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3

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EMERGIN ECHNOLOGIE BY PRODUCT

by

4 CONVERSIO Robert S. Reimers, Ph.D.

Department of Environmental Health Sciences

School of Public Health and Tropical Medicine

Tulane University

1430 Tulane Ave.

New Orleans, Louisiana 70112

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INTRODUCTION

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With t h e increase of industry i n Louisiana, the d ispos i t ion of hazardous waste has become a major p o l i t i c a l , technological , and p u b l i c h e a l t h concern of t h e 1980 ' s . A s a r e s u l t of these concerns, four i n t e re l a t ed projects have been j o i n t l y sponsored by the Louis iana Board of Regents, t h e Department of Na tu ra l Resources and the o f f i c e of the Governor. The ob jec t ive of t h i s pro jec t is t o eva lua te technological a l t e r n a t i v e s f o r resource recovery and by-product conversion and disposal f o r s ign i f i can t indus t r ies located i n Louisiana. T h i s paper is an interim report evaluat ing emerging technologies per t inent t o t h e objec t ive of t h i s conference. Legis la t ion has been a major f ac to r behind the accelerated i n t e r e s t i n high-technology waste management a l o n g w i t h c o r p o r a t e concerns about t h e impact of i n d u s t r i a l wastes on human h e a l t h and t h e n a t u r a l environment. T h i s l e g i s l a t i o n has been developed a s a r e s u l t of t h e Resource C o n s e r v a t i o n and Recovery A c t (RCRA) o f 1 9 7 6 and t h e Comprehensive Environmental Response Compensatory and L i a b i l i t y A c t of 1980 (Superfund). The first act has promulgated hazardous waste regulat ions t ha t have been i n force s i n c e 1981. The i n t e n t of RCRA w a s t o emphasize hazardous waste management a l t e r n a t i v e s e l e c t i o n towards resource recovery. Some may argue tha t some of the r e g u l a t i o n s of t he A c t may impede ra ther than enhance t h i s object ive. The Superfund A c t is intended t o provide ''clean-upff of s e v e r e l y mismanaged i n d u s t r i a l waste d i s p o s a l s i t es and relates t o the d i rec t ion of current and fu ture waste management p r a c t i c e . T h e main s t r e n g t h of t h e a c t r e l a t e s t o Superfund's l i a b i l i t y p rov i s ions . These p r o v i s i o n s make any person o r company ( i n c l u d i n g t r a n s p o r t e r s o r p r e v i o u s d i s p o s a l f a c i l i t y owners) t h a t e v e r had c o n t a c t w i t h any waste now l o c a t e d a t a problem s i t e l i a b l e t o be he ld a s a " r e spons ib l e par ty" i n t h e c lean up of t h a t site. T h i s means t h a t generators who contracted i n good f a i t h w i t h a d i s p o s a l f i r m y e a r s ago can now f i n d themselves p a r t i a l l y o r e v e n w h o l l y r e s p o n s i b l e f o r t h e unacceptab le consequences of t h a t f i r m s a c t i o n s even i f these act ions were completely legal a t t ha t t i m e (1).

For any waste problem, it i s e s s e n t i a l t o use a management approach t h a t complies w i t h r e g u l a t o r y g u i d e l i n e s , is c o s t effect ive, and i s env i ronmen ta l ly compatible . Obviously, t h e e l i m i n a t i o n o r r educ t ion of hazardous wastes a t i t s source is more desirable t h a n t r ea tmen t on o r o f f s i t e . T h e management of hazardous wastes i m p l i e s a h i e ra rchy of approaches from most desirable t o least. These include:

1. Hazardous Waste Abatement

2. Hazardous Waste Reduction

3. Hazardous Waste Reuse

4. Hazardous Waste Recycle

5 . Hazardous Waste T r e a t m e n t , D e t o x i f i c a t i o n and/or

64 /

Destruction

6. Hazardous Waste Disposal

3

Definitions for the first five terms are elucidated in Table 1 with examples of each. The optimum plan is dictated by both economics and legal constraints. Another reason why all wastes should not be recycled is due to increased energy demands. The choice of management approach will change with the fluctuation of the economic environment. The choice of waste abatement is encouraged by:

1. Escalating raw materials cost; uncertainty of raw material availability.

2 . Increasing costs of energy to process raw materials.

3 . Increasing costs of waste treatment and disposal.

Above factors stimulate the following:

1.

2 .

3.

4 .

5 .

Process change evaluation to avoid or reduce hazardous waste generation.

Initiation of R&D programs on non-waste or low waste technologies.

In-plant combustion to reduce the amount of hazardous waste produced and decrease contamination of potentially recyclable waste.

Serious consideration of side streams, by-products, wastes generated for use as raw materials.

or

Expansion of recycling and recovery of wastes for potential products or raw products for other industries and businesses. Waste generators matched with potential users of this waste as a product.

The estimates of ptential reuse of hazardus wastes ranges from 3% t 20% ( 2 ) . In Canada, an exchange board has been able to match waste generators to potential users for 15 percent of the waste sharing in its bulletins. In Europe, the reuse of hazardous wastes has been observed to be 33 percent (3). In Appendix A, a listing of the various exchange boards is noted. Such a board in Louisiana could effectively reduce hazardous waste volumes regarding the need for treatment. In considering the potential of resource recovery, there are 10 commandments of resource recovery (4) which are shown in Table 2.

Emerging Reuse Treatment Rationale

In developing technology for reuse of hazardous wastes, the treatment rationals may result treating the of total waste load, treatment of a selective waste stream, or catalyzing specific

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TABLE 1

DEFINITION OF TERMS

Definition Examples

1. Waste Abatement: 3

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Substitution of a new primary industrial process for an old process to eliminate or dras- tically reduce the quantity of waste produced.

2. Waste Reduction:

The reduction of the quantity of waste through good house- keeping practices or by the application of concentration technology. Also the reduction in hazardousness of waste through simple in-plant treat- ment.

3. Waste Reuse:

The direct reuse of a waste stream, as is or with very minor modification either by the plant that produces the waste or by others.

4. Waste Recycle:

The reclamation of value from waste streams through the application of unit processes such as distillation, etc.

o Replacement of cyanide in electroplating solutions

o Replacement of solvent based paints by water based ones.

o Separation of waste streams to permit recovery

o Recovery of metals from electrodialysis

o Neutralization of wastes and precipita- tion of smaller volume sludges.

o Use of solvents from electronics industry in paints manufacture

o Use of refinery caus- tic in pulping of wood

o Use of paint sludges as sealants.

o Oil rerefining o Solvent Distillation o Secondary aluminum

o Iron salts from pickle smelting

liquor.

66 3

TABLE 1 (CONT.)

7

5. Detoxification:

The waste is either destroyed or altered to a non-hazardous condition. In addition, the waste may be utilized as an energy source.

6. Disposal:

The waste is disposed of as a hazardous waste at a specified disposal site. These wastes are generally concentrated to reduce trans- port and handling costs.

o Refining sludge land farming

o Desensitizing and detox- ifying explosive wastes

o Utilizing spent o i l s and sludges as fuels.

o Selective biological conversion of PCBs to aliphatic hydro- carbons.

o Some heavy metal

o Deepwelling of wastes

selected wastes

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TABLE 2

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TEN COMMANDMENTS OF RESOURCE RECOVERY ( 4 )

1.

2. Thou shalt not expect to find a gold mine in your waste.

Thou shalt have the waste at your disposal.

3. Thou shalt not believe in total resource recovery.

4. Thou shalt not produce anything from refuse which no one wants to buy.

5. Thou shalt not forget the cost of resource recovery.

6 . Thou shalt dispose the residue.

7. Thou shalt activate the energy in waste with the least possible losses.

8. Thou shalt have different recovery systems for different types of wastes.

9. Thou shalt have different recovery systems for differenet countries,

10. Thou shalt take care of your environment when making resources.

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processes. During recent years, thermal processes have vastly improved with respect to combustion efficiency of toxic organics, energy recovery of hazardous wastes, and the final residues of a less or non-hazardous nature. Recent publications elucidate innovative thermal process which will oxidize persistent organics such as PCBs, dioxins, and etc. (5, 6, and 7).

Over the last thirty years, the treatment of selective waste streams has been utilized to promote the reuse of hazardus wastes. In general, these wastes are concentrated and then separated by extraction or distillation. The two most widely applied recycle systems are solvent recovery and waste oil refining. These are briefly described below:

1. Solvent Recovery - The variety of solvents which can be processed in recovery operations include

a. Halogenated hydrocarbons such as methylene chloride and tetrachloroethylene used in degreasing, metal cleaning, and dry cleaning.

b. Aliphatic and aromatic hydrocarbons, alcohols, acetone, hexane, and butyl acetate used in various chemical process industries such as paint manufacturing, printing operations and industrial paint uses.

I -__. ( 8 ) :

c. Numerous special solvents such as freon and phenol.

If simple mixtures of solvent and contaminant have a large difference in volatilities, then a simple distillation process can be used to effect separation. The waste is heated in a container where the solvent is vaporized and condensed and the contaminants or residue is drawn off for subsequent disposal. With more complex mixtures, a fractional distillation process can be used which will separate out various solvents from wastes

2. Oil Rerefininq - A traditional process used for waste rerefining is the acid-clay process (9). This

process has been reduced in recovery efficiency to 75% as a result of additives and detergents. The resulting residue is an acid tar and spent clay which is hazardous due to high leachable metals such as lead and a corrosive leachate. As a result of this problem, Phillips Petroleum Company has developed a new process which recovers over 90 percent of the oil and produces less filter cake, pretreated aqueous wastes discharged into the sewer, and lower metals contents in the recycled oils. As the state of the art increases, even better results may be obtained.

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Finally, where the cost of technology change is not feasible, then the addition of a catalyst may be used to alter a hazardous waste into a recyclable product. Catalysts which have been utilized in existing processes are metallic oxides (Fe203, Ni02, T 02, etc.), peroxides, and irradiation with uftraviolet light. These catalysts have been utilized in enhancing oxidation processes such as ozonation or hydrogen peroxide oxidation (10). More recent studies reporting hazardous waste treatment processes modifications have indicated in many cases enhancement of treatment and/or conversion by additions of acclimatized microbes, genetic microWs, and enzyme applications or by exposure of selected process streams to non-ionization irradiations such as electrostatic, electromagnetic, or magnetic fields (11). 3

3

Technology Assessment

The processes that have been developed for hazardous waste treatment have been divided into five major classifications. These processes vary from a very simple process treatment such as equalization to a complex process seen as glassifhation. The five major types of waste process operations are elucidated below:

0 -------- PHYSICAL --------- TREATMENT - Processes that, through concentration and/or phase cahnge, alter the hazardous constituents to a more convenient form for further processing or disposal.

CHEMICAL TREATMENT - Processes in which hazardous constituents are altered by chemical reactions. In most cases, this equates to hazard destruction. In some exceptional cases, the resultant product or products may still be hazardous, although in a more convenient form for further processing or disposal.

0 ---------- BIOLOGICAL --------- TREATMENT - Processes which utilize biological organisms (usually microbes) to convert waste to intermediate components or final metabolic end products of C02 and H 2 0 for aerobic systems and CH plus CO for anaerobic systems. Already widesprea4 appl icazion for treating wastewaters, both hazardous and nonhazardous.

7- ----- -- 0

0 THERMAL TREATMENT - Processes that use high temperature as the principal mechanism for waste destruction. (This also involves chemical reactions.)

FIXATION/ENCAPSULATION - Processes in which the hazards of wastes are reduced by immobilization.

0

These processes are listed and elucidated for each category in Table 3.

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TABLE 3 -

TECHNOLOGY

Physical Treatment

Magnetic Processes

Screening and c l a s s i f i c a t i o n

Crushing and grinding

Liqui d/sol i d separat ion

Sedimentation (with o r without floccul a t i on )

F i l t r a t i o n Centrifugation Flotat ion Bel t presses F i 1 ter presses

Drying

D i s ti 11 a t i o n

U U .l J L, b b 4 ..

Comparison of Alternative Technologies for Hazardous Waste Management (1)

DE SCR I PT I ON OF PROCESS OR EOUIPMENT

Magnet i c-separa t ion devices

Standard manufactured u n i t s

Standard manufactured units

Standard manufactured uni t s

EXAMPLE APPLICATIONS

Debris presor t

Separation of oversize material s

Size reduction o f s o l i d material f o r further processing

Remove p a r t i c l e s from 1 i qui ds ; remove excess moisture from sol i d s o r sl udges

Standard S1 udge drying manufactured u n i t s

Mu1 ti t r a y o r packed column w i t h heat ing pu r i f i ca t ion and condensing f o r reuse devices

Sol vent

STATUS

Comnerci a1

Comnercial

C o m r c i a1

C o m r c i a1

CONS I DE RAT I ON S RELATIVE COST

L i m i t ed Low appl ica t ions

Reprocessing o r Low disposal o f mi scel 1 aneous ma teri a1

Fugitive emissions Low

Sol id s t i l l contains some l i qu id

Low

some Mechanical problems Expensive experimental a i r emissions some come rei a 1

Medium C o m r c i a l Scal ing and/or foul i ng F1 a m b i 1 i t y hazard w i t h some sol vents

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DESCRIPTION OF PROCESS

TECHNOLOGY OR EQUIPMENT

Physical Treatment - Continued

EXAMPLE APPLICATIONS

RELATIVE COST STATUS

Comnerci a1

Comnerci a1

Comne r c i a 1

Comnerci a1

CONS1 DERATIONS

Evaporation Single-stage, multi- stage o f vapor- compress i on evaporators t h a t may include crysta l1 i zat ion step

Nuclear wastes Elect rop lat ing wastes

Scaling and/or foul i ng Condensate i s some times contaminated Disposal o f concentrate

Moderately high

Str ipp ing

Steam A i r 0 ther gas

Mu1 ti t ray o r packed colunm wi th gas i n jec t i on

Sul f i de s tri ppi ng T r i chl o w e t hy l ene s t r ipp ing

Limited t o v o l a t i l e components A i r emi ss i ons

Low t o Medium

Absorption Mu1 ti tray o r packed column with appropriate solvent

Standard processes (Supercr i t ica l f l u i d under deve 1 opmen t )

Usually f o r emission control

Disposal o f scrubbing l i q u i d

Low

Solvent Ext ract ion Ext ract ing con tami n an t s f rom s o i l Ext ract ing meta ls from l i q u i d

Contaminated sol vent Moderate1 y high (Supercri t i c a l requires fu r the r

l i q u i d under processin9 f o r development) disposal )

L iqu i d-Liqui d Sol id-L iqu id Supercri t i c a l f l u i d

Medium Adsorption Batch o r continuous adsorption beds usual ly w i th regeneration

Organic adsorption onto carbon Heavy metal adsorption onto res i ns

Comnerci a1 Limited t o low concentrations Disposal o f regenerate

Carbon Resin ( i on exchange, others) Prop r i eta ry systems

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DESCRI PT I ON OF PROCESS

TECHNOLOGY OR EQUIPNNT

Physical Treatment - Continued

W

Membrane processes Standard pnufac tu red un i t s

f a c i l i t i e s

foul ing and/or de te r iora t ion

U1 t r a f i l t r a t i o n w i t h appropriate Reverse osmosis pretreatment D i a1 ys i s Elec t rodia lys i s t o prevent membrane

Freezing Many types o f units

Crystal1 i za t ion Freeze drying Suspension freezing

'j

EXAMPLE APPLICATIONS

Removal of heavy metals o r some organics from groundwater

Sus pe ns ion f reez ing ponds f o r hydrous metal hydroxi des

U 3

STATUS CONS I DE RAT IONS

Recently Separations a r e commercial imperfect

Pretreatment is complex

Experimental Not comnercially o the r than developed drying/ f reezing beds

d

RELATIVE COST

Medium

Low f o r drying beds, high f o r o thers

L

TECHNOLOGY

Chemical Treatment

Neutral i za t i on

Prec ip i ta t ion

Electrochemical processes

4 6

Oxi dat ion

C h 1 o r i ne - con ta i n i ng reagents Ozone Pe rma n ga na t e Peroxide Others

Reduction

Dechl o ri na t i on Sulfonation Other

Photol ys i s

U1 t r a v i o l e t Natural 1 i ght

DESCRIPTION

L, j i

OF PROCESS OR EQUIPMENT APPLICATIONS

J

Chemi ca 1 addi t i on Neutra l izat ion o f and mix tanks ac id and a lka l ine

wastes

Chemical add i t ion Heavy nk ta ls t o produce an removed insoluble s o l i d

D.C. power and p l a t i n g apparatus

Copper remova 1

Chemical addi t ion Trace-organi c and contacting tanks destruct ion

I

STATUS

W Ll

CONS I DERATI ONS

v’ 3

RELATIVE COST

Comnerci a1 Heat release i n Low concentrated appl icat ions Control c o w l ex

Sol ubi 1 i ty 1 aws i n t e r f e r i ng substances

Come r c i a1 Low

some Impuri t ies can Medium comnercial ; upset process

e xper i men t a l some

Some Side-reactions may Medium commercial ; generate other t o high some hazardous experimental consti tuents

Chemical addi t ion Reduction o f some S i de-reactions may Medium comnercial ; generate other t o high and contacting tanks hexavalent chrome

Dechlorination o f some hazardous d iox in experimental const i tuents

Photol amps and Dioxin destruct ion Semi- Foul ing o f Low f o r contacting devices Cyanide destruct ion c o m r c i a l photo-chemi cal natural

devices High Kinet ics f o r UV

L Li i v

OESCRl PTION OF PROCESS

TECH NOLOGY OR EQUIPMENT APPLICATIONS

Chemci a1 Treatment - Con t i nued

G a m i rrad$at ion Shielded i r r a d i a t o r Pesticide destruction

M i sce l l aneous Chemical add i t ion Pesticide chemical treatments and contacting tanks destruction

Catalysis Hydrolysis Other

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STATUS

J

CONS1 DERATIONS

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RELAT I VE COST

Experimental Sophisticated High i w a d i a to r desi gn

Experimental Side-reactions may Varies generate other . hazardous consti tuents

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TECHNOLOGY

B i o1 og i ca l Treatment

Activated sludge 1 agoons

Aerated Anae rob i c Facultat ive

Anaerobic Digestion Compos ti ng T r i c k l i n g f i l t e r s Aerobic b i o f i l t e rs Fe rmen t a t i on Waste-stabil i z a t i o n ponds

Land treatment

Land farming Spray i rri gation In -s i t u augment a t i on

New biotechnologies

Enzyme Cultured bacter ia Gene s p l i c i n g

DESCRIPTION OF PROCESS OR €QUIPMENT

EXAMPLE APPLICATIONS STATUS CONSIDERATIONS

RELATIVE COST

Comnon Commercial system des1 gns

Sui tab le landsi t e and spreading eq u i pmen t

Biochemical add i t ion system

Removal o f organic materials f r o m water

Treatment o f re f i ne ry o i l sludges I r r i g a t i o n o f contami nated groundwater

Comnerci a1 Only e f f e c t i v e on Low biodegradeable o r bioabsorbable cons ti tuen t s Subject t o tox i c

. i n h i b i t i o n

some Potent ia l f o r Low t o experimental ; incomplete Medium some degradation comnercial Pol 1 utant

migration

Experimental F i e l d i s new, so High considerations ( M Y be are no t wel l lower i n understood fu tu re)

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DESCRIPTION OF PROCESS OR EQUIPMENT

EXAMPLE APPL I CATIONS

RELATIVE COST TECHNOLOGY

Thernlal Treatment

Established i nci nera t i on

STATUS

Comnerci a1

CONS I DERATIONS

Stan da rd comnercial l y marketed units

Indus tri a1 inc inera tors Contract hazardous waste i nci nerators

Fuel value Medium Destruction e f f ic iency Disposal o f ash and scrubber bl owdown

t o high F1 u i d i zed bed Mu1 ti pl e hearth Rotary k i l n Liquid injection Shipboard

Fvol v i ng incinerat ion Processes

Developmental u n i t s Dioxin destruct ion Expe r i men t a l Techno 1 o gy not well devel oped

High

Molten s a l t Microwave plasma Plasma a r c

41 41 Codisposal

inc inera t ion Standard units Waste-sol vent

burning

. Organics des t ruc t .an

Conmercial Fuel value Low t o Effec ts on medium emi ssions-control equipment I ndus tri a1 boi 1 er

Cement k i l n L i m e k i In

Pyrolysis Proprietary u n i t s Many comnerci a

ayp roduc t s generated may be hazardous

High t o Me d i um

Convent i ona 1 tempera tures U- tube reac tor Vert i cal - tube reac tor

Wet Air oxidation Autociave U-tube reac tor Vertical -tube

reac tor

Proprietary u n i t s Organics des t ruc t ion

Many Process i s commercia 1 only 85-90% but mostly i n e f f i c i a n t non hazardous waste appl i - ca t ions

Medium

V L. L

DESCRIPTION OF PROCESS

TECHNOLOGY OR EQUIPMENT

F i xation/Encapsulation

Sorption Stabi 1 i zing mater ia ls and

Flyash contacting methods K i l n dust Lime Limestone C1 ays Vermi cul i t e Zeal i tes A1 umi na Carbon Imbiber beads Propr ietary agents

4 ca

Pozzolanic react ion Mechanical equipment f o r mixing and

Lime- f lyash reaction Port land cement

Encapsulation S tab i l i z i ng materi a1 s and

f o r encapsul a ti on Organic polymers mechanical equipment Asphalt Glass i f i ca t i o n Propr ietary agents

w

EXAMPLE APPL I CAT1 ONS

Sol i d i f y i ng hazardous wastes

Sol i d i f y i ng hazardous wastes

Sol i d i fyi 'ng hazardous wastes

'4 LJ 3

Comnerci a1 Long- term effectiveness

Comnerci a1 Organic agents sometimes in te r fe re w i th react ion

some Long- term experimental ; effectiveness

come r c i a1 some

Medium

Medium

Medium t o high

RELATIVE STATUS CONSIDERATIONS COST

a

d

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EMERGING TECHNOLOGIES FOR HAZARDOUS TREATMENT AND DISPOSAL - - The objective of this section is to identify and evaluate

new and emerging technologies for hazardous waste treatment and disposal. Currently emerging technologies include molten salt compustion, fluidized bed combustion, and ultraviolet/ozone destruction. In addition to these technologies, processes employing catalyzed wet oxidation, dehalogenation by the addition of hydrogen in the presence of ultraviolet light, high energy electrons, ultraviolet light/chlorinolysis and catalytic hydrogenation-dechlorination are presently in the developmental phase. Along with these techniques, biological detoxification methodswill be elucidated concerning genetic engineering, microbial, and enzymatic treatment. Miscellaneous developing thermal processing technologies will also be reported.

Current Emerging Technologies

The definition of emerging technologies is processes which have been applied on a pilot or mobile unit phase. In addition, these processes have illustrated both technical and economic advantages to current technologies with a degree of feasible application within the next few years. Presently, there are only three processes which fall into this category (12). A capsulation of these processes is taken from a CRC review conducted by Ebon Research Systems. These processes are shown in Table 4.

Molten - Salt Combustion

IgMolten salt technology has been in existence' for many years, but only recently has molten salt combustion been used for the treatment of hazardous wastes. In the process, hazardous material is combusted at temperatures below its normal ignition point, either beneath or on the surface of a pool of molten salt. Individual alkali carbonate salts, such as sodium carbonate, or mixtures of these salts, are usually used as the melt, but other salts can be employed based on waste characteristics. Containers for the molten salts are made of ceramics, alumina, stainless steel, or iron.

Ideally, during the molten salt combustion process, organic substances are totally oxidized to carbon dioxide and water, while heteratoms such as phosphorous, sulfur, chlorine, arsenic, and silicon are reacted with the

Na2S04, Na2S05, and . Iron from metal containers Na3P0f, orms iron oxide. Most carbonate melt to form NaC1,

Na2sio? organ c substances are destroyed, leaving behind a relatively innocuous residue, while harmless levels of off- gases are emitted. Generally, the salt bath is stable, nonvolatile, nontoxic, and may be recycled for further use until the bath is no longer viable.

Some hydrocarbons combusted by the molten salt process

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TABLE 4

EMERGING TECH1 101 OGIES

I CURRENT EMERGING TECHNOLOGIES PROCESSES THAT ILLUSTRATE BOTH TECHNICAL AND ECONOMIC ADVANTAGES TO CURRENT TECHNOLOGIES WITH A DEGREE OF FEASIBLE APPLICATION WITHIN THE NEXT FEW YEARS,

J

PROCESS .- DESCRIPTION CURRENT STATE MOLTEN SALT COMBUSTION ALLOWS COMBUSTION OF HAZARDOUS MATERIAL UP TO DEMONSTRATOR

BELOW ITS NORMAL IGNITION POINT, USES A SITE COOL GASSIFICATION POOL OF MOLTEN SALTS (ALKALAI CARBONATE

WASTE) SALTS, AND OTHER SALTS DEPENDING UPON

FLUIDIZED BED INCINERATION

UV/OXI DANT

APPLIES A HOT FLUIDIZED BED WHICH ALLOWS UP TO ON-SITE UNIFORM TEMPERATURES, REDUCES ENERGY COMBUSTION SYSTEMS

I

REQUIREMENTS a

ESTABLISHED TECHNOLOGY USING OZONE OR CURRENTLY UTILIZED PEROXIDE, THE USE OF APPLIED FIELDS HAS I N IN-FIELD GREATLY IMPROVED THE OXIDATIVE POTENTIAL, SITUATIONS CATALYSTS HAVE ALSO IMPROVED EFFICIENCY (ULTRASOUND, OXIDES OF COPPER, NICKEL, COBALT, ZINC, CHROMIUM, IRON, MANGANESE, MIXTURES OF PLUTONIUM AND PALLUDIUM AND ENZYMES 1

3

3

3

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v) w t- v) a 3

z 0 m

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LL

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D

are chlorinated hydrocarbons, PCB's, explosives and propellants, chemical warfare agents, rubber wastes, textile wastes, tannery wastes, various amines, contaminated ion exchange resins, tributyl phosphate, and nitroethane.

The technology has progressed from bench-scale through the pilot plant stage to the construction of a demonstration-size coal gasification unit. Additionally, portable units mounted on truck beds have been used.

Advantages of Molten - Salt Combustion of Hazardous Waste

1.

2 .

3 .

4 .

5 .

6.

7 .

8 .

Some of the advantages of molten salt combustion are:

Combustion is nearly complete

Non-polluting off-gases are emitted

Operating temperatures are lower than in normal incineration; thus they are fuel efficient

The system is amenable to recycling generated heat.

The system does not require highly skilled operators, i.e., a professional engineer's license is not required.

A wide variety of hazardous wastes can be combusted.

Bulky wastes can be combusted after pre-sizing.

Many wastes can be combusted incompliance with EPA regulations.

Major Problems with Molten Salt Combustion of Hazardous taste

--- __.- ----- --- ----- - _.----

Some problems with molten salt combustion of hazardous wastes are:

1. Particulate emissions from some wastes are high, although generally less than from normal incineration.

2. The technology is not readily adaptable to aqueous wastes

3

3. The molten salt bath must be bubbling (but not ebullient) to promote efficient combustion.

4. Eventually waste salt and ash must be disposed of, or the fluidity of the melt will be destroyed.

A hazardous waste with greater than 20% ash cannot be combusted.

5 .

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6. Detailed economic information for a demonstration-sized system is not currently available (1980).

Hazardous Wastes Destroyed b~ Molten Salt Combustion

PCB s

Chloroform

Perchloroethylene distillation bottoms

Trichloroethane

Tributyl Phosphate

Nitroethane

Monoethanolamine

Diphenylamine HC1 - Rubber tire buffings

Para-Arsanilic Acid

Contaminated Ion Exchange Resins (Dowex and Powdex)

High-Sulfur Waste Refinery Sludge

Acrylics Residue

Tannery Wastes

Aluminum Chlorohydrate

Pesticides and Herbicides - Chlordane

Malathion

Weed B Gon

Sevin

DDT Powder

DDT Powder plus Malathion Solution

2,4-D Herbicide-Tar Mixed Waste

-- Real and Simulated Pesticide Containers

Plastic, rubber, and a blend of these

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>

.>

3

Feasible Pesicides - and Nitrile Herbicides

Pesticides Nitrile Herbicides

dieldrin trifluralin

heptachlor

aldrin

toluidine

2,4,5-T dichlorobinil

MCPA

Phosphorous Insecticides (feasible)

diasinon

disul f onton

phorate

parathion

Explosives - and Propellants

TNT

glyceryl nitrate

diglyceryl tetranitrate

glycol dinitrate

trimethylolethane trinitrate

diethylene glycodinitrate

PETN

DPEHN

Tetryl

Cyclonite

Feasible

JP type hydrocarbon fuel

ethyl alcohol

hydrazine and its derivatives

Chemical Warfare Agents Destroyed

GB

a4

GB Spray-dried salts

Distilled Mustard, HD

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Lewisite, L

Toxic Gas Identification Sets (Real and Simulated) made of Pyrex, wood, plastic, tin-plates steel, and agent

Fluidized Bed Incineration

Fluidized bed systems have had many industrial uses since the technology was proposed by C. E. Robinson about a century ago, yet fluidized bed combustion of hazardous waste is a relatively new technique. A hot fluidized bed offers an ideal environment for combustion. Air passage through the bed produces strong agitation of the bed particles. This promotes rapid and relatively uniform mixing of carbonaceous materials. Bed mass is large in relation to the quantity of injected waste, and bed temperatures, which usually range from 750-1000°C, are quite uniform.

Hazardous wastes that have been incinerated in a fluidized bed include chlorinated hydrocarbons with a high chlorine content, waste PVC, waste PVC with coal, PVC insulated waste wire, munitions (TNT, RDX, and Composition B), spent HC1 pickling liquor, spent organotin blasting abrasive, and a waste organic dye-water slurry. A listing of various materials used as the bed medium is included in the Unit Operations Section.

Advantages of - Fluidized Bed - Inceneration of - Hazardous Wastes Advantages of fluidized bed combustion of hazardous

waste are:

1. The combustor design concept is simple and does not require moving parts after the initial feed of fuel and waste.

2. Fluidized bed combustion has a high combustion efficiency.

3 . Designs are compact due to high volumetric heating rates.

4. Nitric oxide formation is minimized because of low gas temperatures and -low excess air requirements. Low excess air requirements also reduce the size and cost of gas handling equipment.

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5 .

6 .

7 .

8 .

9.

10 . 11 . 12.

13.

In some cases, the bed itself can act to neutralize some of the hazardous products of combustion.

The bed mass provides a large surface area for reaction.

Temperatures throughout the bed are relatively uniform.

Continued bed agitation by fluidizing air a1 lows larger waste particles to remain suspended until combustion is completed.

If the hazardous waste contains a sufficient caloric value, a fluidized bed combuster can oprate without auxiliary fuel.

Excess heat generated by fluidized bed combustion of wastes with high caloric value can be recycled.

Fluidized beds are able to process aqueous waste slurries . As the bed functions as an efficient heat sink, major variations in feed consistency and water content take a long time to effect temperature changes in the bed medium.

The heat sink effect also limits radiation from the bed and allows the combustion system to be shut down for considerable periods of time (weekends) and restarted with little or no pre- heat time.

Major Problems with Fluidized - Bed Incineration of Hazardous Waste

- -

Some problems with fluidized bed combustion of hazardous waste are:

1.

2.

3.

4 .

Bed diameters and height are limited with design technology; therefore, maximum volumetric flow rates per unit are limited.

Removal of inert residual material from the bed (such as ash) can be difficult in some instances.

In systems where temperature must be controlled at lower limits because of other thermal considerations, increased residence time can cause carbon buildup in the bed.

Certain organic wastes will cause the bed to agglomerate, thereby reducing its effectiveness.

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5 .

Hazardous

Particulate emissions are a major problem with fluidized bed combustion. In some cases, particulates are high even when emissions are passed through a Ventui scrubber.

Wastes Destroyed Isy Fluidized Bed Incineration HC1 pickling liquor (spent)

Organotin in spent steel slag blasting abrasive

Organic dye slurries

Red dye slurry (1-methylaminoanthraquinone and starch gum)

Yellow dye slurry (dibenzpyrenequinone and benz anthrone)

Chlorinated Hydrocarbons

W C waste from a chemical plant

W C mixed with coal

WC insulation over copper wire

Chlorinated hydrocarbon waste containing 80% chlorine

Munitions (slurry)

TNT

RDX (cyclotrimethylenetrinitramine)

Composition B

W/OZONE DESTRUCTION

Ozone treatment is an established technology for the treatment of some hazardous wastes. Recent studies show that a combination of ultraviolet light with the ozonation process is a more effective technique for destroying hazardous waste than the use of ozonation alone.

The addition of UV light to the ozonation process has greatly expanded the number of compounds that can be destroyed. Exposed halogen atoms, unsaturated resonant carbon ring structures, readily accessible multi-bonded carbon atoms, and alcohol and ether linkages are particularly susceptible to UV/ozone systems. Compounds with shielded multi-bonded carbon atoms, sulfur compounds, and phosphorous compounds are less susceptible to

3 87

W/ozonation.

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A combination of ozone with UV treatment has been used to destroy PCB's, 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) , nitrobenzene and related derivatives, and the hydrazine family of fuels.

Many complex decisions representing trade-offs are necessary to implement a well-designed, efficiently operated, economic UV/ozonation system. This technology has advanced considerably in recent years, and is close to state-of-the-art for many hazardous wastes. Some wastes which are difficult to oxidize are not treatable by this technology. Reaction kinetics plays a large role in the decision to apply UV/ozone technology to the treatment of a specific waste. Although UV/ozonation is much more limited in the variety and concentration of wastes that can be treated (when compared to conventional incineration, molten salt combustion, or fluidized bed combustion), it is still a viable technology for the treatment of certain hazardous wastes.

Advantages of W/Ozonation

Some advantages of W/ozonation are: -

1.

2 .

Aqueous or gaseous waste streams can be treated.

Capital and operating costs are not excessive as compared to incineration.

3.

4. The system is readily adaptable t on-site

Chemical carcinogens and mutagens can be treated.

treatment of the hazardous waste.

5 . UV/ozonation can be used as pretreatment or as a final treatment to supplement partial treatment systems.

6. Modern systems are usually automated, thereby reducing labor.

Disadvantaqes of W/Ozonation Some disadvantages of W/ozonation are:

1. Ozone is a non-selective oxidant; therefore, the waste stream should contain primarily the hazardous waste and constituents of interest.

2. UV/ozone systems are generally restricted to 1% or lower concentration levels of hazardous compounds. Most hazardous substances treated by this process are in the ppm levels.

88

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3 . Ozone decomposes rapidly with increasing temperature; therefore, excess heat can reduce efficiency.

4. High power costs.

Hazardous Wastes Destroyed W/Ozonation Technoloqy

PCB I s

TCDD (2,3,7,8-tetrachlorodibenzo-p-dioxin)

OCDD (octachlorodibenzo-p-dioxin)

Chlorodioxins (other dioxins are feasible)

Hydrazine

Monomethyl hydrazine

Dimethyl hydrazine (unsymmetrical)

Copper process waste stream

Nitrobenzene

Superiority of Molten Salt Combustion, Fluidized gee Incineration, and UV/Ozonation & Landf ills -- -

All of the emerging technologies--molten salt, fluidized bed, and UV/ozonation--can be considered as alternatives to landfill disposal of hazardous waste. The intent of the emerging technologies is waste destruction, or at least attenuation to acceptable levels. Landfills either store waste in specialized containers or attempt to prevent its spread from the area where it was dumped.

The future fate of hazardous wastes stored in landfills is, in many cases, unknown. Other forms of containment that do not attempt to destroy the hazardous waste may share the same uncertain future. If cost is not considered, the use of technologies that destroy hazardous wastes should be considered far superior to landf ill storage. However, insufficient information exists to compare the emerging technologies on a cost/benefit basis with established landfill practices.

Molten Salt Incineration -- and Fluidized - Bed Incineration -- vs. Conventional Incinerat ion

Both these technologies employ sufficiently high temperatures to efficiently destroy many types of hazardous wastes. Molten salt technology can meet EPA regulations regarding a minimum high temperature and residence time for

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the treatment of certain wastes, even though it employs much lower temperatures than are used in conventional incineration. Compliance with the regulations is achieved with much higher combustion efficiency, reducing the emissions to lower levels. EPA regulations regarding combustion criteria (Federal Register, Volume 43, Number 243, pp. 59008, 59009, December 18, 1978, #250.45.1 Incineration) state that the incinerator shall operate at temperatures greater than 1000°C, greater than 2 seconds resident time, and greater than 2% excess oxygen for the incineration of hazardous wastes. Halogenated aromatic hydrocarbons, such as PCBIs, must be incinerated at more than 12OO0C, and greater than 2 seconds residence time, with greater than 3% excess oxygen. Combustion efficiency must equal or exceed 99.9%. However, there is an exception. Other conditions of temperature, residence time, and combustion efficiency are permitted if an equivalent amount of combustion is demonstrated. Because of its higher combustion efficiency, molten salt combustion complies with the regulation exception. PCB's are combusted by molten salt technology at lower temperatures, yet the combustion efficiency requirement of 99.9% was exceeded by molten salt technology with a combustion efficiency greater than 99.9999% and a nominal residence time of 0.25-0.50 sec. Although both processes have some problems with particulate emissions, they have less problems with particulates than conventional incineration techniques.

Molten salt combustion and fluidized bed incineration can be considered as capital intensive for start-up costs. The same can be said for conventional incineration. Little information exists for the costs of molten salt combustion. The cost statistics for fluidized bed incineration are better known at the pilot plant stage. Fluidized beds and molten salt baths function as heat sinks, and can, in some instances, use the hazardous waste combusted as fuel. Thus, they are potentially less expensive than conventional incineration techniques.

DEVELOPING TECHNOLOGIES

These technologies for the treatment of hazardous are still in the developmental stage. Most of these technologies have been studied only at the bench level: a few are at the pilot plant stage. The technologies reviewed include catalyzed wet oxidation of toxic chemicals, the dehalogenation of compounds by treatment with ultraviolet light and hydrogen, electron irradiation of toxic compounds in aqueous solution, UV/chlorinolysis of hydrazine in aqueous solution, and the catalytic hydrogenation dechlorination of polychlorinated biphenyls (PCB's) .

Wet air oxidation experiments were conducted in a titanium autoclave, but only batch oxidations were investigated. The ultraviolet light/hydrogen technology for

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d

the dehalogenation of compounds has advanced from bench scale to the pilot plant stage. This system is not designed to process waste streams with much more than 1% toxic organic content. The electron treatment of trace organic compounds in aqueous solution has been investigated in the laboratory at MIT. The UV/chlorinolysis of hydrazine in aqueous solution has been tested on 8,000 liter batches of wastewater. The catalytic hydrogenation-dechlorination studies of PCB's took place in an autoclave. A listing of these processes are shown in Table 5.

A description of each process, experimental details, The following lists the plus results and discussion follow.

various chemicals treated by specified processes:

LIST OF TOXIC SUBSTANCES TREATED BY CHEMICAL TECHNOLOGIES

Wet Air Oxidation -- 2,4-D

Glycolic Acid

Pentachlorophenol

Ethylene dibromide

Malathion

Acetic Acid

PCB s

TCDD (tetrachloro-p-doxin)

Kepone

Dehalogenation/W-hydrogen (HZ)

Arochlor 1254 (PCB)

Tetrabromophthalic anhydride

Kepone

Electron Irradiation

2,3,4-Trichlorobiphenyl

4 Monochlorobiphenyl

Monuron

W/chlorinolysis

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TABLE 5

I 1 , DFWOPING TF CHNOI 0 GI FS THESE PROCESSES ARE I N THE PILOT PLArT STAGE, THEY HAVE DEMONSTRATED GREAT POTENTIAL I N ENERGY SAVINGS AND RESOURCE RECOVERY a

PROCESS DESCRIPTIO1 - MODAR PROCESS WATER I S PLACED AT A SUPER CRITICAL THIS PROCESS IS I N

STATE (LESS THAN 3740C AND 218 ATMS), ORGANICS AND GASES ARE VERY SOLUBLE, DESTROYS PCB'S AND ALLOWS FOR POWER

THE PILOT PLANT STAGE

GENERATION OF WASTE (GREATER THAN 5% ORGANI c CONTENT)

PLASMA ARC

SEQUENCING BATCH R EA C TO RS

USAGE OF MICROWAVE TO ASSIST I N THE THIS PROCESS IS I N OXIDATION OF ORGANICS I N THE PRESENCE THE PILOT PLANT

OF OXYGEN AT LOW PRESSURES, STAGE

THIS PROCESS IS A MORE FLEXIBLY ACTIVATED THIS PROCESS I S SLUDGE SYSTEM, T t j IS SYSTEM ALLOWS FOR MOVING TO FULL-SCALE

OPERATION BETTER ADAPTATION TO ORGANICS,

SOLVENT AND METALS THESE PROCESSES ARE BASED ON SOLVENT THIS PROCESS IS RE CO VE RY EXTRACTION, METALS PRECIPITATION, AND MOVING TO FULL-SCALE

OTHER STANDARD TECHNIQUES, THESE OPERATION PROCESSES ARE BEING REFINED TO BECOME ECONOMICALLY FEASIBLE 6

3

c LJ 3 b u i t L/

11 , DE VELOP I N G TECHNOLOGIFS - CONTINUED

PROCESS CATALYZED WET OX1 DATION

DEHALOGENATION WITH UV AND HYDROGEN

BETA TREATMENT OF TOXIC ORGAN I CS

r.sl w

UV/CHLOR I NOLY s I s

CATALYTIC HYDROGENATION DECHLORINATION

DESCRI PT I ON THESE PROCESSES HAVE BEEN USED FOR YEARS, THEY USE COCATALYSTS SUCH AS BROMIDE AS NITRATE ANIONS I N ACIDIC SOLUTIONS TO DESTROY ORGANICS AT l o ~ O c l

THIS PROCESS BREAKS OFF HALOGENS BY REDUCTION CHEMICALLY, THIS HAS BEEN USED WITH KAPONE i

THIS PROCESS USES'AN ELECTRON BEAM AND HAS BEEN SUCCESSFUL FOR ORGANICS DESTRUCTION AND PATHOGEN TREn'ITMENT,

THIS HAS BEEN USED TO OXIDIZE REDUCED WASTE CONTAINING HYDROZINE, COULD BE PROBLEMS WITH CHLORINATED RESIDUES,

THIS I S A CATALYTIC REDUCTION OF ORGANIC COMPOUNDS i

J 3

CURRENT STATE SCALE OPERATIONS

AT THE PILOT PLANT STAi(3E

AT THE COMMERCIAL STAGE

AT THE PILOT PLANT STATE

AT THE PILOT PLANT

STAGE

J

Hydrazine

Monomethylhydrazine

Dimethylnitrosamine

Unsymmetrical dimethylhydrazine

Catalytic Hydrogenation-Dechlorination

PCB's (Arochlor 1242, KC-400)

Destruction -- of Toxic Chemicals a Catalyzed Wet Oxidation Wet air oxidation (WAO) is a commercially proven

technology for the destruction of organics in wastewater and sludges. In conventional wet air oxidation, waste is pumped into the system by a high-pressure pump and mixed with air from an air compressor. The waste is passed through a heat exchanger and then into a reactor where atmospheric oxygen reacts with the organic matter in the waste. The oxidation is accompanied by a temperature rise. The gas and liquid phases are separated, and the liquid is circulated through the heat exchanger before discharge. Gas and liquid are both exhausted. through control valves. System pressure is control led to maintain the reaction temperature as changes occur in feed characteristics (i.e., organic content, heat value, temperature). The mass of water in the system serves as a heat sink to prevent a runaway reaction that might be caused by a high influx of concentrated organics (13).

IT Enviroscience, Inc., of Knoxville, Tennessee, has developed a proprietary catalyzed wet oxidation process based on information in U.S. Patent 3,984,311 (4) (Originally assigned to the Dow Chemical Company, and now assigned to IT Enviroscience for development and commercialization). This process uses a cocatalyst system consisting of bromide and nitrate anions in an acidic, aqueous solution to destroy either organically contaminated aqueous waste or organic residues. Destruction of waste organics is accomplished by mixing a waste with the catalyst system and oxygen (or air) at temperatures greater t6an 100°C (15).

Advantages of the IT Enviroscience catalyzed wet oxidation process are best understood relative to the conventional technologies of uncatalyzed wet oxidation and incineration. In comparison to straight wet oxidation, the catalyzed process achieves high levels of destruction of a variety of organic chemicals at significantly lower temperatures and pressures. Conventional wet oxidation requires temperatures approaching 3OO0C and high pressures to achieve greater than 90% destruction of soluble organics. The catalyzed process operates at less than severe conditions. It also produces no aqueous bottoms product;

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all nonvolatile organics stay in the reactor system until oxidized. The homogenous cocatalyst enables the system to treat water insoluble compounds.

In comparison to incineration of hazardous wastes of aqueous wastes, the catalyzed wet oxidation process has several advantages. Little or no added energy is required and auxiliary fuel is usually not consumed. It has few unit operations and functions at low temperatures and pressures. Vent gas volume and vent gas scrubber effluent are lower than those produced by incineration and are readily adaptable to polishing treatment if required for control of trace toxic releases. With few unit operations and low volume streams, the oxidation system is potentially portable and can be relatively easily developed in pilot-plant tests (15)

The system is projected to be capital intensive from a cost standpoint. Depending on the type of waste and desired destruction rate, capital outlays of $850,000-$1,300,000 are projected (1980).

DEHALOGENATION OF COMPOUNDS By TREATMENT WITH ULTRAVIOLET LIGHT AND HYDROGEN

A patent for a process to dehalogenate compounds by treatment with ultraviolet (UV) light and hydrogen (H2) has been assigned to Atlantic Research Corporation, Alexandria, Virginia (16). The process is effective for halogenated organic compounds with at least one C-halogen group and works in the absence of any substantial amount of oxidizing agent. The halogenated compound is reduced when carbon- halogen lingages are broken (halogens are liberated during the process). The treatment may result in further degradation of the partially dehalogenated compound. Different degrees of dehalogenation are primarily related to the energy in the C-halogen bond and can be compensated by employing higher or lower energy UV radiation.

The process has been demnstrated successfully on Arochlor 1254 (a polychlorinated biphenyl) in methanol and on tetrabromopthalic anhydride in methanol. However, the majority of work has been done on Kepone, both in methanol and water. Degradation of Kepone was found to be pH dependent. When reactions were run in 0.1, 1.0, and 5% NaOH, the latter caustic level gave the best degree of degradation. More than 99% removal of Kepone has been observed in less than 90 minutes. In tests that compared the W + H2 process with UV/ozone or straight UV treatment, the quantity of unreacted Kepone or Arochlor 1254 remaining after a given time was always less for the UV + H2 runs.

Several degradation products were observed including mon-, ai-, tri-, tetra, and pentahydro derivatives of Kepone. Isotopic studies performed indicated that the

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hydrogen in these compounds comes from hydrogen added during the process.

Based on successful bench studies, a pilot plant for the treatment of higher levels of Kepone was built by the Atlantic Research Corporation and was in use during 1980. Economic data regarding the system is currently unavailable. The successful treatment of Kepone implies the system should be adaptable to PCB's and a variety of other organic hazardous wastes in the ppm or lower range (17).

ELECTRON TREATMENT OF TRACE TOXIC ORGANIC COMPOUNDS - AQUEOUS SOLUTIOK-

As part of a National Science Foundation-sponsored program at the Massachusetts Institute of Technology (MIT), the effect of electron bombardment on trace toxic organic compounds was studied in pure water solutions and in model systems containing trace organics in water. Trace organic compounds studied included Monuron (a persistent herbi_ci.de of the urea type), 2,3,4l trichlorobiphenyl, and 4 monochlorobiphenyl (16) .

Although the Van De Graaff generator successfully treated toxic organics, scale-up of the system would be projected as highly cost-intensive. Few hazardous waste generators have access to a high energy accelerator. Since the test samples were placed in Petri dishes and irradiated on a moving belt, little can be inferred as t the type and cost of scale-up feed mechanisms. Moreover, the organics were irradiated in nearly pure water. The attenuating effect of turbidity may be substantial when irradiating a heterogeneous water system.

Consequently this technology, although successful during ideal laboratory conditions, does not appear to be amenable to scale-up from either a cost or industrial standpoint.

W/CHLORINOLYSIS HYDRAZINE IN DILUTE AQUEOUS SOLUTION

A process was developed at Rocky Mountain Arsenal for the United States Air Force by the IIT Research Institute for the UV/chlorinolysis treatment of wastewater containing hydrazine (HZ) in concentrations varying from a few to several thousand parts per million. Some of the wastewater also contained varying amounts of monomethylhydrazine (MMH) , dimethylnitrosamine (DMMA), and unsymmetrical dimethylhydrazine (UDMH) (19).

Samples of the end products of the chlorinolysis process with and without UV were analyzed for end products. Even though the initial end products of the chlorinolysis reactions (N2, CH30H) are not especially toxic, they may further react with chlorine to form compounds such as CH3CL,

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CC14, and nitrogen trichloride (NC13). NC13 is the most undesirable of these since it is explosive.

When samples of the end products of the process f o r chlorinolysis without UV irradiation were analyzed, significant amounts of chlorinated contaminants were found in the samples. However, no contaminants were found in the end product of the UV/chlorinolysis experiment. Although no cost information was cited, the process successfully treaated various hydrazines. The adaptability of the process to the treatment of other hazardous organics is currently unknown, although it would seem probable many other types of organics could be treated by the process. Careful monitoring for undesirable chlorinated by-products would be warranted when testing UV/Chlorinolysis with other organic compounds (19).

CATALYTIC HYDROGENATION-DECHLORINATION _. POLYCHLORINATED BIPHENYLS

Workers at the Osake Pref ecturalResearch Institute and the Daido Oxygen Company, Ltd. , Japan, investigated several research parameters regarding the catalytic hydrogenation- dechlorination of PCB's. The work was reported in 1979. The authors investigated the use of both a Raney-Nickel catalyst and a carbon-supported palladium catalyst. Reaction ofthePCBtookplace inanautoclavewherePCBwas dispersed and emulsified in an aqueous sodium hydroxide solution containing isopropyl alcohol. Reaction temperatures were kept constant within + 0.5OC (20).

Assuming practically 100% dechlorination of KC-400 PCB, using a Palladium-Carbon catalyst, the constant pressure hydrogenation/dechlorination laboratory method for PCB disposal is promising, the authors noted. They did not cite any economic data or cost projections. Scale-up of the system would be capital-intensive due to the cost of building a stainless steel reactor, and the use of caustic would corrode the stainless steel reactor."

Other Developing Technologies

Application of innovative technologies with respect to biological waste treatment approaches are related to genetic engineering, microbial treatment, enzymatic treatment, and synergistic use of applied-fields to biological systems. Most of these approaches are in their initial stages of development but have advanced to various industrial processing schemes. They are listed in Table 6.

Currently, genetic engineering is in a basic research mode with respect to waste treatment. The most pressing area is the need to evaluate the potential of engineered organisms to colonize polluted habitats or to spread new genetic information to indigenous microbes. Before this genetic engineering can be

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TABLE 6

1 1 1 , ODER DE VEI ,OPING TECHNOLO GIES THESE ARE INNOVATIVE TECHNOLOGIES WHICH ARE I N THE DEV€LOPING STAGES, THEY ARE ELUCIDATED BECAUSE THEY COULD BE UTILIZED TO ASSIST I N CATALYZING EXISTING PROCESSES I N THE NEXT FIVE YEARS,

PROCESS DESCRI PT I ON CU RRENT STATE GENETIC PROCESSES DEVELOPMENT OF MUTANT ORGANISMS I N THE LABORATORY

WHICH CAN BE APPLIED I N EXISTING STAGE SYSTEMS, THIS WORK I S JUST BEGINNING TO ARRIVE I N THE LABORATORY

MICROBIAL SYSTEMS DIFFERENT AND DEVELOPING SEEDS UNDER LOW ORGANICS HAVE BEEN NOTED BUT WITH LITTLE a

CxJ

UNDERSTANDING

I N THE LABORATORY STAGE

APPLIED-FIELDS ( NON- IONI ZATION IRRADIATION)

THIS FIELD APPLICATION HAS BEEN NOTED I N THE LABORATORY TO CATALYZE ORGANICS DESTRUCTION AND STAGE MICROBIAL ACTIVITY,

ENZYME APPLICATIONS THIS USAGE HAS ASSISTED I N MICROBIAL I N THE LABORATORY AND OXIDITIVE PROCESSES, COULD GREATLY STAGE ASSIST EXISTING TECHNOLOGIES,

L: G W J J L, 3 3 3

111 , OTHE R DEVEIOPING TECHNOIOGIES - CONT, I

PROCESS DESCR I PT I ON CURRENT STATF INTENSE PLASMA USAGE OF MICROWAVE TO REACT WITH I N THE LABORATORY TREATMENT ARGON, HYDROGEN AND OXYGEN, STAGE

TEMPERATURES UP TO loo~ooo°F HAVE BEEN REPORTED, OBVIOUSLY, THIS PROCESS IS VERY VIABLE I N DESTRUCTION OF ORGANICS,

3

applied, there is need for more baseline microecosystem delineation on natural and current biological systems in rivers, lakes, and wastewater treatment plants. First applications should be in controlled wastewater treatment systems before approaches in natural systems are attempted. Whether new treatment technologies can be developed expeditiously will depend on the outcome of these studies, yet the promise of incisive gene manipulation urges timely exploration of this approace (21).

In the investigation of microbial detoxification of hazardous wastes, the biodegradation of anthropogenic organics present in waters is a complicated and not a well-developed field. Theprobleminthis area isdueto low concentrationsand nutrient levels. In this area, a biofilm approach appears feasible and the method of treatment could modeled by a fluidized bed approach as noted in biologically active carbon systems. Even though much is known about biological treatment, a great deal of basic information is lacking in the biodegradation of trace-level organics such as physical response to bacteria at low substrate levels, relationship between secondary and primary substrates, toxicity of organics at low levels, the ability to utilize real world application settings, the problem of practical degradation, and interactions among communities of microorganisms necessary to completely degrade compounds (22).

The use of applied fields and enzymes with oxidants has been reported to assist the alteration of toxic organics to a biodegradable form. This has been reported for phenols, anilines, tetrachloroethylene, etc. This catalytic treatment appears to influence the steric effects of these compounds and has not effected the structure compounds of these constituents. This work is still in the bench scale phase of study but will definitely reduce the economics of current biological processes by increasing the efficiency of these treatment processes (2 3). Work at Tulane has noted this phenomena with applied-fields (UV, electrostatic, and electromagnetic fields) (24)

Finally, innovative techniques have been reported in the treatment of hazardous wastes utilizing intense plasma fields and microwave energy sources. The plasma torch is a device that utilizes an electrical discharge to change minute quantities of almost any gas (argon, hydrogen, oxygen2 into the hottest sustainable flame known - up to 100,000 F. This treatment process can greatly alter any organic compound and cause a recovery of energy five times that regained to obtain the (plasma) torch. There has been a great deal of research concerning at the application of microwaves in hazardous waste treatment, but due to the lack of predictability of the resulting products, this work has been slow. Until the mechanismsof these processes are understood, this technology will not be fully utilized, but the advantages of these processes in the health industry promote continued research in this area (5).

100

REVIEW OF EXISTING HAZARDOUS WASTE STREAMS IN LOUISIANA

3

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As a result of the first paper by Dr. Jacobus, Table 7 was developed. In this Table, the existing waste streams were investigated to examine current and reuse emerging product technology. This information was obtained from the following sources (25 , 26, 27 , 28 , 29 , and 3 0 ) . These processes are shown with respect to a given stream. For each EPA category, a listing of alternative technology is reported. These alternative technologies include processes that will either recycle or detoxify the waste. In the State of Louisiana, the below technologies appear to be feasible alternatives for detoxification and/or recycling of hazardous wastes:

1.

2 .

3 .

4 .

5 .

6 .

7.

8 .

9.

10 .

Molten Salt Incineration

Fluidized Bed Incineration

Mercury and Silver Recycle (Microwave oxidizes organics)

Oil Recovery (Usage of electrostatic and

electromagnetic fields)

High Gradient Magnetic Separation (Metals recycle)

Oxidation of Sludges (Alter persistent organics to

degradable forms)

Stripping (Organics recycle)

Solvent Extraction (Organics recycle)

Distillation (Organics recycle)

Phenols fractionation (HC1 recovery)

FUTURE WORK

After meeting with the industrial advisory board, information will be collected and cataloged to idenify pertinent potential alternatives to land disposal for selected waste streams. Data sources to be utilized to determine the quantities and composition of industry-generated wastestreams and reclamation methods of disposal include, but are not limited to, trade technical associations; federal and state agencies; disposal facilities; resource recovery facilities; industrial organizations; the U.S. EPA Hazardous Waste Management Division/OSW contractor prepared reports; and, the UN Economic Commission for Europe low and non-waste technology monographs. Pertinent interviews and site visits, where appropriate, will also be conducted during this phase of the study. Examples may include but are not limited to:

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TABLE 7 - EPA Code/ Emerging Resuse Applications in Louisiana

€ P A COOElCURRENT DISPOSAL MATRIX 3 L P I 1 €PA N

0 t 0 2 0 3 0 4 0 5 0 6

1 4 9 0

D to 0 I 1 c 1 F 2 c 3 F 4

5 6 7 F

F 8 F t t F 12 F 19 K 1 K 16

19 2 0 K

K 22 K 2 1 K 2 8 U . 30 K 45 K 48 K 49

50 51 K

K 52 K at K 6 2 K 69 U It K 7 3 K 4 3

> I C 46 K 106 P 3 P 1 4 P 26 P 30 P 63 P I 2 0 P I 2 3

U 2

1:

, f

7 K

3 K

-J u 1

CLASS u n h u n h un h

i n o r g i n o r g i n o r g i n o r g i n o r g i n o r g i n o r g i n o r g

O f 9 o r 9 o r 9 o r 9 O f 0

i n o r g i n o r g i n o r g i n o r g i n o r g i n o r g o r 9 o r 9 o r 9 o r 9 o r 9 O f 9 or9 o r 0 o r 0 p r t r p e t r p e t r p r t r p r t r

i n o r g i n o r g i n o r g i n o r g i n o r g

o r 9 I n o r 9 i n o i g or9

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NAME i g n i t e b l r c o r r o s i v e

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r l e c t r o p l e t i n g s l u d g e s C y r n i d ~ - ~ l 8 C t r O p l r t i n g s o l u t i o n s

p l a t i n g b a t h s l u d g e s c y r n i d r - s a l t b r t h p o t c l e a n i n g

w a s t e r a t o r w i t h c y a n i d r w r s t c r r t e r s l u d g e s - s o r t i n g o f r l u m i n u m b o t t o m s l u d g e w a s t e w a t e r wood p r r s r r r e

h r r r y ends C8rbOn t e t p r o d u c t i o n h r r v y 0116s r t h y l r n e P i c h l o r ~ d e p r o d n .

h e a r y ends v i n y l chloride p r o d u e t i o n h e a v y ends cumenr h y d r o p r r o r i d r p r o d n .

TDt p r o d u e t i o n r r s t r t . t . t - t r i c h l o r o r t h a n r p r o d n .

h e e r y ends t r i C I a n d t e t r a C l r l h y l e n e s p e n t C r a r t e r e t e r r x p l o s i v r r

O A f f l o a t f r o m p e t r o l e u m r e f i n i n g s l o p o i l l p e t r o l r u m r r f i n i n g

r x c h r n g * r r l u d g r l p r t r o l r u m r e f i n i n g A P I s r p a r a t o r s t u d g e l p r t r o l e u m r r f i n i n g t a n k b o t t o m s ( I e r d e d l l p e t r o l r u m r r f i n i n g r m i r r i o n c o n t r o l s l u d g e l s t e e l p r o d u c t i o n

p i c k l e I i q u o r l s t r r l f i n i s h i n g e m i s s i o n c o n t r o l s l u d g r l l r e d s m e l t i n g

b r i n e from m e r c u r y p r o c r s s f o f C I p r o d n c h l o r i n r p r o d u c t i o n w a s t e

d i r t i l l a t i o n b o t t o m s l a n i l i n r p r o d u c t i o n i n h t o r m u l a t i o n ,

w r s t e w r t e r s l u d g e Hg cell p r o d n . C I e c r o l I n

b r n z e n e t h i o l b r n z y l c h l o r i d r

c y a n i d e s ( s o l u b l e C N s a l t s ) h y d r o c y a n i c a c i d

v a n a d i u m p e n t o x i d 8 t o a r p n e n r

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ALTERNATE TECHNOLOGY n o l t b n s r l t , f l u i d i z e d b e d mollen s e l t . f l u i d i z e d b e d m o l t r n s r l t . f l u i d i z e d b e d

p o t . and p u r i f i c a t i o n p p t . and p u r i f i e r t i o n

r e d u c t i o n . p p t . and p u r i f i c a t i o n o r g e n i c P b - o r o n r t i o n . r r c o v r r y

microrev* plesme t o Hg. r e c o v e r y r d s o r p t i o n . o p t . and r e c o v b r y

p p t . . e l r c l r o t y l i c r e c o v e r y s o l v e n t extraction. d i s t i l l a t i o n s o l v r n t e a t r e s t i o n . d i s t i l l a t i o n s o l v r n t e x t r a c t i o n , d i r t i l l e l i o n s o l v r n t e x t r r c t i o n . d i s t i l l a t i o n s o l v e n t o x t r r c t i o n . d i s t i l l a t i o n

p o t . . r e c o r r r y o x i d e t i o n , p p t . . HMS o x i d a t i o n . p p t . . HYS . o x l a a t i o n . p o t . . HMS

m o l t a n s e l t . fluidized b e d s o l v e n t e x t r e e t i o n , d i s t i l l r t i o n s o l v e n t e x t r a c t i o n . P i s t i l l r t i o n s o l v r n t r x t r r c t i o n . d i s t i l l r t i o n

s o l v e n t r x t r r c l i o a . a d s o r p t i o n s o l v e n t e x l r a c t i o n . d i s t i l l a t i o n s o l v e n t o x t r a c t i o n . d i s t i l l a t i o n s o l v r n t e x t r a c t i o n . d i s t i l l a t i o n

m o l t e n selt, f l u i d i z e d b 8 d s o l v e n t e x t r a c t i o n . d i s t i l l e t i o n

a p p l i e d f i e l d s . r x t r a c l i o n a p p l i e d f i r l d s . e x t r r c t i o n

e p p l i r d f i e l d s . e x t r a c t i o n s r p a r r t i o n , HwS s r p r r r t i o n . HYS

o z o n r t i o n microrare. r l r c t r o l y s i s

e p p l i e d f i O l d S , b X t f b C t l O n

n e u t r r l i z e t i o n . o r o n a t i o n microware, e l r c t r o l y s i r

d i s t i ~ ~ r t i o n i o n e x c h a n g r

p y r o l y s i r . r r d u c t i o n m o l t r n salts, UV. o z o n r m o l t e n salts. U V . ozone

p p t . . r x t r ~ c t i o n p y r o l y s i r . r e d u c t i o n

s o l r e n t e r t r r c t i o n . s t r i p p i n g s o l v e n t r ~ t r r c l i o n . s t r i p p i n g

ONC VI'RlX - P A G E ?

102

U U U U U U U U U U U U U U U u U U U U U U U U U U U U U U U U U U U U U U U U

8 o r g 12 o r g 32 i n o c g 36 org 41 ocg 43 org 44 o r g 52 o r g 57 o r g 67 o r g 7 4 o r g I7 o r g 6 0 org $ 7 o r g 90 o r g

103 o r g 105 o r g 112 o r g 122 o r g 128 o r g 129 o r g 133 i n o r g

151 i n o r g 154 o r g 159 o r g 160 org 170 org 1 6 6 o r g 196 o r g 2 1 0 o r g 2 1 1 org 2 2 0 org 2 2 1 o r g 2 2 3 o r a 2 2 7 orp 2 2 0 org 233 o r g 2 3 9 o r g 242 org

147 org

b C t y l I C b C i d

C I l C l u l l l ChrOlS4tb r n i I i n r

c h l o r o d r n r . l o c h o x i r r n r - 2 - c h l o ~ o m r t h y l 'EPI.

r t h r n r . c h l o r o . r i n y l c h l o r i d r . chlor o t o r n crrro1r

c y c l o h r x r n o n r r t h r n r . 1 . 2 - d i b r o m o 'EDI)'

2 - b u t r n r . 1 . 4 - d i c h l o r o r t h y l r n r . d i c h l o r o

r r t h r n r . d i c h l o r o . m r t h y i r n r c h ~ o r i d r " c r r b r m o y l chloridr. d i m r t h y l

1 . t - d i m r t h y l h y d r r x i n r Q i m r t h y l a u l f r t o

2 . 4 - d i n i t r o t o l u r n r * t h y 1 r c 0 t . t .

f o r m r l d r h y d o h r x r c h t o r o b u t r d ~ r n r

h r r r c h l o r o p h r n r h y d r r x t n r

mrlric r n h y d r i d r mr r e u r y mot h r n o l

ME K MEK p r r o x i d

p - n i t r o p h r n o p h e n o l

p y r i d i n r l r t r r c h l o r o r t h y r n r

t r t r r c h l o r o m r t h r n r .carbon 1.1. t o l u r n e

t o l u r n r d i r m i n r TO I

1 . 1 . 2 - t r i c h l o r o r l h y l r n r t r i c h l o r o r t h r n r

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r h : s h i p o u t of a t r t r si = s u r f r c r impoundmrnt

i nc I f I f

I f i n c , t f

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i ac i ac

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t f . r i i n j r h

i n c . l f

i n c . 1 1 i n c , l t i ne i n e I f

i n c . l f i n e

r o l r r n t r x t r r c t i o n . s t r i p p i n g r o l r r n t o x r r d u c t i o n . r o l r r n t 01 r o l r r n t 01 r o l v r n t ox r o l v r n t 01 r o l r r n t ex r o l r r n t e x r o l r r n t o x r o l v r n t ox r o l r r n t ox r o l v r n t o x

r o l r r n t 01 r o l r r n t o x r o l r r n t o r

f a c t i o n . i t r i p p i n g p p t . . p u r i f i c r t i o n f a c t i o n . r t r i p p i n g rrctioa. a t r i p p i n g r r c t i o n . r t r i p p i a g r r c t i o n . i t r i p p i n g r r c t i o n . a t r i p p i n g r r c l i o n . s t r i p p i n g r r c t i o n . a t r i p p i n g r r c t i o n . r t r i p p i n g r r c t i o n . s t r i p p i n g r r c t t o n . s t r i p p i n g

r r c t i o n . r t r i p p i n g r r c t i o n . r t r i p p i a g r r c t i o n . s t r i p p i n g

r o l v r n t e x t r a c t i o n . s t r i p p i n g r o l r r n l r x t r r c t i o n , r t r i p p i ? g r o l r r n t r x t r r c t i o n . s t r i p p i n g r o l r r n t r r t r r c t i o n . s t r i p p i n g

o x i d r t i o n r o l r r n t r x t r r c t i o n . s t r i p p i n g p p t . . rlretrolyria, r r c o v r r y r o l r r n t r x t r r c t i o n . s t r i p p i n g r o t v r n t r x t r r c t i o n . a t r i p p i n g r o l v r n t e x t r a c t i o n . s t r i p p i n g a o l r r n t r x t r r c t i o n . r t r i p p i n g r o l r r n t o x t r a c t i o n . i t r i p p i n g s o l v e n t r r t r r c t i o n . s t r i p p i n g s o l v e n t r x t r r c t i o n . s t r i p p i n g - r o l v r n t r x t r r c t i o n . s t r i p p i n g r o l v r n t e x t r a c t i o n . s t r i p p i n g r o l v r n t r x t r r c t i o n . s t r i p p i n g r o l r r n t r x t r r c t i o n . r t r i p p i n g r o l v r n t r r t r r c t i o n . s t r i p p i n g r o l v r n t r x t r r c t i o n , r t r i p p t n g r o ~ v r n t e x t r a c t i o n , r t r i p p i n g r o l v r n t o x t r a c t i o n , r t r b p p t n g r o l r r n t r x t r r c t i o n . s t r i p p i n g

103

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-9

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.J

1.

2.

3.

4 .

5 .

6 .

7 .

8 .

9.

10.

11.

Ed NSF, Program Director

Earnest F. Gloyna, Dean of Engineering, University of Texas at Austin

Norbert B. Shomaker, U.S. EPA Solid and Hazardous Waste Research Division Cincinnati, Ohio

David Shultz, Southwest Research Institute, San Antonio, Texas

Marvin B. Rubin, U.S. National Focal Point on Low and Non-Waste Technology, Bureau of Industrial Economics, Dept. of Commerce, Washington, D.C.

Robert B. Pojasik, Vice-president and Technical Director, Roy F. Weston, Inc., Woburn, Mass.

Amir A. Metry, Vice-President, IU Conversion Systems, Inc., Horsham, PA.

James W. Patterson, Director, Industrial Wastes Elimination Center, Illinois Institute of Technology, Chicago, IL.

Director of EPA/Stae of California study to document and evaluate emerging technologies which offer promise for ameliorating hazardous waste disposal problems..

Battelle Columbus Laboratories and Chemistry Abstracts to obtain Further Literature Sources and data concerning stream makeup and potentially developing technologies.

-

Geraldine Cox , Chemical Manufacturing Association, Washington, D.C.

A matrix will be developed for each SIC group of importance to the state of Louisiana as determined by DNR which will identify potentially reclaimable constituents of typical wastestreams. Candidate management technologies will next be identified for each constituent or group of constituents.

After completion of this work, pertinent international experts will be contacted to obtain information of potential processes not currently utilized in the United States. This is very important since in Japan, Korea, China, and Europe the recycle of waste has currently progressed at a greater rate than in the United States. These countries have been under resource limitation f o r m a n y y e a r s d u e t o a l a c k o f o f n a t u r a l resources.

104

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_. - -_._I-- ---I

Oppelt, E. T., Thermal Destruction Options for Controlling Hazardous Wastes11 Civil Engineering - ASCE pp. 72-75 (Sept., -- -- 1981).

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Fochtman, E.G., et a&., Chlorinolysis treatment of hydrazine in dilute aqueous solution. Presented at Symposium of Environmental Chemistry of Hydrazine, Tyndall Air Force Base, Florida (1979)

Yasuhiro, H. &., Conversion of polychlorinated biphenyls to useful materials by a catalytic hydrogenation- dechlorination method. Presented at the American Chemical Society Meeting in Honolulu, Hawaii (1979).

Johnson, J.B. and Robinson, S.O., "Opportunities for Development of New Detoxication Processes through Genetic Engineering", in Detoxication of Hazardous Waste, edited by J.H. Exner, Ann Arbor Scienie Publishers, Ann Arbor, Michigan, pp. 301-314 (1982).

Rittman, B.E. and Kobayashi, H., "Microbiological Separation for Trace-Organics Rmoval", edited by J.H. Exner, Ann Arbor Science Publishers, Ann Arbor, Michigan, pp. 323-347 (1982).

Alberti, B.M. and Klibanov, A.M., "Peroxidase for Removal of Hazardous Aromatics from Industrial Wastewaterll, edited by J. H. Exner, Ann Arbor Science Publishers, Ann Arbor, Michigan pp. 349-356 (1982).

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28. Dilloy, A.P., Pesticide Disposal and Detoxification - Process and Technologies, -- Noyes Data Corporation, ParE -Neaersey, pp. 587 (1981).

I_- -- --

29. LaGrega, M.D. and Henduigy, L.K., Toxics and Hazardous Wastes, Proceedings f the Fifteenth MrdzATl-anmc I x s G E i Waste Cnference, Butterwrth Publishers, Boston, Ma., pp. 697 (1983).

30. Alleman, J.E. and Kavanaugh, J.T., Industrial --- Wastes --f

Proceedings of the Fourteenth Mid-Atlantic Industrial Waste Conference, Butterworth Publsihers, Boston, Ma. pp. 612 (1982) .

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107 3