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Treatment of Solid Waste

Note: The source of the technical material in this volume is the Professional Engineering Development Program (PEDP) of Engineering Services. Warning: The material contained in this document was developed for Saudi Aramco and is intended for the exclusive use of Saudi Aramcos employees. Any material contained in this document which is not already in the public domain may not be copied, reproduced, sold, given, or disclosed to third parties, or otherwise used in whole, or in part, without the written permission of the Vice President, Engineering Services, Saudi Aramco.

Chapter : Environmental File Reference: ENV10202

For additional information on this subject, contact K. Hibrawi on 873-0211

Engineering Encyclopedia

Environmental Treatment of Solid Waste

CONTENTS

PAGES

METHODS OF PHYSICAL TREATMENT OF SOLID WASTE......................... 1 Manual Separation....................................................................................... 6 Mechanical Separation ................................................................................ 6 Density............................................................................................. 7 Optical............................................................................................ 10 Magnetic ........................................................................................ 10 Screening................................................................................................... 11 Vibratory Screens .......................................................................... 11 Rotary Screen................................................................................. 12 Disc Screen .................................................................................... 12 Shredding .................................................................................................. 12 Mills............................................................................................... 13 Shears............................................................................................. 13 Grinding .................................................................................................... 15 Tubs ............................................................................................... 15 Mills............................................................................................... 16 Baling ........................................................................................................ 16 Example Problem 1. Volume reduction by materials separation and recovery of recyclables...................................... 17 Filtration .................................................................................................... 19 Filter beds ...................................................................................... 19 Drums ............................................................................................ 19 Presses............................................................................................ 20 Flocculation ............................................................................................... 21 Precipitation............................................................................................... 21 Flotation .................................................................................................... 22

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Evaporation ............................................................................................... 22 Ponds ............................................................................................. 22 Drying Beds ................................................................................... 23 METHODS OF CHEMICAL TREATMENT OF SOLID WASTE...................... 27 Oxidation ................................................................................................... 28 Reduction .................................................................................................. 29 Neutralization ............................................................................................ 29 Calcination................................................................................................. 31 Ion Exchange............................................................................................. 31 Other Chemical Methods........................................................................... 32 LANDFARMING AND COMPOSTING AS SOLID WASTE TREATMENT METHODS .................................................................................. 34 THERMAL DESTRUCTION METHODS OF SOLID WASTE TREATMENT. 41 Incineration................................................................................................ 41 Pyrolysis .................................................................................................... 58 Emerging Technologies............................................................................. 58 Microwaving.................................................................................. 58 Plasma Arc..................................................................................... 59 SOLIDIFICATION AND STABILIZATION AS SOLID WASTE TREATMENT METHODS .................................................................................. 60 Cement-Based ........................................................................................... 61 Thermoplastic-Based................................................................................. 63 Silicate-based............................................................................................. 65 Vitrification ............................................................................................... 66 GLOSSARY ......................................................................................................... 68 REFERENCES...................................................................................................... 69

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METHODS OF PHYSICAL TREATMENT OF SOLID WASTE The primary purpose of physical treatment methods is to reduce the total quantity of solid waste that requires disposal. This reduction in weight and/or volume can be accomplished by one, or a combination of the following methods: Manual separation Mechanical separation Screening Shredding Grinding Baling Filtration Flocculation Precipitation Flotation Evaporation

Source separation in many cases will result in less overall processing of waste and in the recovery of a higher quality product. Removing materials such as glass from the source stream will reduce incinerator maintenance problems. The high thermal temperatures of incinerators can actually melt glass. The molten glass then causes airflow through the incinerator to decrease; this reduced airflow adversely affects combustion. Figures 1 through 4 illustrate possible flow diagrams for the separation and recovery of selected materials from commingled and source-separated municipal solid waste. All these systems use a variety of the physical methods listed above. All the designs would be improved by the addition of weighing scales throughout the process. It is essential to know what materials are entering the plant and also to know the recovery efficiencies for the sorting processes.

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Commingled MSW Collection vehicle Receiving area Front-end loader used to spread waste for presorting Front-end loader, floor and inclined conveyor system Second-stage manual presorting Inclined conveyor Bag breaker Conveyor First stage manual sorting Conveyor Screening (trommel or disc) Conveyor Paper Cardboard Plastics Glass Aluminum cans Tin cans Conveyer Oversized material Conveyor Magnetic separation Conveyor Truck Shredding Ferrous metals Bagged commingled recyclable materials Paper Plastics Glass Aluminum cans Tin cans Cardboard Source-separated materials in see-through bags Bulky items White goods Other contaminants Cardboard Other large items Collection vehicle Source-separated materials

First-stage manual presorting

Second stage manual sorting

Landfill

Combustion

Compost for intermediate landfill cover

Flow diagram for the separation and recovery of selected materials from commingled municipal solid waste Figure 1

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Mixed paper Collection vehicle Receiving area Front-end loader used to spread waste for presorting Manual sorting Front-end loader, floor, inclined, and picking conveyor Manual sorting Conveyor leading to baler Baling Forklift Storage of bales Forklift Shipping Paper

Bulky items Cardboard Contaminants

Cardboard

Flow diagram for the separation and recovery of source-separated waste: and cardboard Figure 2

mixed paper

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Commingled plastic and glass Collection vehicle Receiving hopper Conveyor Manual sorting Conveyor Manual sorting Conveyor Vibrating screen Mixed glass conveyor Glass crusher Forklift Glass crusher Forklift Shipping Residual materials to landfill Clear glass crushed for storage Plastics separated according to type

Flow diagram for the separation and recovery of source separated waste: commingled glass and plastic Figure 3

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Commingled aluminum and tin cans Collection vehicle Receiving hopper

Conveyor Overhead magnetic Tin cans, baled or crushed

Conveyor Pulley magnet Tin cans, baled or crushed

Aluminum cans Baler or can crusher Forklift or pneumatic conveyor Storage of baled or crushed cans Forklift Shipping

Flow diagram for the separation and recovery of source-separated waste: aluminum and steel (tin) cans Figure 4

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Manual Separation Manual separation of solid waste can either be accomplished at the source (for example, at the home) or at a central collection station. "Curbside collection" at the home has the primary advantage of eliminating the resident's need to drive to a central collection point. Some cities provide multiple containers for the homeowner to sort the waste by types, such as glass, plastic, paper and wet garbage. This separation process minimizes the labor of the sanitation employees, but waste generators may not like the extra sorting effort. A second method of curbside recycling is for the city to provide only a single recyclable waste container. The homeowner bags wet garbage, or other materials the city cannot recycle, separately. The waste collector performs the sorting of the recyclables at the time of the pickup. The frequency of waste collection will help to determine if sanitation workers will agree to this method of collection. A once-per-week collection frequency makes hand sorting of garbage an undesirable activity. Concern for the possibility of transmitting communicable disease is another negative for handsorting. Manual separation can be undertaken at a central collection point called a Materials Recovery Facility (MRF). Waste generators can bring the waste to the MRF and do most of the sorting by placing the material in separately marked bins. Another method is to have the sanitation workers do the sorting at the MRF. The Rolla, Missouri MRF uses a combination of these methods. Wastes at the Rolla MRF are placed in separate bins by the waste generators. Bins are available for paper, plastic milk jugs, other plastics, glass (by color), aluminum and other metals. Sanitation workers then ensure the sort has been done correctly, remove colored milk caps (that can't be locally recycled) and prepare the sorted wastes for further processing steps. If the bulk of the waste separation is performed by the sanitation workers, the MRF will often have a conveyor belt system that brings the unsorted waste past a worker, who then removes the recyclable materials as the waste passes the worker's station. These conveyor systems haven't changed in concept since the turn of the century. The worker's protective equipment has increased, and the conveyor facilities are now mostly air conditioned for worker comfort and odor/pest control. Mechanical Separation Materials can be sorted by their physical properties: density (to sort light and heavy fractions); optical clarity ( to sort glass or plastic by color); and electrostatic charge/magnetic permeability (to separate ferrous and non-ferrous metals).

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Density Density separation can divide wastes into light fractions (such as paper, plastics and organics) and heavy fraction (such as metals, wood and other heavy inorganic materials). Air classification is the most popular of the methods, but devices called stoners and heavy media separators are also used. A technology that is called "flotation" will be discussed in another section. In an air classifier, as shown in Figure 5, refuse enters the upper part of a chamber with air blowing into the chamber from below. If the upward air velocity is high enough to overcome the force of gravity on the particle, the particle will rise; small, heavy particles will fall to the bottom of the chamber. Components suspended in the air stream are called "air classified light fraction." Materials that settle out of the air stream are called "air classified heavy fraction." Paper and plastics will concentrate in the light fraction, causing the light fraction to have a higher heating value than the heavy fraction. Unfortunately, air classifiers are sensitive to drag forces on the irregularly shaped particles. Spherical particles are collected at different efficiencies than are flat particles of the same weight and density. The more uniform the feed waste is the more consistent will be the collection efficiency. Air classifiers are also sensitive to moisture content, which is absorbed differently by various waste materials. Wet paper tends to stick together and will attract dirt . The larger, relatively light paper fraction will carry into the light fraction with its load of dirt. Shattered glass from a hammer mill can become imbedded in the paper and carry into the light fraction. A variation of the air classifier is called the air knife (shown in Figure 6). The device works well with a waste stream that has already undergone some separation. The air current carries paper and plastic with the air, while heavier materials fall more directly. Another density classifying variation, known as a stoner, is shown in Figure 7. Air blows through a porous deck and separates the material by differences in terminal velocity. Stoners work well over a relatively narrow size range. So-called heavy media separators have found popularity in the automobile recovery industry. A pre-shredded feedstock with a high aluminum percentage is placed in a liquid with a high specific gravity. The aluminum floats on the liquid, and the higher density materials settle or remain below the surface.

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Light fraction

Shredded refuse

Ajustable baffle

Ajustable baffle

Heavy fraction

Schematic of the air classification concept Figure 5

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Air Knife

Plenum

Refuse

Air from fan

Light material

Heavy material

Schematic of an air knife Figure 6


Light and heavy materials to be separated Heavy material that sinks to the bottom of stratified bed is conveyed upslope by the deck's vibration

Light material that is suspended and stratified floats downslope

Discharge of light material Uniform supply of fluidizing air applied below porous deck Porous deck sloped (about 4o) and vibrated in a straight line reciprocating motion

Discharge of heavy material

Schematic of a stoner Figure 7

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Optical Optical separation was popular in the 1970s and 1980s, but has fallen out of favor and is rarely mentioned in current texts. The optical sensors were intended to sort glass by color, but the sensors proved unreliable because the glass was frequently dirty or because the labels on the glass interfered with the device that measured the optical properties. An optical sorter might prove useful on a waste stream that was already presorted as glass and had been precleaned before the sorter. Magnetic Magnetic systems are used to separate ferrous and non-ferrous materials. In the three- magnet system shown in Figure 8, the pickup magnet lifts ferrous material from the shredder belt; then the transfer magnet brings the material around the curve of the belt and agitates the material. The "no magnet" space before the discharge magnet is critical: as the material falls from the belt, non-ferrous material that is caught behind the magnetic material is released. The third magnet lifts the ferrous material back to the belt where it is discharged to the next step in the process.

Continuous belt Discharge magnet Pickup magnet Transfer magnet Ferrous material Solid wastes from shredder Nonferrous materials

Typical magnetic separation system Figure 8

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Screening Many components in the waste stream have a characteristic size. Therefore, it is possible to sort waste by size to achieve a series of waste streams with a higher percentage of certain components. However, sorting by screening can never be 100% effective because of the overlap in component sizing. Placing a screening mechanism before a shredder will reduce loads on the shredder by removing small particles first. Various screening devices have been developed, including vibratory screens, rotary screens and disc screens. Vibratory Screens Vibratory screens are excellent at separating relatively dry materials such as glass and metals. A typical vibrating screen is shown in Figure 9.

Typical vibrating screen used for size separating commingled waste Figure 9

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Rotary Screen The rotary drum, or Trommel screen, is useful for protecting shredders in refuse derived fuel (RDF) plants from oversized material. The large-diameter (8 to 10 feet ) perforated drum rotates and sizes the waste stream as the waste passes through the drum center. (See Figure 10.)

Rotation Shredded refuse Angle of inclination

-1/2 in.

+1/2 to -4 in.

+4 in.

Schematic of a rotary drum screen Figure 10

Disc Screen The disc screen (shown in Figure 11) is made up of a rotating shaft containing a number of discs. Particles float down the length of the rotating disc/shaft system. Particles will likely orient with the largest dimensions horizontal (it's hard to stand a coin on edge, for example), so smaller particles pass down through the discs. The systems work well for cans and bottles, but rather poorly for mixed flows of plastics, paper, and textiles. Shredding The size distribution of raw refuse is shown in Figure 12. It was noted in the discussion of screening methods that the overlapping of sizes complicates the screening process. Shredding, often preceded by screening, is a common method of making the waste size more uniform. Both a variety of mills and shears can be used to shred waste.

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Mills Mills are of several types: flail mills, vertical shaft hammer mills, and horizontal shaft hammer mills. The vertical shaft hammer mill (Figure 13) is the most successful at achieving size reduction, but at the cost of high maintenance and energy consumption. The steel hammers that are pinned to the central shaft beat the waste to smaller and smaller sizes. Shears The shear shredder is made up of two parallel counterrotating shafts with a series of discs mounted perpendicularly that serve as cutters. Waste material is reduced in size by the shearing or tearing action of the cutter discs.

Large fraction

Small fraction

Schematic of a disc screen Figure 11

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Newsprint

100

90

Cardboard 80

70 Paper 60

Percent composition

Garbage 50

Yard and garden waste

40

Metal

30

Glaass

20

Plastic 10 Miscellaneous organics Inerts 0 4 8 12 16 20

Typical component size (in.)

Typical size distribution of raw refuse Figure 12

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Drive motor

Infeed

Ballastic ejection

Neck section

Discharge

Schematic of a vertical shaft hammer mill Figure 13 Grinding Grinders are actually another form of the shredders that were discussed in the preceding section. Some varieties are tub grinders and mills. Tubs A tub grinder resembles a large diameter wash tub on wheels. It is a variety of mobile, hammermill shredder. The tub grinder is often used for yard wastes, pruning and construction debris. The waste is fed into the top of the tub, and then falls into a horizontal hammermill. The grinders are often diesel-powered and may even have their own attached crane for loading material in the tub.

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Mills A grinding mill operates much the same as a shredding mill but has a lower power input and uses time and multiple passes to do the work rather than brute force. Baling Baling is used at recycling centers to reduce the volume of waste. This volume reduction eases storage requirements and cuts transportation costs. Some new equipment can produce usable commercial products (such as fireplace logs) directly from waste cardboard and paper. Balers are an alternative to compactors and operate at 100-200 pounds per square inch pressure to produce compact bales of solid waste or recovered materials. Bale weight is in the range of 500 to 800 kg. Cardboard and Paper Since up to 50% of municipal solid waste (MSW) is paper, significant reductions in landfill volume can be obtained through cardboard and paper recycling. Larger department stores and grocery stores often have their own cardboard balers. The baler compresses the waste paper and automatically bands the material together with wire to ease transport methods. A forklift and pallet system is normally used for transport within the facility. A baler used for paper and cardboard is shown in Figure 14. Aluminum Cans Aluminum is one of the easiest and cost effective materials to recycle. The cans are sometimes baled, using the same baling equipment that is used for cardboard. They can also be crushed and blown into trailers for shipping. Single can crushers are available for home and office use to reduce waste volume at the source.

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Baler used for paper, cardboard and cans Figure 14

The following example problem illustrates the effectiveness of recycling in extending landfill life. Example Problem 1. Volume reduction by materials separation and recovery of recyclables. A community with a population of 40,000 has a per-capita solid-waste disposal rate of 7 pounds per day (as collected). The distribution of components and nominal density and compaction factors are for a typical landfill disposal. Determine the annual landfill area requirements without any materials recovery and with a recovery of 75% of the glass and paper and 80% of the metals and cardboard. By what factor could such recovery extend the useful life of the landfill?

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Solution: Computation table. *Given or measured values.


As collected (no recovery) Component % by wt. * Food Waste Paper Cardboard Plastics Glass Ferrous Metal Tin Cans Aluminum Miscellaneous 12 44 5 4 10 5 5 4 11 100% lb. 1000 lb. * 120 440 50 40 100 30 50 40 110 1000 lb. density, lb./ft.3 * 18 5 3 4 12 20 6 4 10 volume, ft.3 per 1000 lb. 6.7 88.0 16.7 10.0 8.3 2.5 8.3 10.0 11.0 161.5 ft.3 normal comp. factor * 0.35 0.20 0.25 0.15 0.60 0.35 0.18 0.18 0.25 fill volume, ft.3 2.3 17.6 4.2 1.5 5.0 0.9 1.5 1.8 2.8 37.6 ft.3 wt. for disposal, lb. 120 110 10 40 25 10 10 8 110 443 lb. Collected with recovery density, lb./ ft.3 * 18 5 3 4 12 20 6 4 10 disposed volume, ft.3 6.7 22.0 3.3 10.0 2.1 0.5 1.7 2.0 11.0 59.3 ft.3 normal comp. factor * 0.35 0.20 0.25 0.15 0.50 0.35 0.18 0.18 0.25 fill volume, ft.3 2.3 4.4 0.8 1.5 1.3 0.2 0.3 0.4 2.8 14.0 ft.3

(27 ft.3 / yd.3 ) 3 = 718 lb./ yd. 37.6 ft.3 (27 ft.3 / yd.3 ) 3 D with recovery = 443 lb. = 854.4 lb./ yd. 14.0 ft.3 Calculation of approximate annual landfill area without recovery: Average weight of daily waste collected = (40,000 persons)(7 lb./day/p.) = 280,000 lb./d. 280,000lb. / d. Daily fill volumerequired = = 390 yd.3 / d. 718lb. /yd.3 Assume a landfill cell cross-section of 2 yd. depth by 8 yd. wide = 16 yd. 2 390 yd.3 Daily cell length = = 24.375 yd. length or 73.1 ft. + .5 ft. face cover = 73.6 ft. 16 yd.2 Daily area = (73.6 ft.)(24.0 ft. + 2.0 ft. partition wall between trenches) = 1913.6 ft. 2/d. Annual area = (1913.6 ft.2/d.)(365 d./yr.) = 698,464 ft.2/yr. 698,464ft.2 / yr. or = 16.03 acres/ yr. 43, 560ft.2 / ac. The change in area (fill life) with material recovery is proportional to the volume change: 37.6 ft.3 = 2.69 or withmaterialrecovery thelandfill life can be extendedby a factor 14.0 ft.3 of about 2.7 D without recovery = 1000 lb.

Calculation of solid waste density:

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Filtration The physical treatment methods that have been discussed so far are meant primarily for relatively dry materials. For high liquid content wastes, it is appropriate to use: filtration, flocculation, precipitation, flotation and evaporation/drying beds. These methods are all meant to concentrate or separate solids from the liquid wastes. Filtration is the physical process of retardation, resulting from the clogging of pore spaces in the filter media. This clogging occurs when solid particles are trapped in the pores. Filtration also occurs due to precipitation and accumulation of dissolved matter. There are three common filtration methods: filter beds, drums and presses. Filter beds Sand filter beds were first used in water treatment plants, but the technology has found its way into wastewater treatment as a final "polishing" of sewage effluent. Beds are now made of sand, coal, dual media (sand plus coal), or mixed media (sand, coal and granite). A filter can reduce suspended solids in wastewater from 25 mg/L to 10 mg/L. If the solids concentration is much higher than 25 mg/L, it is better to remove the solids with treatment such as rapid mix-flocculation-sedimentation than it is with sand. If the sand pores load up too quickly, the drop in pressure across the filter becomes excessive. A sand filter cross section is shown in Figure 15. As the contaminant is captured on the sand, the pressure drop increases, and the filter must be backwashed. The waste flow to the filter is shut off, and water is pumped upward through the filter to rinse the filter media and to wash the contaminant to a collection point. Backwashing normally lasts only a few minutes, finally the washwater is shut off, and the clean filter is returned to operation. A sand filter can also be used to capture petroleum type wastes. The finer the sand and the higher the product viscosity, the greater the product retention. Up to 20,000 parts per million (mg/L) of No. 6 diesel oil can be retained on fine sand. The filters are up to 625 square feet in area, and flow rates over the beds average 3 gallons per minute per square foot of bed area. Drums Drum, or vacuum, filters are often used to dewater sludges. A cylindrical drum is covered with a filter fabric. The drum rotates partially submerged in a vat of conditioned sludge. A vacuum is applied to the inside of the drum through the porous filter media. This vacuum draws the water into the drum, leaving the dewatered filter cake on the outside of the drum. A blade scrapes the drying filter cake from the rotating drum, and the cycle starts over.

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Inlet Main

Wash Troughs

Wash Water Outlet

Graded Filter Sand

Outlet Main

Perfirated Laterals

Graded Gravel

Typical cross section of a rapid sand filter Figure 15

Presses A continuous belt filter press(CBFP) operates on the shear and compressive forces introduced in the sludge cake when the cake is pressed between two moving belts, as shown in Figure 16.

Chemical Conditional Stage Polyelectrolite Solution

Gravity Drainage Stage

Compression Dewatering Stage

Sludge

Mixer

Conditioned Sludge Wash Spray Filtrate Sludge Cake Washwater

Continuous belt filter press Figure 16


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Flocculation Heavy metals removal from wastewater can be greatly increased by the addition of various water-soluble chemicals and polymers in the dual process of coagulation and flocculation. The two processes are used when normal settling rates of suspended particles are too slow for effective clarification. Coagulation is the addition and rapid mixing of a coagulant to neutralize charges and to collapse the colloidal particles . This chemical addition and mixing causes agglomeration and settling of the particles. Rapid mixing destroys the stability of the colloidal system. For agglomeration to occur, the particles must collide; mixing helps that occur. Rapid mix times of 30 seconds to 5 minutes are typical for the 8 cubic meter (maximum size) mixing basins. Flocculation is the agglomeration of colloidal particles that have received coagulant treatment. Flocculation takes place under slower mixing conditions in a 30-minute detention time tank. Common coagulants are alum and iron salts for surface waters, and lime-soda mixes to soften "hard" groundwater. Organic polymers, called polyelectrolytes, are often more effective than these natural materials, at least for surface water treatment. There is no substitute for laboratory jar testing to find the best combination of treatments for a particular water or waste stream. Coagulants can also be added to wastewater settling tanks to promote better removal of suspended solids. The floc settles out in a sedimentation basin. The basin is sized for a 2 to 4 hour detention time; again, this detention time depends on the treated material. The agglomerated, flocculated waste must be handled properly for disposal. If the process is designed to remove heavy metals, the waste will likely be classified as hazardous. Water and most wastewater sludges can be recycled. The high calcium content in hard water sludge makes it useful for concrete and gypsum additives. Precipitation Heavy metals are often present in liquid waste streams. Metals will precipitate at different pH levels; this precipitation results in an insoluble salt that can be removed as a sludge. Lead, for example, is soluble at acid pH, so lead in pipes is more of a problem at low pH. When an acid waste stream containing heavy metals (such as lead) is neutralized, the metals can be removed by clarification, sedimentation, or filtration. Lime is commonly used as a precipitate; sodium sulfide and sodium bisulfide can also be used, but they present some danger of hydrogen sulfide release during the precipitation process.

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Flotation Flotation works well for low-density solids and hydrocarbon solids that can be separated from liquids by air injection. Finely divided bubbles of air are injected into the liquid and attach to the particles to be "floated." The particles, with their air "life preservers," rise to the water surface and can be mechanically skimmed. Several mechanisms account for the air bubble effectiveness, including actual bubble attachment to the particles, bubble formation at the solid-liquid interface, and air entrapment in larger particles or air integration into the floc itself. Care must be taken to avoid corrosion with air injection. The biology of the well and the use of biocides are factors in flotation effectiveness. Evaporation Evaporation has been used for centuries to separate materials. Our ancestors evaporated salt water in large pans to recover the valuable salt for trade. The technology changed little over the years. Evaporation is defined as a treatment method by which wastewater is dispersed in a vaporous form. Ponds The SAES-A-104, Wastewater Reuse and Land Disposal Engineering Standard addresses two types of evaporation ponds: percolation/evaporation ponds and wastewater evaporation ponds. Percolation is a disposal method by which wastewater is allowed to pass through the soil base of the pond. A percolation pond for wastewater requires the approval of the Chief Engineer, with the concurrence from the General Manager, Exploration; Chief, Preventive Medicine Services; and Chief, Environmental Affairs. Percolation should not be used if the wastewater contains hazardous waste, because of the potential danger of groundwater contamination. If a pond is to be used for evaporation of wastewater, the SAES-A-104 Standard requires the wastewater to be of "at least primary effluent quality," and the pond to be lined to prevent percolation. Primary effluent is defined as the effluent from a process that provides removal of sewage solids so that the effluent contains not more than 500mg/L of suspended solids. The pond liner may be naturally occurring or man-made, and the coefficient of permeability for the liner system must be less than or equal to 1 x 10-8 cm/sec. Wind velocity has a strong effect on pond evaporation rates.

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Drying Beds Drying beds have been used for decades at wastewater treatment plants. The purpose of the beds is to dewater digested sewage sludge economically. The sludge is removed from the beds after drying. The sludge is then disposed of in a landfill or used as a soil conditioner in some countries. Saudi Aramco regulations prohibit sludge use for fertilizer. Drying beds are low cost and low maintenance, and provide a high solids content in the dried product. Nature does the drying work, rather than vacuum or horsepower. Four types of beds are used: conventional sand, paved, artificial media, and vacuum-assisted. A conventional sand bed is shown in Figure 17. Sand beds are useful for cities up to 20,000 persons. Larger cities should consider alternate methods because of the large space requirements for sand beds. Typical area requirements are shown in Table 1. Table 1. Typical area requirements for open sludge drying beds.
Area, Type of sludge Primary digested Primary and trickling-filter humus digested Primary and waste activated digested Primary and chemically precipitated digested
a

Sludge-loading rate,
a

ft /person

lb dry solids/ft2.yr 25-30 18-25 12-20 20-33

1.0-1.5 1.25-1.75 1.75-2.5 2.0-2.5

Corresponding area requirements for covered beds vary from about 70 to 75 percent of those for the open beds. Note: ft2 x 0.0929 = m2 lb/ft2 x 4.8828 = kg/m2 . yr

Two types of paved drying beds are in use: a drainage type and a decanting type. The former type is similar in size or larger than a conventional sand bed. Drying is encouraged by frequent agitation with mobile equipment, and the dried sludge is removed with front end loaders. There is generally less maintenance because there is no sand to be replaced periodically. The decanting bed is shown in Figure 18. The slope of the bed allows supernatant to be drawn off at the bed corners. The drying sludge is also mixed, similarly to the drainage type bed. The decanting design works well for arid, or semi-arid areas. The design requires evaporation and precipitation rates, plus pilot studies, to determine the effectiveness for a particular sludge.

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Artificial media beds have been developed to overcome some of the cost and space disadvantages of the sand and paved beds. Stainless steel wire mesh and polyurethane mesh are used with some success. The polyurethane system works well for dilute sludges, and the system produces a filtrate with low suspended solids. Vacuum drying beds use vacuum on the underside of a stationary, porous, media plate to assist gravity sludge dewatering. Dewatering proceeds over a 2-day period, which is much shorter than with conventional sand filters. Filter size advantages are balanced by the need for further post processing to obtain additional moisture reduction.

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Sand drying bed Figure 17

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Inflow pipe Drawoff pipes

(a)

30 in. minimum total bed depth Sludge Layer 12 in. typ. Slope 0.2-0.3% Sludge level

10-12 ft wide (typ) 1 2

Soil cement (b)

Paved sludge drying bed for decantation and evaporation: (a)isometric view and (b) cross section Figure 18

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Environmental Treatment of Solid Waste

METHODS OF CHEMICAL TREATMENT OF SOLID WASTE Chemical treatment of municipal solid waste usually involves a form of chemical conversion of the waste to a product, following some pre-processing. Chemical treatment is helpful in promoting resource recovery of hazardous substances. Chemical treatment can also produce useful by-products and residual effluents that are environmentally acceptable, which makes chemical treatment a better method of waste management than the traditional landfill or incinerator. Several processes are in common use: Acid hydrolysis Alkaline hydrolysis Oxidation Reduction Neutralization Calcination Ion exchange Other methods, such as dehydrohalogenation

As was discussed briefly in Module ENV 102.01, hydrolysis processes may be used to recover compounds such as glucose and furfural. The chemical process known as hydrolysis occurs when chemical substances react with waste molecules. For example, acid hydrolysis can convert cellulose into glucose. A cellulose molecule (consisting of about 3000 glucose units) is soluble in water and in many organic solvents and is poorly degradable by microorganisms. However, when the cellulose molecule is acid hydrolyzed, glucose and other sugars may be recovered. The process involves treating a suspension of small cellulose particles with a weak acid, heating the particles to between 180 and 230 C under pressure (to prevent boiling and to allow for achieving those high temperatures). The quantity of glucose that is recovered will depend on the characteristics of the waste and the process efficiency. With good process efficiency, for example, and with kraft paper as the cellulose source, approximately 80% of the weight of the kraft paper may be recovered as sugar. The recovered sugars may be converted by biological processes and other chemical processes into alcohols and other industrial chemicals. The general acid hydrolysis reaction for cellulose to glucose is:
acid (C 6H10O5 )n + H 2O nC6H12O6 cellulose glu cose

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Oxidation Chemical reduction-oxidation (redox) reactions can take place with both organic and inorganic chemicals. A redox reaction traditionally involves the gain or loss of oxygen. An oxidation reaction adds oxygen to a compound. An example of an oxidation reaction is FeSO4 changing to Fe2 (SO4)3. However, it is possible to have a redox reaction without oxygen. With organic chemicals, oxidation is defined as the loss of electrons by a chemical ( the chemical donating the electron is oxidized). For inorganic materials, oxidation is better defined as a reaction that raises the oxidation state of an atom. In the previous example, iron (Fe) went from a +2 valence to +3, so it was oxidized. Redox reactions in solid waste are mostly the result of biological activity, but some chemical redox reactions can occur between organic materials and the soil. Some researchers have found the oxidation of aromatic chemicals at soil and clay surfaces, catalyzed by adsorbed oxygen and trace metals. These reactions can particularly occur in aerated unsaturated soil. Chlorinated organics do not seem to undergo such oxidation. Thus, one would expect that it is easier to degrade aromatics than chlorinated solvents under natural aerobic conditions in clay soils. A common method of treating aqueous cyanide wastes is alkaline chlorination. The cyanide is initially oxidized to a less dangerous cyanate form and then to carbon dioxide and nitrogen in the following pair of reactions:
NaCN + Cl 2 + 2NaOH NaCNO + 2NaCl + H2 O

2NaCNO + 3Cl2 + 4NaOH 2CO 2 + N 2 + 6NaCl + 2H2 O

This reaction is pH sensitive: The first reaction must be above pH = 10 for the cyanate to be formed. The second reaction works better at pH = 8. Since hydrogen cyanide gas can be released at acid pHs, one must really watch this reaction! The process can utilize hypochlorite bleach, peroxide or ozone, so the process is useful for cleaning up spills of cyanide or for disposing of cyanide wastes in a treatment method. Another practical oxidation process for waste destruction is the Zimmerman wet air oxidation method. Most organic compounds can be air-oxidized, if there is sufficient temperature and pressure present. This process is an aqueous phase oxidation of dissolved and suspended organics at 175 to 325 degrees Centigrade with enough pressure to prevent excessive evaporation. With air bubbled through the liquid, the process is fuel efficient and usually self-sustaining. Even some pesticides can be destroyed by this method.

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Reduction A reduction reaction is a reaction that involves a decrease in valence from a gain of electrons. A reduction-type reaction can be useful for the disposal of hexavalent chrome, a highly toxic waste that is dangerous to both man and the environment. The hexavalent chrome can be reduced to the much less toxic trivalent chrome by reacting the hexavalent form with sulfur dioxide and lime. Reduction can also be used with most other metals to create an easily removed precipitate. Redox treatment methods can, in general, be used for both in-situ and ex-situ waste disposal procedures. Neutralization Many wastes, especially liquids, sludges and slurries, may be highly acidic or alkaline. The best first step in treatment is to bring the waste to almost neutral pH. This neutralization process will ease handling and improve the effectiveness of follow-on treatments. Neutralization effectiveness is easily measured by pH change, and acid-base reactions are among the most often used processes in wastewater treatment. Several methods of neutralization are practical: Mixing multiple waste streams to achieve a neutral pH Adding lime slurries to acidic wastes Adding caustic soda or soda ash to acidic wastes Adding carbon dioxide to alkaline waste Adding sulfuric acid to alkaline wastes

All of these methods are effective, but it should be noted that, under RCRA regulations, such operations cause a facility to be regulated as a treatment-storage-disposal (TSD) operation. Even where RCRA does not apply, indiscriminate neutralization can be dangerous. The reactions can give off considerable heat (exothermic reactions). In the case of cyanide at high pH, overly enthusiastic neutralization could cause cyanide gas release, if the pH were to become acidic during neutralization. Materials can be neutralized in a simple reaction vessel as shown in Figure 19. Occasionally, sludges are treated in situ by mixing soda ash or lime with the sludge in a pond or lagoon. Neutralization on a small scale is also useful for disposing of laboratory chemicals. Since stack flue gases often have a high carbon dioxide content, such gases can be used to neutralize alkaline wastes. Good practice calls for bringing the waste to a near neutral pH (6 to 8), rather than to simply a
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RCRA non-hazardous waste condition (2 < pH < 12.5) .

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MIXER

pH meter

Neutralized effluent

Neutralizer

Waste stream

Chemical neutralization treatment system for waste management Figure 19

Calcination The recovery of the large amount of calcium that is needed for the softening of hard waters is economically attractive. To be used again, the dried, calcined, dewatered sludge must not contain much magnesium. Calcination is the process of heating dried solids to drive off carbon dioxide. Both calcium oxide (CaO) and Magnesium Oxide (MgO) are produced by the calcining process. Incidentally, the carbon dioxide driven off in the calcining may be used for carbonation of the softened water. Ion Exchange An ion exchange system selectively exchanges ions from a chosen material in the waste stream for the exchange medium. Two types of exchange systems are available: cation exchangers and anion exchangers. Cation exchangers are employed to remove positively charged materials (metals), and anion exchange units are used to remove negatively charged materials, such as organics. The primary use for ion exchange has been to remove metals from ground waters and surface waters. Metals are concentrated in the resin column and can then be removed by backflushing with water. The resin bed is then recharged by passing dilute acid through the bed. It is possible to achieve removal efficiencies of better than 99 %, with an effluent quality of less than 100 ppm of metal.
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Most water hardness is due to the presence of calcium and magnesium hardness. The water can be softened by passing the water through an ion exchange resin. Generally, the ion that is exchanged with the hardness is sodium, as indicated in the following equation:
Ca(HC3 ) 2 + 2NaR CaR2 + 2NaHCO3

where R is the ion exchange material. With this reaction, calcium or magnesium has been removed from the water and replaced by an equivalent amount of sodium. This process removes almost 100 % of the water hardness until the exchange capacity of the resin is reached. At this point, "breakthrough" has taken place. The resin is taken off line and backwashed with water containing a high sodium content. The hardness on the resin will enter the backwash water as follows:
CaR2 + 2NaCl 2NaR + CaCl2

The resin bed is now ready to remove additional hardness; however, the CaCl2 must be disposed of, or a recycle use for it must be developed. Ion exchange can also occur naturally in soil, particularly clay soils. The capability of a soil to retain and exchange cations is called the cation exchange capacity. Clays have a higher cation exchange capacity than other inorganic particles because clays have a large surface area, with numerous charge sites. It is important to note that ion exchange of metallic ions with soil may be partially reversible: exchange sites which are saturated can release cations as concentrations of contaminants decrease in groundwater. This means that, as groundwater contamination is remediated, more and more contamination that was bound up in a clay soil can be released: consequently, the clean-up effort will take far longer than expected. The exchange sites can also release cations if the pH is lowered. Ion exchange in the natural environment is, therefore, more of a retardation, than an attenuation process. In addition, the exchange capacity of the subsurface material can be so saturated that the contaminant transfer is not affected by ion exchange, and contaminant transfer goes unretarded. Other Chemical Methods The safe treatment of PCBs and dioxins is a major concern when handling solid waste. A dechlorinization process was developed as an alternative to incineration of chlorinated compounds. The underlying principle of dechlorinization is the removal of the chlorine atoms from the compounds. The dechlorinization process employs synthesized reagents to break down the chlorinated molecules or to form other compounds that are less toxic to the environment and man.

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The most often used dechlorinization processes use polyethylene glycols (PEG) that have reacted with alkali metals to bring about the dechlorinization. The two most common processes are called the Alkali Polyethylene Glycol Process (APEG) and the Potassium Polyethylene Glycol Process (KPEG). Either process will work in the field or the traditional plant. Removal efficiencies of 99.5 % have been demonstrated. This efficiency, although certainly desirable, is well below the efficiency of the best incinerators. Three factors must be considered for any chlorine destruction process: Temperature of the material Contact time between the contaminant and the reagent Moisture content of the soil

Elevating the waste temperatures from 20 to 80 Centigrade increases the reaction efficiency from 50 % to 90 %. Contact time varies from 4 to 8 hours for ex-situ work, up to an average of 7 days for in-situ treatment. Water adversely affects the reaction; soil moisture is, therefore, a factor in the extended contact time required for in-situ treatment. Both APEG and KPEG appear to have equal effectiveness. At this point in time, the major concern with dechlorinization is that the reaction byproducts have not yet been well defined. Since U.S. EPA has stated that dioxin is one of the most toxic substances known, it is well to proceed with caution when attempting to destroy the material.

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LANDFARMING METHODS

AND

COMPOSTING

AS

SOLID

WASTE

TREATMENT

Landfarming and composting are so similar in concept and requirements that the two processes will be discussed together. A landfarm is a biological treatment method that employs soil and associated microorganisms as the treatment medium. The natural physical, chemical, and biological actions all come together to degrade and immobilize the waste constituents. Some types of waste are not actually degraded, and are incorporated only into the soil. When that occurs, landfarming becomes a shallow, unlined landfill and is, therefore, a method of disposal, not treatment. Composting is the process of making a nonputrescible (non-rotting) soil amendment from solid waste. Many components of municipal solid waste are organic in origin and are therefore biodegradable. Paper, yard waste, food waste and some textiles, such as cotton and wool, can all be composted. Composting of waste will occur readily, if there are present appropriate microorganisms, adequate aeration, temperature in the correct range, required nutrients, pH and sufficient moisture. Landfarming has been used for: Oily sludges and waste oils, such as separator sludge, slop oil emulsion solids, induced and dissolved air flotation float, and leaded and unleaded tank bottoms. Half-lives of the materials are typically 200 to 500 days. Oil loading rate is usually the governing factor, although heavy metals in wastes such as tank bottoms are sometimes limiting. Organic sludges and liquids. Any waste that can be degraded biologically can be landfarmed if regulations permit it. Halogenated sludges must be handled very carefully to avoid problems during the sludges' slow decay time. Sludges from wastewater treatment plants. Heavy industrial activity in a community can cause high metals content in sewage sludge. Sludges are monitored periodically to ensure the waste stays within the plant's operating permit.

Careful attention must be made regarding the composition of the waste when considering a land disposal option. The US EPA has ranked all hazardous wastes based on their intrinsic hazard, volume, and phased land disposal. "Land ban" restrictions were enacted in three steps with the final enactment in May 1990. In order for land disposal (and also impoundment or deep well injection) to receive approval, listed hazardous wastes must be pretreated to pollutant concentrations below specified concentrations. It must also be demonstrated, to a reasonable degree of certainty, that there will be no migration of hazardous constituents from the disposal site.
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Saudi Aramco has established guidelines (Refinery Instruction Manual 5.881) for landfarming wastes as follows: 1. Landfarmable wastes: API separator sludges (less than 20 ppm organic lead) Air flotation sludges Biological waste treatment sludges Recovered oil emulsions Tank bottoms (excluding gasoline tanks) Crude tank bottoms MEA sludge Oil contaminated soil (less than 20 ppm lead) Desalter bottoms

Perhaps even more important than the list of what can be landfarmed, is the list of what the Instruction Manual says can not be accepted for landfarming: 2. Wastes not acceptable for landfarming: TEL tank bottoms Leaded gasoline tank bottoms Sweetening process sludges Sludge from sulfuric acid treating Caustic sludges Spent acid Catalyst from conversion processes Asphalt waste
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The general concept behind the list of materials unacceptable for landfarming is to avoid materials that are toxic and bioaccumulate such as lead, or to avoid materials that would drastically change the soil pH, such as sulfuric acid sludge. No crops for human or livestock consumption should be grown in soils where wastes have been applied if there is a possibility that hazardous or toxic materials could be assimilated into the consumable portion of the crop. The migration of such toxic materials is often difficult to determine; for example, a grain crop may show potentially harmful residues in the stalk of the plant, but not in the consumable grain. Landfarming works best when the applied waste material is biodegradable, and when the waste is incorporated into the soil in a low enough concentration that degradation can take place. The practice follows agricultural principles most closely; hence, comes the name landfarming. As with any good farm, several steps are taken to stimulate bacterial growth: Aeration pH adjustment Nutrient addition Moisture control Mixing of waste and soil

Just as with any biological process, bacteria have a dominant role in the degradation and conversion of many organic wastes. Bacteria are plentiful in the environment and generally in the waste materials. The reader is referred back to Module ENV 102.01 for a discussion of other organisms that have a role in biological degradation. The most recognized and efficient bacteria for degrading petroleum products are: Achromobacter, Acinetobacter, Alcaligenes, Arthomobacter, Bacillus, Flavobacterium, Nocardia, Pseudomonas, and Corynebacterium. Bacteria require: A carbon source (carbon dioxide or organic carbon) An energy source (light, inorganic or organic, oxidation-reduction reactions) Inorganic nutrients such as phosphorous and nitrogen Traces of certain metals (iron, manganese, magnesium, calcium, sodium and copper)
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Bacteria also are categorized by their atmospheric oxygen requirements as aerobic (require atmospheric oxygen) anaerobic (require a lack of atmospheric oxygen) or facultative anaerobic (function with or without oxygen). This environmental need will determine the type of bacteria that are available to function in the treatment process. The oxygen requirement also determines the rate at which treatment will progress and the resulting end products, which differ with aerobic or anaerobic biological activity. For example, methane will be a product of anaerobic activity but not of aerobic action. Most of the bacteria types listed for petroleum product degradation are classified as aerobic bacteria. Other critical environmental factors are temperature, pH, and moisture content. Optimal biological activity occurs within a fairly narrow range of temperature and pH for specific groups of bacteria although some activity can occur at less than an optimum rate outside the preferred range of temperature and pH. Generally, a warm environment (20-50 C) encourages biological activity. The optimum for many bacteria is 35 C, although higher temperatures (about 55 C) may be optimal for some bacteria. Fortunately, the bacteria most effective for petroleum products prefer temperatures between 35 C and 45 C. The higher temperatures are also desired for the destruction of pathogenic (disease-causing) microorganisms. A near neutral pH range of about 6.5 to 7.5 is best for most bacteria. Soil pH of less than 5.5 is considered unacceptable. Several other soil and site characteristics will determine the suitability of an area for landfarming: Soil depth must be greater than 2 feet. Restrictive subsoils must be greater than 8 feet from the surface. Highly permeable soil, such as sand, gravel, rocks and stone are undesirable. High salinity or alkalinity can interfere with biological processes. High background levels of certain metals or organics can make it difficult to determine how "clean" the site is. A water table closer to the surface than 8 feet (in sandy soil) or 6 feet (in loamy sand) is unacceptable due to probability of off-site pollution migration.

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Moisture is critical to bacterial and other microbiological activity since about 80% of the cell weight is water and since the nutrients for bacteria must be in solution to pass into the cell. Supplemental water may be required for landfarming or composting municipal solid waste. On a weight basis, the favorable moisture content for landfarming varies from 10-30%, depending on the soil texture. This is equivalent to 50-70% of the soil water holding capacity. It is important not to totally saturate the soil, or the bacteria will "drown," and the process will become anaerobic. The desirable moisture content for composting is usually in the 50% range. In non-arid climates with mild temperatures, these moisture contents can be achieved with two inches per month of rainfall or applied water. With Saudi Arabia's summer temperatures and minimal rainfall, considerable monitoring and adjustment will be needed to reach these moisture contents. In landfarming, wastes are applied uniformly to the land, either by spreading the wastes or by injecting the wastes just beneath the surface. A disk harrow or rototiller (for small scale operations) is used to mix the waste and soil. Cultivation maximizes the soil-waste contact. Furthermore, cultivation provides aeration to enhance the biological process. The cultivation takes place in only the first 10 to 30 cm of soil depth (called the "zone of incorporation"), but the "soil treatment zone" appears to extend to as much as 1.5 meters. Thus, landfarming is primarily a shallow depth, aerobic process. It is common to till the soil at three week intervals for at least the first three months of degradation. Landfarming works best primarily with organic wastes, but landfarming can also remove other contaminants. Suspended solids are removed by filtration on the soil and by physical settling. Heavy metals can be adsorbed onto soil particles. Heavy metals also can be precipitated or can undergo ion exchange with the soil. Some soils , particularly clays, have a high sorption capacity for metals. Still, metals are often somewhat problematic. To stabilize a heavy metal waste usually requires an alkaline pH. Such a high pH may not be optimum for bacterial action. Metals may not be actually toxic to the microorganisms in the soil. However, a high metals concentration may affect later plant growth when the site is closed. Plant uptake can also act as a removal mechanism. Finally, the waste can simply volatilize, or can be blown from the site on airborne dust. Thus, a heavy metal, such as lead, can actually be transported from the site. Both sandy and clay type soils have worked well for landfarms. Organic loadings as high as 5 to 10% of the soil volume (first 10 to 30 cm) are practical. Wastes are sometimes covered in cold climates. Covering the waste raises the temperature and encourages bacterial growth. Loading rates of 250 tons per acre per year are typical for petroleum wastes and are limited to 300 dry tons per year per acre by SAES - A-104. For landfarming to be successful, the rate and frequency of waste application must not exceed the assimilative capacity of the site. This assimilative capacity is based on: Capacity limits. Conservative, immobile wastes accumulate in the soil and eventually reach a level at which the site must be closed.

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Rate limits. Non-conservative waste constituents will degrade, but the cumulative amount applied must be compared with the cumulative amount degraded over time. Refinery Operating Instruction 5.883 allows the reapplication of sludge when the oil and grease content in a section of the landfarm is lowered to 2% or less for two successive samplings. Application limits. If the application rate is too high, waste can leave the site in water runoff or waste can volatilize excessively.

Mathematical models are available to evaluate these various limits. A simple first order reaction equation is often applied to determine the time required to degrade a waste to a final soil concentration as follows: t where: t C0 Ct K = = = = time to degrade initial soil concentration final soil concentration first order rate constant = ln(Ct/C0)/-K

Removal efficiencies for common wastes can be remarkably high with landfarming: In a Canadian study, a waste with 15,000 micrograms/gram each of benzene and toluene was reduced to the required limits in soil of 5 and 30 micrograms/gram for the two compounds, respectively, in less than 11 days. Benzo(a)pyrene in the same waste took 294 days to degrade. Finally, arsenic, a heavy metal that does not degrade, caused the abandonment of the site after four years when the toxic limit (50 micrograms/gram) for arsenic was reached. In a California laboratory experiment using soil contaminated with weathered crude, the contamination was reduced from 3700 ppm to 1000 ppm in just 80 days. This experiment involved daily water addition, oxygenation and nutrient addition. A "control" sample, which was untreated, went from 3700 to 3500 ppm in the same period. In a follow-up field pilot study, nutrient and surfactant addition were required to get readings below 1000 ppm - water and aeration alone would not do it. The 1000 ppm standard is a common site clean-up limit used by regulatory agencies in the United States.

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As stated previously, composting is used to turn MSW into a usable, useful product. Most composting operations begin with the removal of the approximately 10% non-degradable fraction, prior to starting the composting process. Glass, metal and plastic that do not compost are all potentially valuable to sort and recycle. Removal of hazardous waste is particularly important, although very difficult to achieve in practice. The wastes to be composted are then shredded. The shredded materials are then placed in "windrows" on the ground surface where the composting takes place. The primary difference between composting and landfarming is that composting takes place on the ground, while landfarming takes place in the ground. Composting, like landfarming is an aerobic process which requires moisture control (40-65%, with 50% being optimal), temperature (55 C, or 131 F) for three consecutive days to kill pathogens) and thorough oxygenation. The very high temperatures are achieved even in winter due to the biological activity of the waste. The oxygenation can be obtained by either of two methods: agitated piles, or static piles. In the agitated method, the piles are 6-10 feet high and 14-25 feet at the bottom. Equipment such as a Willibald side slicer is used to shave off a portion of the pile, moving it laterally and aerating it at the same time. A "straddling turner" can also be used to aerate the pile in place. In the static method air is pulled or passed through the pile with an air blowing system. Pulling the air through the pile by a system of surface grates or piping has the advantage of allowing treatment of the exit air for odors. Blowing air through the pile allows the addition of moisture or heat to the pile to control temperature and soil humidity. Besides time, temperature and turbulence, the ratio of carbon-to-nitrogen has been found to be rather critical in composting. The desirable C:N ratio is 20-30:1, with 30:1 often considered as an optimum. Low C:N ratios can result in ammonia off gassing - a highly irritating odor. High C:N ratios will eventually have a lower growth rate as the nitrogen is used up in the process. The whole composting process can take from 2 weeks to 18 months, depending on the degree of process control. A 2.5 acre facility can handle approximately 50 tons per day of compost (assuming a 2 month holding time), while each additional acre gains an additional 50 tons per day capacity.

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THERMAL DESTRUCTION METHODS OF SOLID WASTE TREATMENT Great progress has been made in thermal destruction methods compared to the open burning of trash that was practiced until recent times. Open burning of waste is still a factor in some less populated rural areas. However, the pressure of urban and population growth has virtually eliminated open trash burning in major population centers. In New York City, for example, until the 1970s almost every multi-family housing unit (apartment house) had a single chamber incinerator that was only a little improvement over open burning. Single chamber incinerators were banned in New York in the 1970s, and replaced by trash compactors at each apartment house. Open burning gives little volume reduction, compared with more effective incineration methods, and sufficient organic residue remained in the partially burned waste to still attract vermin and cause odors. There is still a place in smaller communities for the open burning of yard clippings (grass and small branches), but even a relatively small community should consider composting these wastes for a mulch or fertilizer. Thermal processes have lost some popularity recently as the method of choice for hazardous waste destruction. The threat of incomplete waste combustion, even if the threat is unfounded, has caused the U.S. public to oppose new incinerator locations. Three types of thermal destruction methods will be discussed in greater detail: incinerators, pyrolysis, and the "emerging technologies" of microwaving and plasma arc. Except for vitrification, which will be discussed in the next section, thermal technologies are ex situ processes: the waste must be transported to the processing unit. Incineration Thermal treatment, to most people, means the incineration of waste. Incineration can be defined as the burning of substances by controlled flame in an enclosed area. The desirable features of incineration are that incineration: Detoxifies hazardous waste by destroying organic compounds Reduces the volume of the waste Converts liquid wastes to solids by vaporizing any fluids present in the waste Sterilizes medical wastes Recovers waste heat from high heat content wastes

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Incineration can be designed to treat waste in any physical state-solids, liquids, sludges, slurries and gases. Incineration has been especially successful at destroying organic matter in waste. Removal efficiencies as high as 99.9999 % have been reached. Air emission regulators refer to such efficiencies as "six-9s" treatment level. Incinerator effectiveness depends on three factors, which are often cited as the three "T"s of combustion: Temperature of the combustion chamber Time -- the residence time of the waste in the chamber Turbulence -- the amount of mixing of the material with air while in the chamber.

In addition, oxygen (from the air), if present in excess, will drive the combustion reactions to completion more quickly. If a stoichiometric quantity of oxygen is all that is available, the reaction will still eventually go to completion. However, excess air will greatly increase the rate at which combustion is achieved. Different materials also have different excess air requirements. Air that is sufficient to burn natural gas cleanly, for example, is insufficient for a heavy fuel oil. Black smoke would result from the incomplete fuel oil burn. Even propane and natural gas (methane) have different air fuel requirements; a burner that is sized for propane will produce excess carbon monoxide if it is used with natural gas. Normal combustion temperatures vary between 900 1500 Centigrade, and occasionally much higher temperatures are experienced. One of the major difficulties with burning unsorted municipal waste is the tremendous range in heat content of the waste. Raw, wet garbage requires a great deal of supplemental fuel to burn; plastics, in contrast, have so much heat content that they can heat damage the incinerator walls. Most modern incinerators employ two combustion chambers. The first chamber's function is to convert the compound to a gas and initiate the combustion process. The second chamber completes the combustion of the gases. Auxiliary fuel to maintain combustion is normally added in the primary (first) chamber and sometimes in the secondary chamber. A twochamber incinerator is shown in Figure 20. The grate where the waste material is placed in this incinerator is fixed in position. Such an incinerator can support a grate loading of about 30 lb/hr-ft2. If the as-received heating value of the waste is 4000 to 5000 Btu/lb, then the heat release rate from the grate will be 120,000 to 150,000 Btu/hr-ft2. Although the fixed grate might prove satisfactory for a small apartment house incinerator, most larger incinerators employ a so-called "spreader stoker" to spread the waste on the grate and to ease ash removal. Several varieties of spreader stokers are shown in Figure 21.

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Charging door with overfire air ports

Flame port

Secondary air port

Curtain wall

Primary combustion chamber

Secondary combustion chamber

Fixed grates

Cleanout doors underfire air ports

Mixing chamber

Curtain wall port

Cutaway of an in-line multi-chamber incinerator Figure 20

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(a) Stationary

(b) Dumping

(c) Oscillating

(d) Traveling

Types of grates available for combustion of solid fuels Figure 21

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The spreader stokers in Figure 21 throw the fuel mechanically across the grate from the fuel hopper in the right-hand side of the drawings. The grates in Figure 21 (a) are still fixed in place. This fixed grate system requires the ash to fall through the grate without any grate movement. Airholes in the grate for the underfire air can be blocked by the refuse, which affects combustion efficiency. In Figure 21 (b), the grates can be rotated mechanically to dump ash into the bottom ash pit. The air holes can be smaller in size; the smaller air holes lessen the chance of unburned waste dropping into the ash pit. Two types of oscillating or travelling grates are shown in Figure 21 (c) and (d). This style of grate lessens the blockage of air holes and generally improves combustion. Heat release rates for a spreader stoker can approach a million Btu/hr-ft2, which is six to eight times that of a stationary grate incinerator. All of these systems, except for the stationary grate, could be considered for use in refusederived fuel (RDF) combustion because of the uniformity of the fuel. Unprocessed fuel is so variable that a different type of grate has proved to work better. Figure 22 illustrates a stairstep grate arrangement, with every other step being held stationary. The moveable steps are slowly moved back and forth, pushing the refuse towards the ash hopper. As the refuse falls from one step to the next, its surface area is exposed for a longer and longer time. It is essential to provide this mixing or turbulence capability when working with unprocessed refuse. In Figure 23, a mass-fired municipal combustor is repeated here from Module ENV 102.01. This incinerator is used for the large-scale conversion of municipal solid waste , with energy recovery to electrical energy as used in Los Angeles, California. The detailed steps of the process are given after the figure. By using a conversion from megawatts (million watts ) to Btu/hr, one can estimate the amount of energy produced by municipal refuse. If the overall combustion-to-energy conversion efficiency is 33% (typical), then one must put in 3 megawatts to get 1 megawatt output: 3 megawatts x 3.413 x 106 Btu/hr/megawatt = 1.02 x 107 Btu/hr if refuse = 6000 Btu/lb, then 1.02 x 107 Btu/hr 6000 Btu/lb = 1700 lb/hr per megawatt out

Thus, almost a ton of refuse per hour is required to generate a megawatt of electricity. Although this sounds like a great deal of refuse, a city of 25,000 persons producing 5 lb/person/day of refuse will equate to 2.6 tons per hour of waste. The generation of 3 megawatts of electricity from this amount of waste should be compared very carefully to the option of landfilling the waste.

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Mechanically fired incinerator with reciprocating grates Figure 22

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Section through a typical continuous-feed mass-fired municipal combustor that is used for energy production from municipal solid waste. (courtesy of County Sanitation Districts of Los Angeles County, California) Figure 23

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The operations of the process in Figure 23 are: 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13. 14. 15. 16. Solid wastes are received from the collection trucks. Wastes are temporarily held in a storage pit (about 2 days waste volume capacity). An overhead crane transfers the waste from storage to the charging chute. The charging chute conveys wastes to the furnace chamber. The waste is burned in the furnace chamber. The grates retain wastes while they are burned. The combustion chamber burns gases and small organic particles that rise due to a forced air draft. Temperatures are generally in excess of 1600 F. The boiler recovers heat from the hot gases using water-filled tubes for the production of steam. The steam is used to drive a turbine-generator to produce electricity. Ammonia injection is used to control the NOx (nitrogen oxides). A dry scrubber is used to control the SO2 (sulfur dioxide and acid gas control by neutralization with lime). A fabric filter (bag house) system is used to collect particulates. A fan is used for inducing a draft to help overcome head loss through the air pollution-control equipment and to supply air to the combustion process. Cleaned gases are discharged through a high stack for atmospheric dispersion. Ash and unburned residue from the grates fall to a hopper where they are quenched with water. Furnace ash and fly ash from the dry scrubber and bag house are conveyed to ash treatment and disposal facilities. Ash should be tested against hazardous waste disposal criteria.

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In the preceding Figure 23, a baghouse was used for particulate control. Baghouses will likely work better than electrostatic precipitators (ESP) for applications in mass burn incinerators because of the variability of the fuel input. ESP's are very sensitive to a particle property called resistivity. The ESP efficiency will vary as the fuel feed resistivity varies, and the fuel feed naturally will vary greatly with municipal waste. Solid wastes principally contain these elements: carbon, hydrogen, oxygen, nitrogen, and sulfur. Lesser quantities of other elements (various metals, for example) may be found in the ash residue. When the waste is burned with the addition of stoichiometric quantities of oxygen (or air) that is needed for complete combustion, the typical gaseous products are carbon dioxide (CO2), water (H2O, flue gas), nitrogen (N2) and small amounts of sulfur dioxide (SO2). The reactions for the oxidation or combustion of C, H, and S (and their atomic weights) as contained in municipal solid waste are as follows: for carbon: for hydrogen: for sulfur:
C + O2 12 32 2H 2 + O2 4 32 S 32.1 + O2 32 CO2

2H2O

SO2

The stoichiometric amount of air that is required for each of the above combustion reactions may be calculated as follows: If it is assumed that dry air contains 23.15% oxygen by weight, the amount of air required for the oxidation of 1 pound of carbon, hydrogen and sulfur, respectively, will be: (32/12) (1/0.2315) = 11.52 lb. air/lb. carbon (32/4) (1/0.2315) = 34.56 air/lb. hydrogen (32/32.1) (1/0.2315) = 4.31 lb. air/lb. sulfur

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An example of the calculation for determining the amount of air required for the combustion of an organic solid waste follows. Note that in step 2 of the Problem, the %'s are given in % by volume; in step 3 - 5, the %'s are by weight. Example Problem 2. Determination of the stoichiometric amount of air required for the combustion of an organic solid waste. Determine the amount (lbs and ft3) of air that is required for the complete combustion of one ton of an organic solid waste. Assume that the composition of the organic waste to be combusted is given by C5H12. Assume the specific weight of air is 0.075 lb/ft3 Solution: 1. Write a balanced stoichiometric equation for the oxidation of the organic compound based on oxygen:
C 5H12 + 8O2 72 256 5CO 2 + 6H2O

2.

Write a balanced equation for the oxidation of the organic compound with air. In combustion calculations, dry air is assumed to be comprised of 21% oxygen and 79% nitrogen. Thus, the corresponding reaction to that given in Step 1 for air is
C 5H12 + 8O2 + 30.1N 2 5CO 2 + 6H 2O + 30.1N2

3.

Determine the amount of air required for combustion, assuming air contains 23.15% oxygen by weight
O2 Air required = required = 256 (2000 lb / ton) = 7111lb / ton 72 7111lb / ton = 30,717 lb / ton 0.2315

4.

The amount of air required for combustion can also be computed using the factors, given previously.
Air Air 60 (2000 lb / ton) 11.52 = 19, 200lb / ton 72 12 required for hydrogen, H = (2000 lb / ton) 34.56 = 11 ,520 lb/ ton 72 Total air required = 19, 200 + 11 520 = 30,720lb / ton , required for carbon , C =

5.

Determine the volume of air required for combustion. Volume of air = (30,717 lb/ton)/(0.075 lb/ft3) = 409,560 ft3/ton

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Solid waste combustors are designed to operate as either mass-fired units or RDF units. A mass fired combustor uses commingled, unseparated solid waste with little or no processing. An RDF unit uses refuse-derived fuel, a processed waste which has had much of the noncombustible material removed. Approximately 23% of the U.S. units are of this type. Mass-fired units have some design considerations that may not be important when using RDF: The nature of the waste can be quite variable and may contain unsuitable materials. The crane operator can reject large unsuitable objects or attempt to blend high- and low-moisture content materials. Potentially hazardous materials may be contained in the waste. The combustor design should be such that the risk of damage to equipment and the risk of injury to personnel will be minimized.

The use of RDF can provide a combustible product that is more consistent and may be processed (although more expensive) to a pellet or cube form (sometimes called densified RDF or d-RDF) that can be burned by itself or mixed with other fuels. RDF combustion units are typically smaller than mass-burn combustors, but some space will be required for the processing of the fuel. Because of RDF's greater uniformity of materials and heat value, an RDF combustor burns more efficiently than a mass-burn combustor. Air pollution control is also easier with an RDF unit than with a mass burn combustor. Tables 2, 3 and 4 show typical data on the analysis of combustibles in solid waste and the composition of the residue following the combustion of commingled municipal solid waste. Fly ash ( the material from the stack) and bottom ash (any non-combusted organic and inorganic materials) are usually combined for final disposal in a landfill or as landfill cover. This disposal method is somewhat controversial due to the likely presence in the ash of metals, such as lead, zinc, mercury, chromium, and cadmium. These metals can leach out at the landfill and affect vegetation, and leaching into the groundwater is possible if precipitation infiltration is not prevented. Incinerator scrubber sludge disposal presents similar challenges. US EPA recently proposed that incinerator ash be classified as a RCRA hazardous waste. This classification would restrict ash disposal to only designated hazardous waste disposal facilities and would increase the cost of waste disposal. Some recycling uses have been developed for fly ash. Those uses include adding the fly ash to bricks and concrete to improve the product's strength.

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Table 2.

Typical data on the ultimate analysis of the combustible materials found in residential commercial and industrial solid wastes.
Percent by weight (dry basis)

Type of waste Food and food products Fats Food wastes (mixed) Fruit wastes Meat wastes Paper products Cardboard Magazines Newsprint Paper (mixed) Waxed Cartons Plastics Plastics (mixed) Polyethylene Polystyrene Polyurethane Polyvinyl chloride Textile, rubber, leather Textiles Rubber Leather Wood, trees, etc. Yard wastes Wood (green timber) Hardwood Wood (mixed) Wood chips (mixed) Glass, metals, etc. Glass and minerals Metals (mixed) Miscellaneous Office sweepings Oils, paints Refuse-derived fuel (RDF)

Carbon 73.0 48.0 48.5 59.6 43.0 32.9 49.1 43.4 59.2 60.0 85.2 87.1 63.3 45.2 48.0 69.7 60.0 46.0 50.1 49.6 49.5 48.1 0.5 4.5 24.3 66.9 44.7

Hydrogen 11.5 6.4 6.2 9.4 5.9 5.0 6.1 5.8 9.3 7.2 14.2 8.4 6.3 5.6 6.4 8.7 8.0 6.0 6.4 6.1 6.0 5.8 0.1 0.6 3.0 9.6 6.2

Oxygen 14.8 37.6 39.5 24.7 44.8 38.6 43.0 44.3 30.1 22.8 4.0 17.6 1.6 40.0 11.6 38.0 42.3 43.2 42.7 45.5 0.4 4.3 4.0 5.2 38.4

Nitrogen 0.4 2.6 1.4 1.2 0.3 0.1 <0.1 0.3 0.1 <0.1 0.2 6.0 0.1 2.2 10.0 3.4 0.1 0.1 0.2 0.1 <0.1 <0.1 0.5 2.0 0.7

Sulfur 0.1 0.4 0.2 0.2 0.2 0.1 0.2 0.2 0.1 <0.1 <0.1 0.1 0.2 1.6 0.4 0.3 0.1 <0.1 <0.1 <0.1 0.2 <0.1

Ash 0.2 5.0 4.2 4.9 5.0 23.3 1.5 6.0 1.2 10.0 0.4 0.3 4.3 2.0 3.2 20.0 10.0 6.3 1.0 0.9 1.5 0.4 98.9 90.5 68.0 16.3 9.9

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Table 3.

Typical data on the ultimate analysis of the combustible components in residential municipal solid waste.
Percent by weight (dry basis)

Component Organic Food wastes Paper Cardboard Pastics Textiles Rubber Leather Yard wastes Wood Inorganic Glass Metals Dirt, ash, etc.

Carbon 48.0 43.5 44.0 60.0 55.0 78.0 60.0 47.8 49.5 0.5 4.5 26.3

Hydrogen 6.4 6.0 5.9 7.2 6.6 10.0 8.0 6.0 6.0 0.1 0.6 3.0

Oxygen 37.6 44.0 44.6 22.8 31.2 11.6 38.0 42.7 0.4 4.3 2.0

Nitrogen 2.6 0.3 0.3 4.6 2.0 10.0 3.4 0.2 <0.1 <0.1 0.5

Sulfur 0.4 0.2 0.2 0.15 0.4 0.3 0.1 0.2

Ash 5.0 6.0 5.0 10.0 2.5 10.0 10.0 4.5 1.5 98.9 90.5 68.0

Table 4.

Composition of residue from the combustion of commingled municipal solid waste.


Percent by weight Component Partially burned or unburned organic matter Tin cans Other iron and steel Other metals Glass Ceramics, stones, bricks Ash Total Range 3-10 10-25 6-15 1-4 30-50 2-8 10-35 Typical 5 18 10 2 35 5 25 100

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Besides incineration's use for refuse disposal, several types of incinerators have been employed for wastewater sludge disposal . These methods of sludge disposal include: multiple-hearth incineration, fluidized-bed incineration, and co-incineration. A multiplehearth incinerator is shown in Figure 24. These units are complicated and are, therefore, usually practical only at the larger wastewater plants. Multiple-hearth units have also been used at chemical plants for the recalcining of lime sludges. The sludge cake is fed onto the top hearth and slowly raked to the center. The sludge drops to the second hearth and is raked to the outside. The process alternates between layers until the cake is dry. Sludge cakes range from 15 to 50% solids, and average cake loadings are approximately 5 to 15 lb/ft2 -hr (25 to 75 kg/m2 .hr).

Typical multiple-hearth incinerator Figure 24

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The fluidized bed incineration method is shown in Figure 25. These units contain a sand bed and fluidizing air orifices under the sandbed. Air is injected at 3 to 5 pounds per square inch (20 to 35 kilo newtons per square meter) to fluidize the bed. The mass of suspended sand and gas, when at temperature and active, expands to about double its at-rest volume. Water evaporation and combustion of the sludge take place very quickly due to the turbulent action of the bed. The combustion gases and entrained ash are scrubbed, usually with a venturi scrubber. The scrubber water is then returned to the fluidized bed to improve overall removal efficiency.

Fluidized-bed incinerator Figure 25

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Co-incineration means the practice of mixing sewage sludge with normal municipal solid waste . The goal is to reduce the combined cost of incinerating sludges and solid wastes. Sludges can be dewatered to a 10 to 15% moisture content. Ratios of 1 pound dry sludge to 5-8 pounds of solid waste sludge have proved effective. This ratio depends on the type of incinerator process used. Another common method of incineration, particularly for hazardous wastes, is the rotary kiln incinerator. The rotary kiln, which is shown in Figure 26, is a cylindrical shell that is mounted on its side on a slight incline. As the kiln rotates, the wastes pass through and are combusted. The technology was adopted from the traditional cement kiln. In fact, it is now common practice to use hazardous wastes with a high heat value instead of natural gas or other fuels to heat cement kilns. The three "T"s of incineration are almost ideally met in the long combustion chamber of a cement kiln, and kiln incinerators can accept all phases of waste.

Rotary kiln furnace Figure 26 Example 3 illustrates the waste volume reductions possible with incineration.

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Example Problem 3. Determination of the volume reduction and volume of residue after combustion. Based on a 1000 lb. quantity and a typical composition as given in Table 7, ENV 102.01, determine the quantity and composition of the residue following combustion. Use the ash content of Table 3, ENV 102.02, as equivalent to the inert residue % of the solid waste. Estimate the reduction in volume assuming the specific weight of the residue is 1000 lb./yd.3 and the initial specific weight was 375 lb./yd.3. Solution: 1. Set up a computation table to determine the amount of residue and its percentage distribution by weight. The completed computation table is presented below:
Component Solid waste, lb 90 340 60 70 20 5 5 185 20 -80 60 5 30 30 1000 Inert residue, % 5 6 5 10 2.5 10 10 4.5 1.5 -98.9 90.5 90.5 90.5 68 Residue lb 4.5 20.4 3.0 7.0 0.5 0.5 0.5 8.3 0.3 -79.1 54.3 4.5 27.2 20.4 230.5 % 2.0 8.8 1.3 3.0 0.2 0.2 0.2 3.6 0.1 -34.3 23.6 2.0 11.8 8.9 100.0

Organic Food wastes Paper Cardboard Plastics Textiles Rubber Leather Yard wastes Wood Misc. organics Inorganic Glass Tin cans Aluminum Other metal Dirt, ash, etc. Total

2.

Estimate the original and final volumes before and after combustion. To estimate the approximate initial volume, assume that the average specific weight of the solid wastes in the combustor storage pit is about 375 lb/yd3. Original vol = 1000 lb/375 lb/yd3 = 2.67 yd3 Residue volume = 230.5 lb/1000 lb/yd3 = 0.23 yd3

3.

Estimate the volume reduction Volume reduction = ((2.67 - 0.23)/2.67)100 = 91%

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Pyrolysis Pyrolysis differs from incineration. Pyrolysis is a chemical change in a material that is brought about by the action of heat. Incineration, by contrast, is the combustive destruction of a substance in direct flame in the presence of oxygen. Pyrolysis can be viewed as destructive distillation in the absence of oxygen (or other oxidant). Pyrolysis is designed to convert organic matter (either volatile or semi-volatile) to combustible gas, charcoal, organic liquid, and ash/metal residues. Pyrolysis has a major advantage. The organic liquid fraction produced during the pyrolytic reaction can potentially be used as a base for synthetic crude oil. The effectiveness of pyrolytic destruction depends on many of the same factors as incineration: Residence time within the retort furnace Rate of temperature rise Final temperature Makeup of the feed material

Pyrolytic furnaces, operating at temperatures between 500 and 800 Centigrade have achieved 99.9999% destruction and better than 50 % volume reductions. Emerging Technologies Two relatively new techniques are finding some uses in solid waste treatment, particularly for the destruction of hazardous waste. These techniques are: microwaving and plasma torch. Microwaving Microwaving, the same technique that has proved indispensable to the modern household, has been adapted for in-situ treatment of wastes. In 1985, the US EPA began a joint project with the Illinois Institute of Technology Research Institute (IITRI) on the use of radio frequency (RF) heating for soil decontamination. RF heating uses electromagnetic energy that is directed through electrodes in the soil to create molecular vibration and rotation. This uniformly heats the soil. This technique was first used in the 1970s to recover oil from oil shale and tar shale. The original research involved heating rocks to 200 - 400 Centigrade, but because most contaminants have boiling points less than 150 Centigrade, the RF research now primarily involves these lower temperatures.

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Laboratory experiments using fuels and solvents have produced over 95% removal at temperatures of 100 -150 Centigrade. Actual field tests on an abandoned fire training area were equally promising. A 500 cubic meter test site was established. A trailer-mounted 40 KW RF generator was used to heat 39 electrodes, which were placed in the soil in rows of 13 electrodes each. A vapor barrier was placed over the site to collect escaping soil gas. The captured gas was transported to a vapor condenser for separating liquid hydrocarbons and to a carbon bed to treat the remaining volatile organics. A 560 liter/min vacuum was applied to the vapor barrier to ensure all the vapors were captured. The RF energy was applied to the site over 12 days. At the 8 day point, the target temperature of 150 Centigrade was achieved and maintained for the next 4 days. The removal efficiencies were measured for volatile aliphatics and aromatics, and semi-volatile aliphatics and aromatics. The process removed 97% of the semi-volatiles and 99% of the volatiles. Total energy consumed was approximately 800 KW - hr/yd3. The removal of the higher boiling point compounds is brought about by the steam distillation provided in the native soils. Underlying soils at the site were predominantly fine- to coarse-grained sandstone, with interbedded shale and overlying unconsolidated sand. The test soils were 95% sand, with 5% by weight finer than sand. Mineralogically, the soils were at least 98 % alpha quartz, with no clay, as determined by X-ray diffraction. Such a site provided almost an ideal test location to prove the value of the RF heating. Other soils with a higher clay content may be less amenable to the technique. Plasma Arc Plasma arc technology is actually a variation of the pyrolysis technique. However, instead of the 500 to 800 Centigrade of normal pyrolysis, the plasma arc operates at 5,000 to 15,000 degrees Centigrade. Wastes are fed into the thermal plasma, and the wastes become disassociated into their basic atomic components. The atoms then recombine in a reaction chamber to form carbon monoxide, nitrogen, hydrogen, and small amounts of methane and ethane. The process also produces some acid gases, which must be scrubbed from the air stream. Any solids that result from the process are incorporated into the molten bath at the bottom of the chamber or are removed from the exhaust gases by particulate scrubbers or filters. This technology is currently applicable only to fine particle wastes, liquids and pumpable wastes. The high energy requirements needed to achieve these extremely high temperatures would seem to limit the technique's usefulness.

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SOLIDIFICATION AND STABILIZATION AS SOLID WASTE TREATMENT METHODS As was discussed in Module ENV 102.01, the terms solidification and stabilization are sometimes used interchangeably, but they are, in fact, different processes. Solidification is the process of eliminating free liquids from the waste and increasing the bearing strength of the waste to form a more uniform solid. The solidification process involves the waste being bound within the final matrix of the waste and the solidifying agent. Solidification does not necessarily involve a chemical bonding between the waste and the agent. Stabilization is the name given to the process of reducing the hazardous properties of a material by decreasing the mobility or toxicity of the contaminants. These processes improve the handling and physical characteristics of a waste by: Producing a more solid material, which improves the handling and physical characteristics of the waste. Reducing contaminant solubility, e.g., by pH adjustment or sorption phenomena. Decreasing the exposed surface area to reduce reaction rates and loss of material.

Solidification/stabilization systems have been used for wastes containing toxic metals and, to a lesser extent, volatile organic compounds (VOC) and semi-volatile organic compounds (SVOCs). The technologies are being used for: remediation of hazardous waste sites; treatment of residues from other treatment processes, e.g., thermal treatment ash; and the cleanup of land where large amounts of contaminated soil are found. Included among solidification/stabilization systems are: Pozzolan-portland cement and lime-fly ash pozzolan systems Thermoplastic encapsulation Silicate-based Sorption Vitrification

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The first process entraps the wastes in a concrete mixture, with the pozzolan-portland cement matrix being stronger than the lime-fly ash mix. Thermoplastic microencapsulation usually involves blending the waste with melted asphalt. Silicate-based processes use soluble silica materials and cement to stabilize wastes. Sorption is the process of absorbing free liquids through the addition of sorbents such as activated carbon, clays, zeolites, anhydrous sodium silicate, and gypsum. Vitrification is a type of thermal process whereby the waste material essentially becomes a glass-like substance. Complete and uniform mixing of the waste and agent is critical. This mixing can be done well with ex-situ applications. For in-situ applications, the addition and mixing of the agent with the waste is much more difficult. In such cases, the agent is injected under pressure into the waste in a liquid or slurry form at a spacing which attempts to accomplish complete agent/waste contact. The potential for contaminant loss is usually measured by leaching tests, such as the RCRA TCLP test. The primary difficulty with many hazardous wastes is that the waste will fail the TCLP toxicity test. In essence, this means that the material will leach a toxic substance when exposed to the pH found in most landfills. Solidification/stabilization processes prevent or minimize this leaching. The combined material can then pass a TCLP test, and the material is no longer considered hazardous. The solidification/stabilization processes will now be discussed in greater detail. Cement-Based The pozzolan-portland cement systems entrap wastes in a concrete matrix. Lime-fly ash pozzolan systems use the same technique, but the resulting lime-fly ash matrix is not quite as strong as the pozzolan-portland cement matrix. Portland cement is made by firing a mixture of limestone and clay (or some other silicate) in a kiln at high temperatures. The kiln clinker is ground into powder. This powder is a mix of calcium, silicate, aluminum and iron oxides. Tri- and di-calcium silicates are the main ingredients. In cement stabilization, after the waste material is mixed with the cement, water is added to hydrate the mixture. Water is only added if the waste material lacks sufficient water to make a good mixture. The hydration of the cement forms a crystalline structure. This structure is made of calcium alumino-silicate. A hard, rock-like, monolithic mass results. A monolith is a solid, block of waste material with high structural integrity. In some cases, the monolith is not the end product of the solidification/stabilization process; however, after placement in the disposal site, the materials may continue to cure into a reasonable form of monolith. Cement-based stabilization works best for inorganic wastes, particularly those wastes which contain heavy metals. The high natural pH of the cement is excellent at maintaining the metals in an insoluble hydroxide or carbonate salt form. Lead, copper, zinc, tin, and cadmium are all "fixed" in this fashion.
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Organic wastes, by contrast, tend to interfere with the hydration process. This lessens final material strength. Additives can be incorporated into the organic contaminant to reduce this interference. Additives that have proved beneficial include clays, vermiculite, and soluble sodium silicates. Cement-based stabilization/solidification has been used with plating wastes that contain heavy metals. Cement has also been employed with wastes containing PCBs, oils and oil sludges; wastes containing vinyl chloride and ethylene dichloride; resins; plastics; asbestos; and sulfides. In-situ stabilization has worked well for arsenic, lead, zinc, copper, cadmium and nickel. A pozzolan is a substance that reacts with lime in the presence of water to make a cemetitious material. When alumino-silicious material reacts with lime and water, the material which is formed is called pozzolanic concrete. Several materials have pozzolanic properties: fly ash, ground furnace slag, pumice, and cement kiln dust. Just like Portland cement-based materials, the pozzolans work best for inorganic wastes. This stabilized material is considerably weaker than Portland cement, and the pozzolan waste has varying consistency. Some products resemble soil; other products are similar to the Portland cement-based material. Regardless of the texture, leaching tests show the hazardous substances to be bound up very well by the matrix. Fly-ash-based products even work well for some organics. Apparently, the unburned carbon in the fly ash may adsorb organics from the waste. Thermoplastic-Based Hazardous wastes can be stabilized by mixing molten thermoplastic materials with the waste at high temperature. Although asphalt is the most common thermoplastic used, other materials include paraffin, bitumen, polyethylene, polypropylene, and sulfur. After cooling, the solidified material is referred to as a thermoplastically coated waste. In this technique, the waste materials do not bind chemically with the thermoplasitc material; rather, the wastes are microencapsulated by the thermoplastic. The typical disposal method is to place the material in drums for ultimate disposal. RCRA prohibits the landfilling of "free" liquid wastes, but these stabilized wastes no longer have free liquid in the waste. Free liquids are defined as liquids that readily separate from the solid portion of the waste under ambient temperature and pressure. Waste to bitumen ratios of 1:1 or 1:2 are common. To date, most of the disposals using this thermosetting method have been with radioactive wastes or so-called mixed wastes (radioactive and other substances). The radioactivity drives the ultimate disposal method. Bitumen may have commercial application for stabilizing oil- and gasolinecontaminated soils. The hydrocarbon- contaminated soil is used to dilute the bitumen, which is then used as paving or road-patching material. One concern with thermoplastic techniques is the possibility that the waste can act as a solvent and eventually deteriorate or destroy the thermoplastic material.
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Silicate-based Commercial processes for the stabilization of metals have employed siliceous materials for a long time. In one particular process, silica reagents are acidified to form a monosilic acid solution. Metal-containing wastes are added to the bath and stabilized. In another process, liquid-soluble silicates and cement are used for in-situ soil stabilization when metals such as lead, copper and zinc are present. Sorbents Sorption is the process of adding a material to the waste to absorb free liquid Some materials that are popular as sorbents are: Activated carbon Clays Zeolites Anhydrous sodium silicate Fly ash Bottom ash Cement kiln dust Gypsum

In picking a sorbent material, consideration must be paid to the amount of material needed to eliminate the free liquid in the waste. Compatibility with the waste material is a necessity. An acid sorbent can release hydrogen cyanide or produce hydrogen sulfide, if the sorbent is used improperly. Alkaline sorbents can release ammonia or carbon dioxide. Sorbents that contain carbon can become pyrophoric when used on hydrocarbon wastes. A pyrophoric substance catches fire spontaneously when exposed to air!

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Vitrification Vitrification has been used for both organic and inorganic wastes. It works with both in-situ and ex-situ materials (in-place ad removed from original site). This flexibility has made vitrification very popular as a remediation technique. The basic principles of vitrification are primarily the same as the production of glass. Hightemperature electrodes are used to melt the wastes. Pyrolysis destroys the organics; inorganics are fixed in place by the glass matrix. An ex-situ application appears very much like a glass plant. The wastes are introduced into the furnace along with silica, soda and lime. The organics, which are driven off, are captured and treated, and the inorganics are incorporated into the glass. In-situ vitrification involves the insertion of large electrodes into the soil to produce a large electric current to heat the soil and waste mixture. Graphite and glass frit is spread on the soil surface to start the process. A hood is placed over the site to collect any off-gases for later treatment. A high-voltage source (typically, a 4,160 volts, 3000 KW electrical source) is applied across the electrodes. This produces temperatures of 1600 - 3600 Centigrade. Insitu vitrification is limited by: High groundwater Buried metal objects The need for large quantities of glass-forming material in the soil

Once started, the molten mass grows downward and outward. It can reach a depth of 30 feet and a total melted mass of 1000 tons. Melt rates of 4-6 tons per hour are to be expected. Since soil porosity is decreased by the glassification process, the net volume of waste decreases as the mass cools. Most of the other stabilization techniques actually cause a volume increase. Asbestos waste has been treated by vitrification. A pilot plant in England has been in use since 1984. Approximately 500 kg per day are mixed with glass debris and other glass additives at 1400 Centigrade for 10 hours. This makes the asbestos amorphous and causes the asbestos to mix with other silicates. After cooling, the non-toxic product can be used as an aggregate filler in concrete. Table 5 shows several examples of the various stabilization technologies that have been discussed in the preceding sections.

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Site/ contractor Cu, Cr, Ni Pb, Cd Oil sludges, Pb. Cr, As Oil/solids Cd, Cr, Pb Oil sat: soil Pb (1000 ppm) PCBs (200 ppm) As (1-200 ppm) Sludges (viscous) Sludges Various Lime NA 10-25% Kiln dust 20% Lime and kiln dust ~15% CaO ~5% kiln dust In situ In situ Continuous Continuous flow In situ Soils Pozzolanic and proprietary ~30% Continuous feed (mixer proprietary) design 90,000,000 gallons Sludges Chemfix proprietary NA, proprietary Continuous flow (proprietary process) 100,000 yd3 Sludges, variable Onsite 150,000 yd3 Dry-landfill Varied 7-15% (cement) Concrete batch plant Varied, 15-30% In situ Landfill NA >Varied, ~20% average Onsite Average 15% Onsite ~1% 16,000 yd3 Sludge Portland cement 20% >0 In situ Onsite

Containment (concentration)

Treatment volume

Physical form

Binder

Percentage binder(s) added

Treatment (batch/ Disposal continuous (onsite/ in situ) offsite)

Scale of Volume increase, operation % Full scale Full scale Full scale

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Portland cement and silicates (Toxsorb)TM KiIn dust (high CaO content) Full scale (site delisted 1985) Full scale 62000 yd3 (plus 5000 tons of surface debris) ~235,000 yd3 12,000 yd3 20 million gal/yr 90,000 gal. (445 yd3) 3000 yd3 Sludges (synthetic oil sludges) Sludges Portland cement and proprietary Lime Onsite >~9%+ (TSCA cells) Onsite lined cells >~14% Full scale Full scale In-plant process >Estimated Full scale 10% >4-10% Full scale Offsite (secure landfill) Onsite (secure landfill) Onsite landfill Waste acid PCBs (< 500 ppm), dioxins Creosote wastes Various/combined

Midwest, U.S. Plating Company, Envirite Marathon Steel Phoenix, AZ Silicate, Tech. N.E. Refinery ENRECO

Amoco Wood River Chemfix

Pepper Steel & Alloy, Miami, FL VFL Technology Corporation

Vickery, OH Chemical Waste Management Wood Treating, Savannah, GA Geo-Con, Inc. Wyandotte, MI Treatment Plant Chem Met Chem Refinery, TX HAZCON Combined metals, sulfur, oil sludges, etc. Al (9500 ppm) Ni (750 ppm) Cr (220 ppm) Cu (2000 ppm)

Table 5. Case studies for stabilization technologies (modified from U S EPA).

Metalplating, WI Geo-Con, Inc.

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GLOSSARY aerobic bacteria Bacteria that generate water, carbon dioxide, organic acids and inorganic minerals in the presence of oxygen, appropriate nutrients, and moisture. Bacteria that generate water, carbon dioxide, organic acids, and inorganic minerals in the presence of appropriate nutrients, and moisture, but without the presence of oxygen. American Petroleum Institute A material that does not degrade readily and therefore will tend to build up in the food chain. Examples are the pesticide DDT and PCBs. A chemical reaction that requires heat to be added to complete the reaction. A chemical reaction that produces heat. Bacteria that have the ability to grow either with or without the presence of oxygen. A waste is treated in-place, or removed from its original site. Liquid-containing soluble soil matter, organic acids, and inorganic material products of the decomposition of waste. A material that will not break down in a "reasonable" length of time when exposed to conditions in a landfill, sunlight, weathering, etc. All materials degrade over a time, if the period is long enough. The study of how elements combine in predetermined quantities to form compounds. For example, the exact amount of oxygen needed to form carbon dioxide from carbon.

anaerobic bacteria

API biocumulative

endothermic exothermic facultative anaerobes in-situ/ex-situ leachate nondegradable

stoichiometric

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REFERENCES Arabian American Oil Company, Refinery Operating Manual 5.881, December 15, 1994. Arabian American Oil Company, Refinery Operating Manual 5.883, February 13, 1990. Arabian American Oil Company, Monitoring Program for Oily Waste Landfarms, undated. Ayers, Kenneth W., et.al., Environmental Science and Technology Handbook, Government Institutes, Inc., Rockville, Maryland 20850, 1994. Beak Consultants Limited, Manual for Landspreading of Petroleum Industry Sludges, PACE Report No. 81-58, December 1981. Dev, et.al., "Field Tests of RF Soil Decontamination Process," Proceedings of Superfund National Conference and Exhibition (1988). Fair, G. and Geyer, J. Water Supply and Waste Water Disposal, Wiley, New York, New York, 1961. Golueke, Clarence G., "Bacteriology of Composting," BioCycle, January 1992. Henry, J. and Heinke, G., Environmental Science and Technology, Prentice Hall, Inc., Englewood Cliffs, New Jersey, 1989. LaGrega, Michael D., et.al., Hazardous Waste Management, McGraw-Hill, Inc., New York, New York, 1994. Pfeffer, John T., Solid Waste Management Engineering, Prentice-Hall, Inc., Englewood Cliffs, New Jersey, 07632, 1992. Salvato, Joseph A., Environmental Engineering and Sanitation, John Wiley & Sons, Inc., New York, New York, 1992. Spencer, R. and Golob, B. and Selby, M., "Design Elements for Solid Waste Composting," BioCycle, July 1991. Tchobanoglous, George, et.al., Integrated Solid Waste Management: Engineering Principles and Management Issues, McGraw-Hill, Inc., New York, New York, 1993. Tchobanoglous, G. and Burton, F., Wastewater Engineering, Treatment, Disposal and Reuse, Metcalf & Eddy, Inc., McGraw-Hill, Inc., New York, New York, 1991.

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Uziel, Michael, "Cleaning up Weathered Crude: Research Points to Bioremediation," The National Environmental Journal, March/April 1994. Viraraghavan, T. and Robbins T.F., "Saskatchewan's Petroleum Industry Explores Landfarming," Industrial Wastewater, March/April 1995. Wentz, Charles A., Hazardous Waste Management, McGraw-Hill, Inc., New York, New York, 1989.

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