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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.

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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 Both solid and liquid wastes must be collected, so mobile pickup is still required
even if a pipe system is in place.
n When multiple liquid waste streams (spent solvents, contaminated wastewaters)
have to be handled separately, multiple pipe collection systems are prohibitively
expensive.
n Outlying SMSEs can be more easily served by mobile systems than a pipe network.
n 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.

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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 Explosions
n Fire
n Generation of flammable gas
n Generation of toxic gas
n Generation of heat
n Solubilization of toxins

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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)

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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 Air stripping (Section 6.2.1)


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

n Neutralization (Section 6.2.4)


n Chemical precipitation (Section 6.2.5)
n Cyanide destruction (Section 6.2.6)
n Chromium reduction (Section 6.2.7)
n Electrolytic recovery (Section 6.2.8)
n Ion exchange (Section 6.2.9)

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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

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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.

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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.

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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, high-
molecular-weight organics, with low solubility, are readily adsorbed. Polar, low-molecular-
weight 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

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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 Reverse osmosis
n Ultrafiltration
n Carbon dioxide liquid extraction

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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

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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

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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 Applicable waste streams


n Stage of development
n Performance
n Residuals generated
n 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

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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 Stage of Performance Residuals Generated Cost


Streams Development
Acid/alkali All acid/alkali Well developed Generally slower than Variable, dependent on Least expensive of
mutual compatible waste comparable technologies quantity of insolubles and all neutralization
neutralization streams except due to dilute concentration products contained in each technologies
cyanide of reagents. May evolve waste stream
hazardous constituents if
incompatible wastes are
mixed

Limestone Dilute acid waste Well developed Requires stone sizes of Will generate voluminous Most cost-effective
streams of less than 0.074 mm or less. Requires sludge product when in treating
5,000 mg/l mineral 45 minutes or more of reacted with sulfate- concentrated wastes.
acid strength and retention time. Can only containing wastes. Stones May be cost-effective
containing low neutralize acidic wastes to over 200 mesh will in treating dilute
concentration of acid pH 6.0. Must be aerated to sulfonate, be rendered acidic wastes
salts remove evolved CO2 inactive, and add to sludge
product

Lime All acid wastes Well developed Requires 15 to 30 minutes Will generate voluminous More expensive than
of retention time. Must be sludge similar to limestone crushed limestone
slurried to a concentration (200 mesh)
of 10 to 35% solids prior to
use. Can under-(below pH
7) or over- (above pH 7)
neutralize

Caustic soda All acid wastes Well developed Requires 3 to 15 minutes of Reaction products are Most expensive of all
retention time. In liquid generally soluble, however, widely used alkaline
form, easy to handle and sludges do not dewater as reagents (five times
apply. Can under- or over- readily or as easily as lime the cost of lime)
neutralize including pH 13 or limestone
or higher

Sulfuric acid All alkaline wastes Well developed Requires 15 to 30 minutes Will generate large Least expensive of
except cyanide of retention time. In liquid quantities of gypsum sludge all widely used acidic
form, but presents burn when reacted with calcium- reagents
hazard. Highly reactive and based alkaline wastes
widely available

Hydrochloric All alkaline wastes Well developed, Requires 5 to 20 minutes of Reaction products are Approximately twice
acid but rarely retention time. Liquid form generally soluble as expensive as
applied due to present burn and fume sulfuric on a
high reagent cost hazard. More reactive than neutralization
sulfuric equivalent basis

Carbonic acids, All alkaline wastes Emerging Retention time 1 to 11/2 Will form calcium Approximately 3 to 4
liquid carbon except cyanide technology minutes. In liquid form, carbonate precipitate when times as expensive as
dioxide must be vaporized prior to reacted with calcium-based sulfuric. Therefore,
use. Can only neutralize alkaline wastes limited to
alkaline wastes to pH 8.3 applications using
and point 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

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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

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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 NaCNO + 2NaCl + H20


2NaCNO + 3Cl2 + 6NaOH 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 NaCNO + NaCl


2NaCNO + 3NaOCl + H20 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 Reduction through the use of sodium metabisulfite or sodium bisulfite


n 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


3H2SO3 + 2H2CrO4 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, wood-
preserving 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 Solidification/stabilization technologies (see Section 6.3.1)


n 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 Off-gas


treatment Residuals
(1) (2) (3) (optional)

(4)

Stabilized and solidified


Water media
Oversize rejects
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)

Characteristics Affecting Processing Feasibility Potential Interference


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 Releases ammonia gas
ammonium compounds
Use of acidic sorbent with sulfide wastes Releases hydrogen sulfide
Use of alkaline sorbent (containing carbonates such May create pyrophoric waste.
as calcite or dolomite) with acid waste
Use of siliceous sorbent (soil, fly ash) with May produce soluble fluorosilicates
hydrofluoric acid waste
Presence of anions in acidic solutions that form Cation exchange reactions leach calcium from S/S
soluble calcium salts (e.g., calcium chloride acetate, product increases permeability of concrete, increases rate
and bicarbonate) of exchange reactions.
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 Organics may interfere with bonding of waste materials.
(PAHs)
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.
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
Characteristics Affecting Processing Feasibility Potential Interference
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 Interferes with pozzolanic reactions that depend on
dichromate, and carbohydrates. formation of calcium silicate and aluminate hydrates.
Nonpolar organics (oil, grease, aromatic May impede setting of cement, pozzolan, or organic-
hydrocarbons, PCBs) polymer S/S. May decrease long-term durability and
allow escape of volatiles during mixing. With
thermoplastic S/S, organics may vaporize from heat.
Polar organics (alcohols, phenols, organic acids, With cement or pozzolan S/S, high concentrations of
glycols) 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.
Solid organics (plastics, tars, resin) Ineffective with urea formaldehyde polymers; may retard
setting of other polymer S/S.
Oxidizers (sodium hypochlorite, potassium May cause matrix breakdown or fire with thermoplastic
permanganate, nitric acid, or potassium dichromate) 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 cement-
based S/S.
Soluble salts of magnesium, tin, zinc, copper and May cause swelling and cracking within inorganic matrix
lead exposing more surface area to leaching.
Environmental/waste conditions that lower the pH of Eventual matrix deterioration.
matrix
Flocculants (e.g. ferric chloride) Interference with setting of cements and pozzolans.

Soluble sulfates > 0.01% in soil or 150 mg/L in Endangerment of cement products due to sulfur attack.
water
Soluble sulfates > 0.5% in soil or 2000 mg/L in Serious effects on cement products from sulfur attacks.
water
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
Characteristics Affecting Processing Feasibility Potential Interference
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 Combustion
Fuel Air Particulate
Removal

Waste Combustion Gas


Feeding Conditioning
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 Operating Parameter Effect of Performance Example Feeds of


Affected Concern
Heating value Rotary kiln Rotary kiln temperature, Feed capacity, fuel usage. Plastics, trash.
flue gas residence time.
Density Rotary kiln Weight of material held by Feed capacity. Brominated sludge (high
kiln. density sludge).
Halogen and Quench system, air Pump cavitation, pH Feed capacity, caustic Trial burn mixture,
sulfur content pollution control control, blowdown rate, usage. brominated sludge.
equipment design and particulate emissions.
operation.
Moisture Feed system Increased fuel usage to
maintain temperature.
Particle size Cyclone, SCC, ducts, Kiln draft, particulate Fouling of duct, cyclone, Soils, brominated
distribution wet electrostatic emissions excess oxygen SCC, process water system, sludge, vermiculite.
precipitation (WEP), control, temperature and instruments.
instrumentation. control.
H:Cl ratio of _____ Incinerators ability to As H:Cl ratio decreases, C2Cl6C6l6, C2HCl and
POHCs. thermally destroy thermal stability of POHCs similar compounds.
POHCs/PICs. increases and oxidation of
PICs is reduced. Under
oxygen starved conditions,
the tendency to form PICs
increases as the N:Cl ratio
decreases.
Any fusion Rotary kiln, cyclone, Kiln draft, temperature, Slagging of kiln, plugging of Plastic, trash,
characteristics ducts, quench elbow, excess O2 control. instruments and downstream brominated sludge.
(determined by instrumentation equipment.
chemical
characteristics,
e.g., alkalis).

6-29
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 Pyrolysis
n Wet air oxidation
n 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 oxygen-


poor 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).

n 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.

n 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.

n 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.

n 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
n 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.

n 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.

n 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 Applicable waste streams


n Stage of development
n Performance
n Residuals generated
n 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 Applicable Waste


Potential Waste Management/Treatment Alternative
Objective Type(s)

Waste minimization

Source reduction All Raw material substitution Process redesign


Product reformulation Waste segregation

Recycling Concentrated inorganic Crystallization Evaporation/distillation Solvent extraction


liquids (e.g. plating, Ion exchange Electrodialysis Thermal decomposition
etching solutions)
Dilute inorganic liquids Ion exchange Reverse osmosis Donna dialysis/coupled
(e.g. plating rinses) Electrodialysis transport
Concentrated organic Neutralization followed by recovery such as distillation, evaporation, stream
liquids (e.g. solvents with stripping, or use as a fuel.
acid/alkali)

Waste exchange Concentrated liquids Recycling Reuse in process with Mutual neutralization
lower raw material
specifications
Dilute organic liquids Mutual neutralization

Pretreatment Liquid with solids Screening Sedimentation Filtration


Distillation Flotation Setting
Centrifugation Equalization
Liquid-two-phase Decanting Flotation Centrifugation
Extraction Distillation Equalization
Liquid or sludge with Cyanide destruction
cyanide through chlorination
Liquid or sludge with Chromium reduction
hexavalent chromium
Sludge Vacuum filtration Filter press Centrifugation
Other dewatering
Bulky solids Shredders Hammermills Crushers

Neutralization Acidic waste Limestone Lime Caustic soda


Alkaline waste Sulfuric acid Hydrochloric acid Carbonic acid (CO2)
All Mutual neutralization

Treatment and disposal Metal-containing liquid Precipitation and


clarification
Trace organic-containing Adsorption
liquids
Dilute organic-containing Biological treatment Chemical oxidation Ozonation
liquid Air stripping Incineration
Concentrated organic Distillation Steam stripping Evaporation
liquid Extraction Supercritical fluids Wet air oxidation
Incineration Use as a fuel
Inorganic sludges and Solidification Encapsulation Landfill
solids
Organic sludges and solids Incineration Wet air oxidation

6-34
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. Summary of recovery/reuse technologies for corrosive wastes (Wilk et al., 1988)

Applicable Waste Stage of Residuals


Process Performance Cost
Streams Development Generated
Evaporation/ Metal plating Well-established Plating solution Impurities will be Can be cost-
Distillation rinses; acid for treating plating recovered for concentrated, effective for
pickling liquors rinses reuse in plating therefore, recovering
bath. Rinse water crystallization/ corrosive plating
can be reused filtration system solutions from
may be required rinse waters
Crystallization H2SO4 pickling 20 to 25 systems 97-98% recovery Ferrous sulfate Cost-effective if
liquors; currently in for H2SO4 (80- heptahydeate treating large
HNO3/HF; operation (fewer 95% metal crystals (can be quantities of waste
pickling liquors; applications for removal) traded or sold)
caustic aluminum caustic recovery)
etch solutions
99% HNO3 and Metal fluoride
50% HF crystals (can recover
recovered additional HF by
thermal
decomposition)
80% recovery Aluminum
NaOH hydroxide crystals
(can be traded or
sold)
Ion exchange 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; rack- used 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)
Electrodialysis Recovery of Units currently 85% recovery of Metals which can be Cost-effective for
chromic/sulfuric being sold, but etching solution. treated, disposed, or specific
acid etching limited area of 45% copper regenerated for applications
solutions application. 5 in removal; 30% reuse (chromic/sulfate
operation zinc removal acid etchants)

Recovery of Several in Works best when Chromic acid can be Low capital
plating rinses operation copper returned to plating investment; cost
(particularly concentrations are bath; rinse water effective for
chromic acid rinse in the 2 to 4 oz/gal can be reused specific

6-37
Applicable Waste Stage of Residuals
Process Performance Cost
Streams Development Generated
waster) usage application
(chromic acid
rinses)
Recovery of Marketed, none in 3 M HF/HNO3 2M KOH Soln Cost-effective for
HNO3/HF pickling operation to date recorded which can be large quantity
liquors recycled back to the generator
pretreatment step
for this ED
application
Reverse osmosis Plating rinses Corrosive waste 90% conversion Recovered plating Cost-effective for
membranes achieved with solution returned to limited
marketed by four cyanide plating plating bath (after applications.
companies. RD rinses being concentrated Development of a
module systems by an evaporator). more chemically
applicable to Rinsewater reused resistant
corrosives membrane would
available from two make it very cost-
companies effective for a
wider area of
application
Donna Plating rinses; Donnan analysis Data not available Data not available No cost data
dialysis/coupled potentially only lab-scale for Donna analysis for Donnan analysis available for
transport applicable to acid tested (further testing Donna analysis
baths required)
Coupled transport Coupled transport For chromate Average capital
lab and field has demonstrated plating rinse cost for plating
tested. Coupled 99% recovery for applications, sodium shop is $20,000.
transport system is chromate from chromate is Can be cost-
currently being plating rinses. generated: can be effective for
marketed Other plating used elsewhere in specific
rinses should be plant or subjected to applications
applicable, but not ion exchange to
fully tested recover chromic
acid for recycle to
plating solution
Solvent HNO3/HF pickling Commercial-scale 95% recovery of Metal sludge (95% Not available
extraction liquors systems installed HNO3; 70% iron can be
for development recovery of HF recovered by
purposes in thermal
Europe and Japan. decomposition)
No commercial-
scale installations
in U.S.
Thermal Acid wastes Well-established 99% regeneration 98-99% purity iron Expensive capital
decomposition for recovering efficiency for oxide which can be investment. Only
spent pickle pickling liquors reused, traded, or cost-effective for
liquors generated marketed large quantity
by steel industry. waste acid
Pilot-scale stage generators
for organic wastes
(1) RFIEL Reverse flow ion exchange
6.4.3 Solvent Wastes

6-38
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
Applicable waste
management Potential waste management alternative
type(s)
objective
Waste All Raw material Process redesign
Minimization substitution Waste segregation
Product
reformulation
Recycling All Reclamation Reuse (e.g., as a fuel or process solvent)

Pretreatment
Liquid with solids Screening Sedimentation Filtration Distillation
Floatation Settling Centrifugation
Liquid Two Phase Decanting Floatation Centrifugation Extraction
Distillation
Sludge Vacuum filtration Filter press Centrifugation Other
dewatering
Bulky solids Shredders Hammermills Crushers
Low Btu/High Blending
Viscosity
Treatment
Physical Liquid Distillation Evaporation Fractionation Extraction
Steam stripping Air stripping Carbon Resin
adsorption adsorption
Chemical Liquid Wet air oxidation Supercritical water oxidation Ozonation
Other chemical Chlorinolysis
oxidations
Biological Liquid Activated sludge Aerated lagoon Trickling
filter
Incineration All Liquid inyection Rotary kiln Fluidized- Starved air
bed
Other All Pyrolysis Molten glass Circulating
thermal processes Electric reactor fluid bed
Plasma systems Molten salt
Post-treatment
Organic liquid Decanting Dehydrating Fractionatio Thermal
n destruction
Solid/sludge Solidification Encapsulation Thermal
destruction
Aqueous Liquid Carbon adsorption Resin adsorption Air stripping Biological
Ozonation Other oxidations Treatment

6-40
Table 6-8. Summary of solvent treatment processes (Breton et al., 1987)

Applicable waste
Process Stage of development Performance Residuals generated
streams
Incineration
Liquid injection All pumpable liquids Estimated that over 219 Excellent destruction TSP, possibly some PICs and
incineration provided wastes can be units are in use. Most efficiency (>99.99%). HCl if halogenated organics
blended to Btu level of widely used Blending can avoid are fired. Only minor ash if
6500 Btu/lb. Some solids incineration technology problems associated with solids removed in
removal may be residuals, e.g., HCl pretreatment processes
necessary to avoid
plugging nozzles
Rotary kiln incineration All wastes provided Btu Over 40 units in Excellent destruction Requires APCDs. Residuals
level is maintained service; most versatile efficiency (>99.99%) should be acceptable if
for waste destruction charged properly
Fluidized bed incineration Liquids or nonbulky solids Nine units reportedly in Excellent destruction As above
operation-recirculating efficiency (>99.99%)
bed units under
development
Fixed/multiple hearths Can handle a wide variety Approximately 70 units Performance may be As above
of wastes in use. Old technology marginal for hazardous
for municipal waste wastes, particularly
combustion halogenated wastes
Use as a Fuel
Industrial kilns Generally all wastes, but Only a few units now Usually excellent Requires APCDs. Residuals
Btu level, chlorine burning hazardous destruction efficiency should be acceptable
content, and other waste (>99.99%) because of long
impurity content may residence times and high
require blending to temperatures
control charge
characteristics and
product quality
High temperature All pumpable fluids, but Several units in use Most units tested have Waste must be blended to
industrial boilers should blend halogenated demonstrated high DRE meet emission standards for
organics. Solids removal (>99.99%) TSP and HCl unless boilers
particularly important to equipped with APCDs
ensure stable burner
operation
ther Thermal Technologies
Circulating bed combustor Liquids or nonbulky solids Only one U.S. Manufacturer reports high Bed material additives can
manufacturer. No units efficiencies (>99.99%) reduce HCl emissions.
treating hazardous Residuals should be
waste acceptable
Molten glass incineration Almost all wastes, Technology developed No performance data Will need APC device for
provided moisture and for glass available, but DREs should HCl and possibly PICs; solid
metal impurity levels are manufacturing. Not be high (>99.99%) retained (encapsulated) in
within limitations available yet as a molten glass
hazardous waste unit
Molten salt destruction Not suitable for high Technology under Very high destruction Needs some APC devices to
(>20%) ash content development since efficiencies for organics (six collect material not retained in
wastes 1969, but further nines for PCBs) salt. Ash disposal may be a
development on hold problem
Furnace pyrolysis units Most designs suitable for One pyrolysis unit Very high destruction TSP emissions lowers than
all wastes RCRA permitted. efficiencies possible those from conventional will
Certain designs (>99.99%). Possibility of need APC devices for HCl
available commercially PIC formation

6-41
Applicable waste
Process Stage of development Performance Residuals generated
streams
Plasma arc pyrolysis Present design suitable Commercial design Efficiencies exceeded six Requires APC devices for
only for liquids appears imminent, with nines in tests with solvents HCP and TSP, needs flare for
future modifications H2 and CO destruction
planned for treatment of
sludges or solids
Fluid wall advanced Suitable for all wastes if Ready for commercial Efficiencies have exceeded Requires APC devices for
electric reactor solids pretreated to ensure development. Test unit six nines in tests with HCP and TSP, needs flare for
free flow permitted under RCRA solvents H2 and CO destruction
In situ vitrification Technique for treating Not commercial, No date available, but Off gas system needed to
contaminated soils, could further work planned DREs of over six nines control emissions to air. Ash
possibly be extended to reported contained in vitrified soil
slurries. Also use as
solidification process
Physical Treatment Methods
Distillation This is a process used to Technology well Separation depends upon Bottoms will usually contain
recover and separate developed and reflux (99 + percent levels of solvent in excess of
solvents. Fractional equipment available achievable). This is a 1,000 ppm; condensate may
distillation will required from many suppliers; recovery process require further treatment
solids removal to avoid widely practiced
plugging columns technology
Evaporation Agitated thin film units Technology is well This is a solvent recovery Bottoms will contain
can tolerate higher levels developed and process. Typical recovery appreciable solvent. Generally
of solids and higher equipment is available of 60 to 70 percent suitable for incineration
viscosities than other from several suppliers;
types of stills widely practiced
technology
Stream Stripping A simple distillation Technology well Not generally considered a Aqueous treated stream will
process to remove volatile developed and final treatment, but can probably require polishing.
organics from aqueous available. achieve low residual solvent Further concentration of
solutions. Preferred for levels overhead steam generally
low concentrations and required
solvents with low
solubilities
Air Stripping Generally used to treat Technology well Not generally considered a Air emissions may require
low concentration aqueous developed and available final treatment, but may be treatment
streams effective for highly volatile
wastes
Liquid-liquid extraction Generally suitable only Technology well Can achieve high efficiency Solvent solubility in aqueous
for liquids of low solid developed for industrial separations for certain phase should be monitored
content processing solvents/waste combinations
Carbon adsorption Suitable for low solid, Technology well Can achieve low levels of Adsorbate must be processed
low concentration aqueous developed; used as residual solvent in effluent. during regeneration. Spent
waste streams polishing treatment carbon and wastewater may
also need treatment.
Resin Adsorption Suitable for low solid Technology well Can achieve low levels of Adsorbate must be processed
waste streams. Consider developed in industry residual solvent in effluent. during regeneration.
for recovery of valuable for special resin/solvent
solvent combinations.
Applicability to waste
streams not
demonstrated

6-42
Applicable waste
Process Stage of development Performance Residuals generated
streams
Chemical Treatment Processes
Wet air oxidation Suitable for aqueous High Pretreatment for biological Some residues likely which
liquids, also possible fortemperature/pressure treatment. Some compounds need further treatment
slurries. Solvent technology, widely used resist oxidation
concentrations up to 15% as pretreatment for
municipal sludges, only
one manufacturer
Supercritical water For liquids and slurries Supercritical conditions Supercritical conditions Residuals not likely to be a
oxidation containing optimal may impose demands achieve high destruction problem. Halogens can be
concentrations of about on system reliability. efficiencies (>99.99%) for neutralized in process
10% solvent Commercially available all constituents
in 1987
Ozonation Oxidation with ozone Now used as a Not likely to achieve Residual contamination likely;
(possibly assisted by [UV] polishing step for residual solvent levels in the will require additional
suitable for low solid, wastewaters low ppm range for most processing of off gases
dilute aqueous solutions wastes
Other chemical oxidation Oxidizing agents may be Oxidation technology Not likely to achieve Residual contamination likely;
processes highly reactive for well developed for residual solvent levels in the will require additional
specific constituents in cyanides and other low ppm range for most processing
aqueous solution species (phenols), not wastes
yet established for
general utility
Chlorinolysis Suitable for any liquid Process produces a Not available Air and wastewater emissions
chlorinated wastes product (e.g., carbon were estimated as not
tetrachloride). Not significant
likely to be available
Dechlorination Dry soils and solids Not fully developed Destruction efficiency of Residual contamination seems
over 99% reported for likely
dioxin
Biological Treatment Aerobic technology Conventional treatments May be used as final Residual contamination likely;
Methods suitable for dilute wastes have been used for treatment for specific will usually require additional
although some years wastes, may be processing
constituents will be pretreatment for resistant
resistant species

6-43
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 5
Emulsion breaking Most oils subcategory facilities
Equalization 81 (36 unstirred, 45 stirred or aerated)
Physical (Phase Separation)
Air stripping 1
Granular media filtration 10 sand filters, 9 multimedia filters
Carbon adsorption 11
Reverse osmosis 3
Ultrafiltration 3
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 3
Ion exchange 1
Biological
Sequencing batch reactors 1
Biotowers 2
Activated sludge 12
Sludge Dewatering
Plate and frame pressure filtration 34
Belt pressure filtration 6
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
Air Concentrated Spent
Treatment process Sludges
emissions liquid waste stream carbon
Pretreatment operations
Sedimentation X
Granular media filtration X
Oil/water separation X
Physical/chemical treatment operations
Neutralization X
Precipitation flocculation/sedimentation X
Oxidation/reduction X
Carbon adsorption X X
Air stripping X
Steam stripping X
Reverse osmosis X
Ultrafiltration X
Ion exchange X
Wet-air oxidation X
Biological treatment operations
Activated sludge X X
Sequencing batch reactor X X
Powdered activated carbon treatment (PACT) X X
Rotating biological contactor X X
Trickling filter 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 TREATMENT
PRIMARY
SLUDGE * Compost
* Source thickening in the * Incineration
primary clarifier * Drying
* Gravity

STABILIZATION CONDITIONING DEWATERING ULTIMATE


DISPOSAL
* Anaerobic digestion * Ferric chloride * Solid-bowl centrifuge * Land spread
* Aerobic digestion * Lime * Belt filter-press * Landfill
* Wet air oxidation * Lime and ferric * Vacuum filter * Land injection
* Anaerobic -aerobic chloride * Filter press
digestion * Polymer * Drying beds
THICKENING * Chlorine oxidation * Heat treatment * Sludge lagoons
* Lime stabilization * Elutriation * Gravity/low pressure
SECONDARY * Freeze-thaw devices
SLUDGE
* 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 Effect on use/disposal options


Pretreatment: Reduction in Reduces levels of heavy metals and Increases the viability of land
contaminant levels in industrial organics in industrial wastewater application, distribution and marketing,
wastewater discharge discharge, thereby lowering the and ocean disposal. Reduces need for
concentration of these constituents in pollution control devices during
the sludge incineration, and prevents problems
with incinerator ash disposal
Thickening: Low-force separation of Increases solids concentration of sludge Lowers sludge transportation costs for
water and solids by gravity or flotation by removing water, thereby lowering all options
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
involving the biological stabilization of all pathogens. Degrades sludge to a distribution and marketing. Often not
sludge in a windrow, in an aerated humus-like material. Increases sludge appropriate for other use or disposal
static pile, or in a vessel mass due to addition of bulking agent options due to cost
Heat drying: Application of heat to Disinfects sludge. Slightly lowers Generally used only prior to
kill pathogens and eliminate most of potential for odors and biological distribution and marketing
the water content activity

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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 Plate and frame pressure filtration


n Vacuum filtration
n 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.

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Table 6-16. Operational Selection Criteria for Sludge Dewatering Processes (U.S. EPA,
1987)

Plant Size Key Criteria


Small Minimum Mechanical Complexity
< 0.08 m3/s Local Repairs and Parts
(< 2 mgd) Minimum operator attendance
Reliable without skilled service
Unaffected by climatic factors
Large excess capacity
Handleable cake
Medium Low operator attendance
0.08 0.44 m3/s Local repair and parts
(2 10 mgd) Transportable cake without nuisance
Mechanical reliability
Competitive O&M costs
Drier cake
Large Lowest O&M costs/ton dry solids
> 0.44 m3 /s 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

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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.

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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.

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Table 6-17. Pollution limit for land application of sludge

Description (*)
Maximum concentration Pollutant accumulation Permissible Annual pollutant
Pollutant limit (**) rate concentration limit (***) accumulation rate
(mg/kg) (kg/ha) (mg/kg) (kg/ha/year)
Arsenic 75 41 41 2.0
Cadmium 85 39 39 1.9
Chrome 3000 3000 1200 150
Copper 4300 1500 1500 75
Lead 840 300 300 15
Mercury 57 17 17 0.85
Molibdene 75 18 18 0.90
Nickel 420 420 420 21
Selenium 100 100 36 5.0
Zinc 7500 2800 2800 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).

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Figure 6-15. Importance factors affecting sludge use/disposal options: (a) sludge
constituents, (b) sludge characteristics, and (c) cost factors

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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 Foundations
n Dikes
n Liner Systems
- Low-permeability soil liners
- Flexible membrane liners (FMLs)
- Leachate collection systems
n Final cover systems

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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 low-
permeability 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.

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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)

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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 Low-permeability soil liners


n Flexible membrane liners (FML)
n 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 Low permeability to waste constituents


n Strength or mechanical compatibility of the sheeting
n Durability for the lifetime of the facility

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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 Discharge to a wastewater treatment plant


n On-site treatment followed by discharge
n 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

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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

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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.

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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.

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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/625/1-79-
011 (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.

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U.S. EPA. 1987. Dewatering Municipal Wastewater Sludges (Design Manual). EPA/625/1-
87/014. 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/R-
93/017 (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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