil.
Flexible Membrane Liners. The purpose of a FML in a hazardous waste landfill is to
prevent the migration of any hazardous constituents into the liner during the period that the
facility is in operation and typically during a 30-year postclosure monitoring period. In
addition, FMLs should be compatible with the waste liquid constituents that may contact them
and be of sufficient strength and thickness to withstand the forces expected to be encountered
during construction and operation.
The design of a lined sewage sludge surface disposal site requires consideration of more
than the performance requirements of the FML; it also requires careful design of the
foundation supporting the FML. The foundation provides support for the liner system,
including the FMLs and the leachate collection and removal systems. If the foundation is not
structurally stable, the liner system may deform, thus restricting or preventing its proper
performance.
The performance requirements of an FML include:
n
n
n
Low permeability to waste constituents

Strength or mechanical compatibility of the sheeting
Durability for the lifetime of the facility
6-63
The designer must specify the necessary criteria for each of these properties based on
engineering requirements, performance requirements, and the specific site conditions.
Leachate Collection Systems. Leachate refers to liquid that has passed through or
emerged from landfilled waste and contains dissolved, suspended, or immiscible materials
removed from the waste. The purpose of a primary leachate collection system in a landfill is to
minimize the leachate head on the top liner during operation and to remove liquids from the
landfill through the postclosure monitoring period. The leachate collection system should be
capable of maintaining a leachate head of less than 30 cm (1 foot). The purpose of a secondary
leachate collection system (sometimes referred to as a leak detection system) between the two
liners of a landfill is to rapidly detect, collect, and remove liquids entering the system through
the postclosure monitoring period. If uncontrolled, landfill leachate can be responsible for
contaminating ground water and surface water.
Leachate is generally collected from the landfill through sand drainage layers, synthetic
drainage nets, or granular drainage layers with perforated plastic collection pipes, and is then
removed through sumps or gravity drain carrier pipes.
Once leachate has been collected and removed from the landfill, it must undergo some
type of treatment and disposal. The most common methods of management are:
n
n
n
Discharge to a wastewater treatment plant

On-site treatment followed by discharge
Recirculation back into the landfill
An extensive body of literature has been developed on the design of liners and leachate
collection systems. For additional information on these systems, including information on
materials specifications, construction procedures, and quality control issues, see the references
U.S. EPA, 1988, and U.S. EPA, 1993.
Landfill Closure and Final Cover Systems
Closure is the procedure, once waste placement in a landfill ends, that renders the site
safe and acceptable to the public. Closure is intended to minimize the environmental and
public health and safety hazards, and prepares the site for the post-closure period. During the
post-closure period, the site may be secured to allow degradation of the waste to proceed.
Once the site has stabilized, it is converted to its planned final end use.
Final cover systems for hazardous waste landfills are designed to provide long-term
minimization of liquid migration and leachate formation in the closed landfill by preventing the
infiltration of surface water into the landfill for many years. Final cover systems also control
the venting of gas generated in the facility and isolate the wastes from the surface
environment. These cover systems are constructed in layers, the most important of which are
the barrier layers. Other layers are included to protect or to enhance the performance of the
barrier layers. A final cover system must be constructed so that it functions with minimum
6-64
maintenance, promotes drainage and minimizes erosion or abrasion of the cover,

accommodates settlement and subsidence so that the cover's integrity is maintained, and has a
permeability less than or equal to the permeability of the bottom liner system component with
the lowest permeability.
Environmental Safeguards at Landfill Sites
Ground-water protection is the most difficult and costly environmental control measure
required at many hazardous waste landfills. Additionally, contamination of surface water and
methane gas buildup must be avoided.
Monitoring
To ensure the components of a landfill are performing their designed function, surface
water and ground water monitoring should be included at all landfills. By sampling from
ground water wells located near the solid waste disposal facility, the presence, degree, and
migration of any leachate can be detected. The main concern with environmental monitoring is
ensuring that the number and location of sampling points are adequate to characterize
background levels (for ground water) and that sampling is frequent enough to determine
whether any performance or other environmental quality standards are being met.
Run-on/Runoff Controls for Surface Waters
The purpose of a run-on control system is to collect and redirect surface waters to
minimize the amount of surface water entering the landfill. Run-on control can be
accomplished by constructing berms and swales above the filling area that will collect and
redirect the water to the stormwater control structures.
Surface water management also is necessary at landfill sites to minimize erosion
damage to earthen containment structures. Design of a surface water management system
requires a knowledge of local precipitation patterns, surrounding topographic features,
geologic conditions, and facility design. Surface water management systems do not have to be
expensive or complex to be effective. The equipment and materials used for construction of the
surface water management system are the same as those used for general earthwork and
foundation construction.
Explosive Gases Control
Methane gas is a product of the anaerobic decomposition of organic waste. At and
around landfills, methane can migrate through soil and accumulate in closed areas (e.g.,
building basements). The accumulation of methane gas in landfills can potentially result in fire
and explosions that can endanger employees, users of the site, and occupants of nearby
structures, or cause damage to containment structures (methane is explosive in confined spaces
when found in concentrations between 5 and 15 percent). These hazards are preventable
through monitoring and through corrective action should methane gas levels exceed specified
6-65
limits in the facility structures. Once methane is collected, it is usually vented into the
atmosphere, flared (burned), or recovered as an energy source.
6.5.2.4 Ocean Disposal
In ocean disposal, municipal wastewater sludge is released into a designated area of the
ocean either from outfall pipes or vessels at the ocean surface. This option has the potential for
severely degrading the local marine environment. Batstone et al. (1989) address the technical
requirements for safe disposal of hazardous waste in the ocean.
6.5.3 Air Emissions
Conventional aerobic biological treatment processes generally do not produce noxious
off gases. Anaerobic biological treatment, however, can produce hydrogen sulfide, a toxic gas
that requires offgas treatment, and methane, a combustible gas that needs to be either collected
for its energy value or diluted below its explosive limit. Biological treatment of wastewater
containing toxic organics typically requires collection and treatment of the offgases to remove
organic contaminants (see Figure 5-6). Similar sorts of treatment are required for air and
thermal stripping technologies that separate contaminants into their gaseous phase. Incineration
technologies require the collection of particulates in stack gases, and treatment of products of
incomplete combustion and acid gases. These air pollution control technologies result in solid
particulate residues that require disposal and liquid wastes that usually require further
treatment.
6.5.4 Concentrated Liquid Waste Streams
Processes such as reverse osmosis and ultrafiltration create concentrated liquid waste
streams. Concentrated wastewaters containing inorganic constituents can be further treated by
precipitation and then dewatered. Evaporation is an alternative method for obtaining residual
solids from concentrated liquid waste streams. Concentrated organic liquid waste streams are
usually incinerated. Deep well injection is another alternative for concentrated liquid wastes.
6-66
6.6
REFERENCES
Batstone, R., J.E. Smith, Jr., and D. Wilson, eds. 1989. The Safe Disposal of Hazardous
Waste: the special needs and problems of developing countries. World Bank Technical Paper
Number 93.
Benedict, A.H., E. Epstein, and J. Alpert. 1987. Composting Municipal Sludge: A Technology
Evaluation. EPA/600/2-87/021.
Breton, M., et al. 1987. Technical Resource Document: Treatment Technologies for Solvent
Containing Wastes. EPA/600/2-86/095 (NTIS PB87129821). Washington, DC.
Fresenius, W., W. Schneider, B. Bhnke, and K. Pppinghaus (eds.). 1989. Waste Water
Technology: Origin, Collection, Treatment and Analysis of Waste Water. Springer-Verlag,
New York, NY.
Hazardous Material Control Research Institute. 1974. Municipal sludge management. HMCR.
Sludge/Wastewater Management Series.
Hazardous Material Control Research Institute. 1975. Municipal Sludge Management and
disposal. HMCRI. Sludge/Wastewater Management Series.
Hazardous Material Control Research Institute. 1977. Disposal of residues on land. HMCRI.
Sludge/Wastewater Management Series.
Hazardous Material Control Research Institute. 1977. Composting of municipal residues and
sludges. HMCRI. Sludge/Wastewater Management Series.
Hazardous Material Control Research Institute. 1978. Acceptable sludge disposal techniques.
HCMRI. Sludge/Wastewater Management Series.
Hazardous Material Control Research Institute. 1978. Treatment and disposal of industrial
wastewater HMCRI. Sludge/Wastewater Management Series.
Hazardous Material Control Research Institute. 1978. Design of municipal sludge compost
facilities. HMCRI. Sludge/Wastewater Management Series.
Hazardous Material Control Research Institute. 1979. Municipal management impact of
industrial toxic material on POTW sludge. HMCRI. Sludge/Wastewater Management Series.
Hazardous Material Control Research Institute. 1980. Composting of municipal and industrial
sludges: design, operations, marketing, health, rules & regs. HMCRI. Sludge/Wastewater
Management Series.
6-67
Hazardous Material Control Research Institute. 1980. Municipal and industrial sludge
composting-materials handling. HMCRI. Sludge/Wastewater Management Series.
Hazardous Material Control Research Institute. 1982. Composting of Municipal and Industrial
Sludges. HMCRI. Sludge/Wastewater Management Series.
Hazardous Material Control Research Institute. 1980; 1983. Municipal and Industrial Sludge
Utilization and Disposal Proceedings Series. HMCRI. Municipal and Industrial Sludge
Utilization and Disposal Proceeding Series.
Hazardous Material Control Research Institute. 1986; 1987; 1988; 1989). Municipal Sewage
Treatment Plant Sludge Management Proceedings Series.
McArdle, J.L., M.M. Arozarena, and W.E. Gallagher. 1987. A Handbook on Treatment of
Hazardous Waste Leachate. EPA/600/S8-87/006 (NTIS PB87152328). Washington, DC.
Offut, C.K., and J.O. Knapp. 1990. The Challenge of Treating Contaminated Superfund Soil.
In: Superfund '90, Hazardous Material Control Research Institute, Silver Spring, MD, pp.
700-711.
Saltzberg, E.R., and J.C. Cushnie, Jr. 1985. Centralized Waste Treatment of Industrial
Wastewater. Noyes Data Corporation, Park Ridge, NJ.
U.S. EPA. 1977. Operator Manual: Stabilization Ponds. EPA/430/9-77-005. Washington,
DC.
U.S. EPA. 1979. Sludge Treatment and Disposal (Process Design Manual). EPA/625/1-79011 (NTIS PB80200546). Washington, DC. [See also U.S. EPA (1974, 1978a).]
U.S. EPA. 1983. Land Application of Municipal Sludge (Process Design Manual).
EPA/625/1-83-016. Washington, DC.
U.S. EPA. 1984a. Waste Analysis Plans: A Guidance Manual. EPA/530-SW-84-012.
Washington, DC.
U.S. EPA. 1984b. Use and Disposal of Municipal Wastewater Sludge (Environmental
Regulations and Technology). EPA/625/10-84-003. Washington, DC.
U.S. EPA. 1985a. Composting of Municipal Wastewater Sludges. Seminar Publication
EPA/625/4-85-014 (NTIS PB88186119). Washington, DC.
U.S. EPA. 1985b. Estimating Sludge Management Costs at Municipal Wastewater Treatment
Facilities (Handbook). EPA/625/6-85/010 (NTIS PB86124542). Washington, DC.
6-68
U.S. EPA. 1987. Dewatering Municipal Wastewater Sludges (Design Manual). EPA/625/187/014. Washington, DC.
U.S. EPA. 1988. Guide to Technical Resources for the Design of Land Disposal Facilities.
EPA/625/6-88/018. Cincinnati, OH.
U.S. EPA. 1991. Issues Affecting the Applicability and Success of Remedial/Removal
Incineration Projects. Superfund Engineering Issue. EPA/540/2-91/004. Washington, DC.
U.S. EPA. 1992. Rotating Biological Contactors. Engineering Bulletin EPA/540/S-92/007.
Washington, DC
U.S. EPA. 1993. Solid Waste Disposal Facility Criteria, Technical Manual. EPA/530/R93/017 (NTIS PB94-100-450). Washington, DC.
U.S. EPA. 1993. 40 CFR Part 503, Standards for the use or disposal of sewage sludge.
U.S. EPA. 1994. Process Design Manual for Land Application of Sewage Sludge and
Domestic Septage. Draft Report Submitted by Eastern Research Group to U.S. EPA Center for
Environmental Research Information, September 16, 1994.
U.S. EPA. 1995. Development Document for Proposed Effluent Limitations Guidelines and
Standards for the Centralized Waste Treatment Industry. EPA/821-R-95-006. Washington, DC.
Weathington, B.C. 1988. Destruction of Cyanide in Wastewaters: A Review and Evaluation.
EPA/600/2-88/031 (NTIS PB88213046). Washington, DC.
Wilk, L., S. Palmer, and M. Breton. 1988. Technical Resource Document: Treatment
Technologies for Corrosive-Containing Wastes, Volume II. EPA/600/2-87/099 (NTIS
PB88131289). Washington, DC.
Water Pollution Control Federation; Water Environment Federation. 1980. Sludge thickening.
MOP FD-1. WPCF/WEF. Alexandria, VA.
Water Pollution Control Federation; Water Environment Federation. 1983. Sludge dewatering.
MOP 20. WPCF/WEF. Alexandria, VA.
Water Pollution Control Federation; Water Environment Federation. 1985. Sludge
stabilization. MOP FD-9. WPCF/WEF. Alexandria, VA.
Water Pollution Control Federation; Water Environment Federation. 1987a. Operation and
maintenance of sludge dewatering systems. MOP OM-8. WPCF/WEF. Alexandria, VA.
Water Pollution Control Federation; Water Environment Federation. 1987b. Activated sludge.
MOP OM-9. WPCF/WEF. Alexandria, VA.
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Water Pollution Control Federation; Water Environment Federation. 1988. Sludge

conditioning. MOP FD-14. WPCF/WEF. Alexandria, VA.
Water Pollution Control Federation; Water Environment Federation.. 1989. Beneficial use of
waste solids. MOP FD-15. WPCF/WEF. Alexandria, VA.
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SECTION 6

PLANNING AND DESIGN OF

6.1.1 Solid and Liquid Waste Characteristics and Volume

Just as pretreatment before discharge to a sewer is essential for effective functioning of

Figure 6-1 identifies potentially incompatible combinations of 12 types of hazardous

Figure 6-1. Compatibility of selected hazardous wastes (Batstone et al., 1989)

HAZARDOUS WASTEWATER TREATMENT PROCESS ALTERNATIVES

Air stripping (Section 6.2.1)

Chemical treatment methods covered in this section include:

Neutralization (Section 6.2.4)

Figure 6-3. Air stripping system diagram (U.S. EPA, 1995)

Figure 6-3a. Compact bed scrubber

Figure 6-4. Carbon adsorption system diagram (U.S. EPA, 1995)

to be exhausted. This condition can be detected by an increase in the pollutant concentration of

Applicable waste streams

Table 6-1. Summary of neutralization technologies (Wilk et al., 1988)

Dilute acid waste

Generally slower than

Requires stone sizes of

Will generate voluminous

All acid wastes

Will generate voluminous

More expensive than

All acid wastes

Reaction products are

Most expensive of all

All alkaline wastes

Will generate large

All alkaline wastes

Reaction products are

All alkaline wastes

Retention time 1 to 11/2

Will form calcium

Figure 6-6. Chemical precipitation system diagram (U.S. EPA, 1995)

management, called selective metals precipitation, can be implemented to concentrate on one

NaCNO + 2NaCl + H20

Reduction through the use of sodium metabisulfite or sodium bisulfite

A diagram of a chromium reduction system using gaseous sulfur dioxide is presented in

Cr2(S04)3 + 3NaHSO4 + 5H20

The hexavalent chromium is reduced to trivalent chromium using sodium metabisulfite,

Figure 6-7. Electrolytic recovery system diagram (U.S. EPA, 1995)

Figure 6-8. Ion exchange system diagram (U.S. EPA, 1995)

Slurry biodegradation is a treatment process where an aqueous slurry is created by

Figure 6-9. Schematic of anaerobic, expanded-bed GAC bioreactor

OTHER HAZARDOUS WASTE TREATMENT PROCESS ALTERNATIVES

Solidification/stabilization technologies (see Section 6.3.1)

S/S binding agents

Stabilized and solidified

Figure 6-10. Elements of a typical ex situ solidification/stabilization process (U.S. EPA,

Characteristics Affecting Processing Feasibility

Volatiles not effectively immobilized; driven off by heat

Use of acidic sorbent with metal hydroxide wastes

Use of acidic sorbent with cyanide wastes

Releases hydrogen cyanide

Use of acidic sorbent with waste containing

Releases ammonia gas

Use of alkaline sorbent (containing carbonates such

May create pyrophoric waste.

Easily leached from cement and lime.

Organics may interfere with bonding of waste materials

Semivolatile organics or polyaromatic hydrocarbons

Organics may interfere with bonding of waste materials.

Oil and grease

Weaken bonds between waste particles and cement by