Incineration of Pesticide Wastes - ACS Symposium Series (ACS

11 Incineration of Pesticide Wastes THOMAS L. FERGUSON and RALPH R. WILKINSON

Downloaded by PURDUE UNIV on July 5, 2016 | http://pubs.acs.org Publication Date: August 15, 1984 | doi: 10.1021/bk-1984-0259.ch011

Midwest Research Institute, Kansas City, MO 64110

Incineration is one of the preferred methods of disposal for a wide range of wastes, including many RCRA-designated hazardous wastes that contain organic pesticides. Currently, a high level of activity is focusing on the evaluation and application of incineration technology. This paper presents an overview of those areas of hazardous waste incineration applicable to pesticide wastes. Research efforts, destruction and removal efficiency determination, and application of incineration techniques to pesticide-containing wastes are reviewed.

Incineration has long been recognized as an effective means for disposing of unwanted organic pesticides and certain wastes from pesticide manufacture. (Organometallic pesticides present special problems due to the potential for metal emissions, and are generally not disposed of by incineration.) As early as 1970, in the interim guidelines for pesticide disposal by the Federal Working Group on Pesticides (1.), incineration was proposed as one of the most appropriate methods of pesticide disposal. In 1974, federally recommended procedures were published under authority of the 1972 amendments of the Federal Insecticide, Fungicide, and Rodenticide Act (FIFRA) that addressed pesticide disposal (2). These recommendations identified an incinerator operating at 1000°C (1832°F) with 2-s retention time in the combustion zone as acceptable for destruction of organic pesticides. Other incinerators, such as those for municipal solid waste capable of effecting complete pesticide destruction, are also acceptable. During this same time frame, i . e . , from the early 1970s to date, a number of research and demonstration studies have been conducted involving pesticide incineration. Most of these concern either the identification of incinerator 0097-6156/84/0259-0181$06.00/0 © 1984 American Chemical Society

Krueger and Seiber; Treatment and Disposal of Pesticide Wastes ACS Symposium Series; American Chemical Society: Washington, DC, 1984.

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T R E A T M E N T A N D DISPOSAL O F PESTICIDE WASTES

operating conditions required t o destroy p e s t i c i d e s or v e r i f i cation that a specific i n c i n e r a t i o n f a c i l i t y i s i n fact operating w i t h an a c c e p t a b l e l e v e l o f d e s t r u c t i o n e f f i c i e n c y . W h i l e much o f t h i s w o r k h a s a d d r e s s e d t h e d e s t r u c t i o n o f p e s t i c i d e s as s u c h , most c u r r e n t a c t i v i t y i s c o n c e r n e d w i t h t h e more g e n e r a l p r o b l e m o f h a z a r d o u s w a s t e i n c i n e r a t i o n . The f o l l o w i n g d i s c u s s i o n s u m m a r i z e s some o f t h e k e y s t u d i e s t h a t have d e a l t s p e c i f i c a l l y w i t h t h e i n c i n e r a t i o n o f p e s t i c i d e s and p e s t i c i d e w a s t e s , as w e l l as h a z a r d o u s w a s t e i n c i n e r a t i o n i n g e n e r a l .


Pesticide

Incineration

S e v e r a l o f t h e key research p r o j e c t s conducted t o assess p e s t i c i d e i n c i n e r a t i o n a r e shown i n T a b l e I . Perhaps t h e s i n g l e b i g g e s t demonstration t o date o f e f f e c t i v e p e s t i c i d e d i s p o s a l was t h e a t - s e a i n c i n e r a t i o n o f A g e n t Orange ( 3 ) . D u r i n g A u g u s t 1977, t h e M/T V u l c a n u s , o p e r a t i n g u n d e r a U.S. E n v i r o n m e n t a l P r o t e c t i o n A g e n c y ( E P A ) p e r m i t i s s u e d t o t h e U.S. A i r F o r c e , i n c i n e r a t e d 8.7 m i l l i o n l i t e r s ( 2 . 3 m i l l i o n g a l l o n s ) o f A g e n t Orange i n t h e m i d - P a c i f i c Ocean. Des t r u c t i o n e f f i c i e n c y was e s t i m a t e d t o be a t l e a s t 9 9 . 9 9 % , and no d e t e c t a b l e 2,3,7,8-tetrachlorodibenzo-£-dioxin (TCDD) was f o u n d i n the stack gas. G e n e r a l E l e c t r i c Company, u n d e r a n EPA p e r m i t , i n c i n e r a t e d n e a r l y 6,000 L (1,500 g a l . ) o f 2 0 % l i q u i d DDT f o r m u l a t i o n s i n a l i q u i d i n j e c t i o n i n c i n e r a t o r near P i t t s f i e l d , Massachusetts, i n S e p t e m b e r 1974 ( 4 ) . The f a c i l i t y u t i l i z e d a v o r t e x c o m b u s t o r o f t h e t y p e n o r m a l l y u s e d f o r d i s p o s a l o f o i l s and s o l v e n t s . Opera t i n g t e m p e r a t u r e s r a n g e d f r o m 870 t o 980°C w i t h r e t e n t i o n t i m e s o f 3 t o 4 s and 120 t o 1 6 0 % e x c e s s a i r . O v e r a l l d e s t r u c t i o n e f f i c i e n c y e x c e e d e d 99.99%. C o n c e n t r a t i o n s o f DDT, DDE, and DDD i n t h e s t a c k gas and s c r u b b e r w a t e r were b e l o w a n a l y t i c a l d e t e c tion limits. I n a s i m i l a r s t u d y , V e r s a r , I n c . , i n 1974-1975, demons t r a t e d f o r EPA t h a t DDT and 2,4,5-T f o r m u l a t i o n s were d e s t r o y e d i n a m u n i c i p a l sewage s l u d g e i n c i n e r a t o r i n P a l o A l t o , C a l i f o r n i a ( 5 ) . The p e s t i c i d e s were added t o s l u d g e ( w h i c h c o n t a i n e d 2 0 % b y w e i g h t o f s o l i d s ) t o f o r m a m i x t u r e t h a t was 2 t o 5% b y w e i g h t i n p e s t i c i d e s . D e s t r u c t i o n e f f i c i e n c i e s r a n g e d f r o m 99.95 t o 9 9 . 9 9 % f o r a n a v e r a g e h e a r t h t e m p e r a t u r e f r o m 600 t o 690°C and a n a f t e r b u r n e r t e m p e r a t u r e f r o m 650 t o 660°C. A two-step l a b o r a t o r y thermal-decomposition a n a l y t i c a l system i n v o l v i n g v a p o r i z a t i o n and t h e r m a l d e s t r u c t i o n was d e v e l o p e d i n 1975 b y t h e U n i v e r s i t y o f D a y t o n R e s e a r c h I n s t i t u t e f o r EPA ( 6 ) . V a p o r i z a t i o n o f p u r e p e s t i c i d e o c c u r r e d a t 200 t o 300°C and was f o l l o w e d b y d e c o m p o s i t i o n i n a q u a r t z t u b e a t t e m p e r a t u r e s e x c e e d i n g 900°C. The d e s t r u c t i o n e f f i c i e n c i e s f o r DDT, K e p o n e , and m i r e x e x c e e d e d 9 9 . 9 9 % a t 2-s r e s i d e n c e t i m e and g r e a t e r t h a n 900°C.


11.

FERGUSON AND WILKINSON

Table I .

Selected Pesticide Incineration Studies


Pesticides

Investigators

System

A g e n t Orange

Ocean C o m b u s t i o n Services

Liquid Injection

DDT

General E l e c t r i c Co.

Liquid Injection

DDT a n d 2,4,5-T

Versar, Inc.

Sewage Sludge

DDT, K e p o n e , and M i r e x

Univ. Dayton Research Inst.

Aldrin, Atrazine, C a p t a n , DDT, M a l a t h i o n , Mirex, Picloram, T o x a p h e n e , and Z i n e b

Midwest Research Institute

Multiple Chamber

C h l o r d a n e , DDT, D i e l d r i n , 2,4-D, L i n d a n e , and 2,4,5-T

TRW S y s t e m s , Inc.

Multiple Chamber

C h l o r d a n e and Hexachlorobenzene

Rockwell

Molten-Salt Bath

PCP-Treated Wooden B o x e s

L o s Alamos N a t i o n a l Lab.

Note:

183

Incineration of Pesticide Wastes

Intl.

DE = d e s t r u c t i o n e f f i c i e n c y ; DRE = d e s t r u c t i o n and r e m o v a l

DE o r DRE (%)

> 99. 99 > 99. 99

99. 9599.,99

> 99..99 Two-Stage Vaporization/ Destruction

Multiple Chamber

> 99,.99

> 99 .99

> 99 .99 > 99 .99

efficiency.

S u b s e q u e n t l y , m o d i f i e d t h e r m a l d e c o m p o s i t i o n s y s t e m s were developed by t h e U n i v e r s i t y o f Dayton t o i n v e s t i g a t e t h e d e s t r u c t i o n o f complex hazardous waste m i x t u r e s ( 7 ) . These systems u t i l i z e d v a r i o u s c o m b i n a t i o n s o f gas c h r o m a t o g r a p h s / m a s s s p e c t r o m e t e r s / c o m p u t e r s w h i c h were i n c o r p o r a t e d i n t o t h e v a p o r i z a t i o n and d e c o m p o s i t i o n p r o c e s s . U s i n g t h e s e s y s t e m s , t h e t h e r m a l d e c o m p o s i t i o n o f DDE, DDT, d i a z i n o n , e n d r i n , h e x a c h l o r o b e n z e n e , K e p o n e , m i r e x , and p e n t a c h l o r o n i t r o b e n z e n e was s t u d i e d , and i n s e v e r a l i n s t a n c e s s t a b l e i n t e r m e d i a t e p r o d u c t s o f i n c o m p l e t e d e s t r u c t i o n were o b s e r v e d . Kepone a t 400 t o 500°C y i e l d e d h e x a c h l o r o c y c l o p e n t a d i e n e , h e x a c h l o r o b e n z e n e , and an u n i d e n t i f i e d c h l o r i n a t e d h y d r o c a r b o n , a l l



184

T R E A T M E N T A N D D I S P O S A L OF PESTICIDE WASTES

o f w h i c h were s t a b l e a t t h e s e t e m p e r a t u r e s . S i m i l a r l y , pentac h l o r o n i t r o b e n z e n e a t 500 t o 550°C y i e l d e d hexachlorobenzene w h i c h was t h e r m a l l y decomposed a t t e m p e r a t u r e s above 650°C. I n 1974 M i d w e s t R e s e a r c h I n s t i t u t e o p e r a t e d a p i l o t - s c a l e m u l t i p l e chamber i n c i n e r a t o r t o e v a l u a t e f o r EPA t h e o p e r a t i o n a l v a r i a b l e s f o r p e s t i c i d e i n c i n e r a t i o n ( 8 ) . The s y s t e m i n c l u d e d a. p i l o t - s c a l e i n c i n e r a t o r , a t h r e e - s t a g e s c r u b b e r s y s t e m , and a s c r u b b e r water t r e a t m e n t system. Nine p e s t i c i d e s (aldrin, a t r a z i n e , c a p t a n , DDT, m a l a t h i o n , mirex,' p i c l o r a m , t o x a p h e n e , and z i n e b ) i n 15 l i q u i d and s o l i d f o r m u l a t i o n s were s t u d i e d . D e s t r u c t i o n e f f i c i e n c i e s g e n e r a l l y exceeded 99.99% o v e r a range o f t e m p e r a t u r e s and r e t e n t i o n t i m e s (~ 950 t o 1100°C, ~ 1.2 t o ~ 6 s, and 80 t o 160% e x c e s s a i r ) . T h i s s t u d y a l s o documented the g e n e r a t i o n of measurable q u a n t i t i e s of cyanide i n the i n c i n e r a t o r o f f - g a s d u r i n g the i n c i n e r a t i o n of organonitrogen pesticides. TRW S y s t e m s , I n c . , c o n d u c t e d a l a b o r a t o r y - s c a l e i n c i n e r a t i o n s t u d y f o r t h e U.S. Army f r o m 1973 t o 1975 ( 9 ) . E l e v e n i n d i v i d u a l p e s t i c i d e f o r m u l a t i o n s and t h r e e m i x e d p e s t i c i d e f o r m u lations containing s i x d i f f e r e n t active ingredients (chlordane, 2,4-D, DDT, d i e l d r i n , l i n d a n e , and 2,4,5-T) were i n c i n e r a t e d i n a liquid injection incinerator. The e x p e r i m e n t a l a p p a r a t u s c o n s i s t e d o f a f u e l a t o m i z e r , c o m b u s t i o n chamber, a f t e r b u r n e r , q u e n c h chamber, and s c r u b b e r u n i t . Destruction efficiencies e x c e e d e d 9 9 . 9 9 % f o r a minimum 0.4-s r e s i d e n c e t i m e a t t e m p e r a t u r e s above 1000°C w i t h 45 t o 6 0 % e x c e s s a i r . M o l t e n s a l t i s a t e c h n i q u e t h a t has b e e n c o n s i d e r e d f o r t h e d e s t r u c t i o n o f p e s t i c i d e s and o t h e r h a z a r d o u s w a s t e s f o r s e v e r a l years. I n a r e c e n t s t u d y b y R o c k w e l l I n t e r n a t i o n a l f o r EPA ( 1 0 ) , t h e d e s t r u c t i o n o f s o l i d h e x a c h l o r o b e n z e n e (HCB) and l i q u i d c h l o r d a n e exceeded 99.99% i n a molten sodium carbonate b a t h a t 900 t o 1000°C w i t h a r e s i d e n c e t i m e o f 0.75 s. For the p i l o t - s c a l e t e s t s , t h e c o n c e n t r a t i o n o f HCB and c h l o r d a n e i n t h e s p e n t m e l t was < 1 ppm. The HC1 c o n c e n t r a t i o n i n t h e o f f - g a s was < 100 ppm. A p r o t o t y p e s y s t e m (100 kg w a s t e p e r h o u r ) w h i c h u t i l i z e s a n o n r e f r a c t o r y m e t a l v e s s e l i s u n d e r c o n s t r u c t i o n and was s c h e d u l e d t o b e g i n o p e r a t i n g i n l a t e 1983 ( 1 0 ) . The u n i t i s d e s i g n e d f o r t r a n s p o r t t o f i e l d s i t e s f o r temporary waste d e s t r u c t i o n such as i n c l e a n u p o f a h a z a r d o u s w a s t e s i t e o r c o n t i n u o u s w a s t e d e s t r u c t i o n a t a waste generator's p l a n t s i t e . I n 1981 t h e Los Alamos N a t i o n a l L a b o r a t o r y i n v e s t i g a t e d f o r EPA t h e t h e r m a l d e s t r u c t i o n o f wooden b o x e s t r e a t e d w i t h p e n t a c h l o r o p h e n o l (PCP). The i n c i n e r a t i o n s y s t e m c o n s i s t e d o f a dual-chamber, c o n t r o l l e d - a i r i n c i n e r a t o r , a s p r a y quench column, a v e n t u r i s c r u b b e r , and a p a c k e d - c o l u m n a c i d gas a b s o r b e r ( 1 1 ) . D e s t r u c t i o n e f f i c i e n c i e s f o r PCP e x c e e d e d 9 9 . 9 9 % f o r c o m b u s t i o n chamber t e m p e r a t u r e s above 980°C, 2 0 % e x c e s s a i r , and a r e t e n t i o n t i m e g r e a t e r t h a n 2.5 s. F o r t h e s e c o n d i t i o n s , TCDD and


11.



185

t e t r a c h l o r o d i b e n z o f u r a n were u n d e t e c t a b l e i n t h e o f f - g a s e s a t a n a l y t i c a l d e t e c t i o n l i m i t s o f 1 ppb and 5 p p b , r e s p e c t i v e l y .


RCRA R e g u l a t i o n s I n t e r e s t i n t h e g e n e r a l t o p i c o f hazardous waste i n c i n e r a t i o n has b e e n s t i m u l a t e d b y t h e R e s o u r c e C o n s e r v a t i o n and R e c o v e r y A c t (RCRA) o f 1976. U n d e r t h i s a u t h o r i t y , EPA h a s e n a c t e d r e g u l a t i o n s a f f e c t i n g f a c i l i t i e s w h i c h g e n e r a t e , s t o r e , t r e a t , and dispose o f hazardous waste. I n c i n e r a t i o n has r e c e i v e d a g r e a t d e a l o f a t t e n t i o n i n t h i s r e g u l a t o r y process because i t i s a t e c h n o l o g y t h a t i s a l r e a d y a v a i l a b l e and p r o v i d e s p e r m a n e n t d i s p o s a l f o r many t y p e s o f o r g a n i c w a s t e s . A w a s t e s t r e a m may be d e f i n e d a s h a z a r d o u s u n d e r RCRA i f i t meets c e r t a i n c r i t e r i a f o r i g n i t a b i l i t y , c o r r o s i v i t y , r e a c t i v i t y , or t o x i c i t y , o r i f t h e waste stream i s s p e c i f i c a l l y i d e n t i f i e d by EPA as a h a z a r d o u s w a s t e . An i n d i v i d u a l w a s t e s t r e a m i s s u b j e c t t o b e i n g c l a s s i f i e d a s h a z a r d o u s ( l i s t e d ) i f i t c o n t a i n s a n y one o f a p p r o x i m a t e l y 375 c h e m i c a l s i d e n t i f i e d b y EPA as h a z a r d o u s constituents. These d e s i g n a t e d c h e m i c a l s a r e f r e q u e n t l y r e f e r r e d t o as A p p e n d i x V I I I compounds b e c a u s e o f where t h e y a r e l i s t e d i n the p u b l i s h e d r e g u l a t i o n . P e s t i c i d e s a r e v e r y much a p a r t o f t h e d e f i n i t i o n o f h a z ardous wastes (Table I I ) . I n f a c t , t h e t o x i c i t y c h a r a c t e r i s t i c o f h a z a r d o u s w a s t e a s d e f i n e d b y RCRA ( r e f e r r e d t o a s e x t r a c t i o n p r o c e d u r e o r EP t o x i c i t y ) i s b a s e d on t h r e s h o l d c o n c e n t r a t i o n s o f e i g h t m e t a l s and s i x p e s t i c i d e s i n a n e x t r a c t o f t h e w a s t e ( T a b l e II-A). S i x t e e n o f t h e s p e c i f i c hazardous waste streams l i s t e d by

Table

A.

B.

C.

II.

P e s t i c i d e s i n RCRA H a z a r d o u s Waste

EP ( E x t r a c t i o n P r o c e d u r e ) 2,4-D Endrin S p e c i f i c Manufacturing Cacodylic Acid Chlordane Creosote

Toxicity Lindane Methoxychlor

Wastes 2,4-D Disulfoton MSMA

Example Appendix V I I I Hazardous Aldrin DDT Amitrole Dieldrin Chlordane Dimethoate Creosote Disulfoton

Source:

Constituents Endosulfan Endrin Heptachlor Methoxychlor

Silvex Toxaphene

Phorate 2,4,5-T Toxaphene

Parathion PCNB Toxaphene Warfarin

40 CFR P a r t 2 6 1 .


TREATMENT AND

186

DISPOSAL OF PESTICIDE WASTES


EPA r e s u l t from the manufacture of nine s p e c i f i e d p e s t i c i d e s (Table I I - B ) . Of t h e a p p r o x i m a t e l y 375 A p p e n d i x V I I I c h e m i c a l s , a b o u t o n e - f i f t h a r e p e s t i c i d e a c t i v e i n g r e d i e n t s ; some e x a m p l e s a r e shown i n T a b l e I I - C . T h u s , c o m p l i a n c e w i t h RCRA i n c i n e r a t o r r e g u l a t i o n s i s d i r e c t l y r e l a t e d to the i n c i n e r a t i o n of p e s t i c i d e s . R e c e n t e f f o r t s have b e e n c o n c e r n e d w i t h t h e a c c e p t a b l e ope r a t i o n of hazardous waste i n c i n e r a t o r s . C u r r e n t l y , the p e r f o r mance s t a n d a r d s f o r i n c i n e r a t o r s b u r n i n g h a z a r d o u s w a s t e a d d r e s s three areas: F i r s t , t h e i n c i n e r a t o r must a c h i e v e a d e s t r u c t i o n and r e m o v a l e f f i c i e n c y (DRE) of at l e a s t 99.99% f o r each of the d e s i g n a t e d Appendix V I I I chemicals p r e s e n t i n the waste feed. I n o t h e r w o r d s , i 0.01% o f t h e r e s p e c t i v e compound i n t h e w a s t e f e e d c a n be e m i t t e d i n t h e i n c i n e r a t o r s t a c k gases. The s p e c i f i c A p p e n d i x V I I I c h e m i c a l s e v a l u a t e d a r e s e l e c t e d by EPA f r o m t h o s e f o u n d i n t h e h a z a r d o u s w a s t e a t r e a s o n a b l e c o n c e n t r a t i o n s and a r e t e r m e d p r i n c i p a l o r g a n i c h a z a r d o u s c o n s t i t u e n t s (POHCs). S e c o n d , HC1 e m i s s i o n s must n o t e x c e e d e i t h e r 1.8 kg/h (4 l b / h ) o r 1% o f t h e HC1 i n t h e s t a c k gas p r i o r t o e n t e r i n g any p o l l u t i o n c o n t r o l e q u i p m e n t , w h i c h e v e r i s g r e a t e r . T h i r d , t h e p a r t i c u l a t e m a t t e r e m i t t e d must n o t e x c e e d 180 mg/DSCM (0.08 g r / D S C F ) , when c o r r e c t e d t o 7% 0 . 2

Most of the ongoing a c t i v i t y r e l a t i n g t o hazardous waste i n c i n e r a t i o n (and t h e r e f o r e p e s t i c i d e i n c i n e r a t i o n ) i s f o c u s e d on i d e n t i f y i n g f a c i l i t i e s c a p a b l e o f m e e t i n g t h e s e r e q u i r e m e n t s and on v e r i f y i n g t h e i r p e r f o r m a n c e . H a z a r d o u s Waste

Incineration

I n c i n e r a t i o n o f h a z a r d o u s w a s t e s i n an a c c e p t a b l e manner r e q u i r e s a r a t h e r s o p h i s t i c a t e d f a c i l i t y i n terms of the a c t u a l i n c i n e r a t o r , i t s a s s o c i a t e d c o n t r o l s y s t e m s , and t h e p o l l u t i o n c o n t r o l devices. E x i s t i n g i n d u s t r i a l p r o d u c t i o n f a c i l i t i e s as w e l l as d e d i c a t e d h a z a r d o u s w a s t e i n c i n e r a t o r s have b e e n i n v e s t i g a t e d for p o t e n t i a l application. I n d u s t r i a l Processes. T a b l e I I I shows s e v e r a l h i g h t e m p e r a t u r e p r o d u c t i o n p r o c e s s e s ( d e s i g n a t e d i n d u s t r i a l f u r n a c e s ) t h a t have been c o n s i d e r e d f o r the i n c i n e r a t i o n of hazardous waste (12). C r i t e r i a c o n s i d e r e d i n e v a l u a t i n g t h e use o f s u c h f a c i l i t i e s i n c l u d e the c o m p a t i b i l i t y of the p r o c e s s w i t h hazardous waste d i s p o s a l , t h e number and a v a i l a b i l i t y o f a p p r o p r i a t e f a c i l i t i e s , and t h e p r o x i m i t y o f t h e f a c i l i t i e s t o s i t e s g e n e r a t i n g h a z a r d ous w a s t e . P r o c e s s c o m p a t i b i l i t y must i n c l u d e c o n s i d e r a t i o n o f o p e r a t i n g c o n d i t i o n s s u c h as t e m p e r a t u r e and r e t e n t i o n t i m e , any a c t u a l o r p e r c e i v e d i m p a c t on p r o d u c t q u a l i t y , and t h e p o t e n t i a l


11.

FERGUSON A N D WILKINSON


187

Table I I I . High Temperature P r o c e s s e s Selected for Further Evaluation Industry Brick Carbon B l a c k P r i m a r y Copper P r i m a r y Lead I r o n and S t e e l


Lime

Glass

Process o r Furnace Tunnel K i l n O i l Furnace Process Réverbératory F u r n a c e B l a s t Furnace B l a s t Furnace Open H e a r t h F u r n a c e Long R o t a r y K i l n Short Rotary K i l n w i t h Stone P r e h e a t e r M e l t i n g Furnace

f o r e m i s s i o n o f hazardous wastes d u r i n g m a t e r i a l s h a n d l i n g opera t i o n s ( f u g i t i v e e m i s s i o n s ) . B a s e d on t h e s e c r i t e r i a , t h e EPA i n i t i a t e d a study t o i d e n t i f y p o t e n t i a l h i g h temperature processes. I n i t i a l l y , most m a j o r p r o c e s s e s w i t h an o p e r a t i n g temp e r a t u r e g r e a t e r t h a n 649°C (1200°F) were i n c l u d e d . T h e r e a r e b o t h t e c h n i c a l and i n s t i t u t i o n a l p r o b l e m s , howe v e r , i n u s i n g most o f t h e s e p r o c e s s e s f o r w a s t e i n c i n e r a t i o n . W h i l e t h e p o t e n t i a l f o r o b t a i n i n g l o w c o s t e n e r g y does e x i s t , t h e r e seems t o be v e r y l i m i t e d p o t e n t i a l f o r t h e u s e o f most o f these f a c i l i t i e s f o r i n c i n e r a t i n g p e s t i c i d e wastes. The wet p r o c e s s cement k i l n i s i n a somewhat d i f f e r e n t c a t egory from o t h e r h i g h temperature i n d u s t r i a l p r o c e s s e s because cement k i l n s have b e e n u s e d t o i n c i n e r a t e s e v e r a l c h e m i c a l w a s t e s and t h e i r DREs h a v e b e e n r a t h e r e x t e n s i v e l y e v a l u a t e d ( 1 3 - 1 5 ) . Cement k i l n s a r e w e l l m a t c h e d t o h a z a r d o u s w a s t e i n c i n e r a t i o n c o n s i d e r i n g t h e i r s i z e (up t o 25 f t i n d i a m e t e r and o v e r 500 f t l o n g ) and o p e r a t i n g t e m p e r a t u r e s o f 1370° t o 1450°C (2500° t o 2650°F) i n t h e k i l n b u r n i n g z o n e . Another important f a c t o r i s t h e i r a b i l i t y t o a d s o r b c h l o r i n e e m i s s i o n s i n t h e cement, t h u s a i d i n g i n m e e t i n g t h e HC1 e m i s s i o n c o n t r o l r e q u i r e m e n t ( 1 6 ) . T e s t s have b e e n c o n d u c t e d on w e t and d r y cement p r o c e s s e s i n t h e U n i t e d S t a t e s , C a n a d a , Sweden, and P u e r t o R i c o f o r w a s t e s c o n t a i n i n g a w i d e r a n g e o f c h l o r i n a t e d c h e m i c a l s , i n c l u d i n g PCBs (13-16). G e n e r a l l y , t h e DREs have b e e n f o u n d t o b e i n t h e r a n g e o f 9 9 . 9 9 % , w i t h no a d v e r s e i m p a c t o n p r o d u c t q u a l i t y o r p l a n t o p e r a t i o n i f c h l o r i n e a d d i t i o n i s r e s t r i c t e d t o l e s s t h a n 1% o f t h e n e t f u e l / w a s t e f e e d . DREs o f l e s s t h a n 9 9 . 9 9 % have b e e n o b s e r v e d , h o w e v e r , where p o o r c o n t r o l o f c o m b u s t i o n a i r e x i s t s and w a s t e i s i n a d e q u a t e l y a t o m i z e d , e v e n when a n a c c e p t a b l e cement p r o d u c t i s b e i n g p r o d u c e d . B u r n i n g w a s t e s as f u e l c a n have a s i g n i f i c a n t e c o n o m i c i m p a c t o n w e t p r o c e s s cement p r o d u c t i o n f a c i l i t i e s , where f u e l


188

T R E A T M E N T A N D DISPOSAL OF PESTICIDE WASTES


c o s t s can r e p r e s e n t p r o d u c t i o n , and may process (16).

as much as 6 5 % o f t h e c o s t o f cement c l i n k e r h e l p extend the economic l i f e of t h i s o l d e r

H a z a r d o u s Waste I n c i n e r a t o r s . M a j o r e f f o r t s have b e e n a p p l i e d t o t h e e v a l u a t i o n o f e x i s t i n g i n d u s t r i a l and c o m m e r c i a l h a z a r d ous w a s t e i n c i n e r a t o r s (Γ7). The number o f t h e s e i n c i n e r a t o r s , i n c l u d i n g t h o s e u n d e r c o n s t r u c t i o n , i s e s t i m a t e d t o be 392 (see Table IV). These f a c i l i t i e s i n c l u d e s e v e r a l t y p e s o f i n c i n e r a t o r s , a l t h o u g h over h a l f are the l i q u i d i n j e c t i o n type. I f one c o n s i d e r s t h e g e o g r a p h i c a l d i s t r i b u t i o n o f t h e s e f a c i l i t i e s on t h e b a s i s o f EPA r e g i o n s , t h e g r e a t e s t number a r e i n R e g i o n s 4 and 6. T e x a s and L o u i s i a n a a r e t h e two s t a t e s w i t h t h e g r e a t e s t number o f f a c i l i t i e s . ( I n f o r m a t i o n on o p e r a t i o n a l h a z a r d o u s w a s t e i n c i n e r a t o r s i n s p e c i f i c l o c a t i o n s can be o b t a i n e d f r o m EPA r e g i o n a l o f f i c e s . )

T a b l e IV. P r o j e c t e d H a z a r d o u s Waste Incinerator Population Type Liquid Injection Hearth Rotary K i l n F l u i d i z e d Bed Other Under C o n s t r u c t i o n Total

Number 213 75 17 5 42 40 392

C u r r e n t l y , t h e r e a r e two p r i n c i p a l a r e a s o f a c t i v i t y i n v o l v e d i n the e v a l u a t i o n of hazardous waste i n c i n e r a t i o n f a c i l i ties. B o t h a r e p r i m a r i l y c o n c e r n e d w i t h DRE d e t e r m i n a t i o n and w i t h HC1 and p a r t i c u l a t e c o n t r o l . The f i r s t a r e a c o n c e r n s E P A s e f f o r t s to f i n a l i z e the o p e r a t i n g p e r m i t s f o r hazardous waste i n cineration f a c i l i t i e s . The s e c o n d p h a s e ( P a r t B s ) o f t h e o p e r a t i n g p e r m i t s f o r many h a z a r d o u s w a s t e i n c i n e r a t o r s a r e b e i n g c a l l e d i n by EPA. The c o m p l e t e d p e r m i t a p p l i c a t i o n must i n c l u d e documentation t h a t the i n c i n e r a t o r i s capable of meeting the p r e s c r i b e d o p e r a t i n g c o n d i t i o n s , i . e . , a ^ 9 9 . 9 9 % DRE, and HC1 and p a r t i c u l a t e c o n t r o l . T h u s , many o f t h e s e f a c i l i t i e s have a l r e a d y conducted t e s t burns or are p l a n n i n g t e s t s soon. The t e s t r e s u l t s w i l l e v e n t u a l l y be made p u b l i c t h r o u g h t h e p e r m i t t i n g process. The s e c o n d a r e a o f a c t i v i t y has t o do w i t h s t u d i e s b e i n g c o n d u c t e d by EPA t o e v a l u a t e i n c i n e r a t o r p e r f o r m a n c e as p a r t o f t h e A g e n c y ' s R e g u l a t o r y I m p a c t A n a l y s i s (RIA) o f h a z a r d o u s w a s t e incineration regulations. As p a r t o f t h i s a n a l y s i s , s e v e r a l 1



11.



189

f a c i l i t i e s burning hazardous waste have been t e s t e d by EPA. Data from these t e s t s are being analyzed to determine compliance with the o p e r a t i o n a l requirements. The r e s u l t s of t h i s study, however, have not yet been published. One i n c i n e r a t o r that has been evaluated rather e x t e n s i v e l y and f o r which t e s t r e s u l t s have been reported i s the l i q u i d chemical waste i n c i n e r a t o r f a c i l i t y owned by the Metropolitan Sewer D i s t r i c t (MSD) of Greater C i n c i n n a t i , Ohio (18). The MSD f a c i l i t y uses a r o t a r y k i l n and l i q u i d i n j e c t i o n cyclone furnace to i n c i n e r a t e a wide v a r i e t y of l i q u i d i n d u s t r i a l chemical wastes. The t o t a l design heat r e l e a s e rate i s 120 m i l l i o n kJ/h (114 m i l l i o n Btu/h). Tests conducted over a wide temperature range (~ 900°C to ~ 1300°C) f o r s i x Appendix VIII chemicals (carbon t e t r a c h l o r i d e , chloroform, hexachlorobenzene, hexachlorocyclopentadiene, and hexachloroethane) have shown DREs equal to or very near 99.99%. In a d d i t i o n to these f u l l - s c a l e t e s t s , EPA has i n i t i a t e d a program to conduct extensive intermediate-scale incinerator s t u d i e s , i . e . , studies t h a t would approximate the a c t u a l condit i o n s that e x i s t i n f u l l - s c a l e i n c i n e r a t o r s but that at the same time would be close enough to the l a b o r a t o r y studies p r e v i o u s l y discussed to allow c o r r e l a t i o n of the r e s u l t s from both scales of operation (19). The EPA Combustion Research F a c i l i t y (CRF) has been constructed to conduct t h i s program at the N a t i o n a l Center f o r T o x i c o l o g i c a l Research (NCTR), J e f f e r s o n , Arkansas. Summary Over the past 15 years, s i g n i f i c a n t e f f o r t has been expended i n e v a l u a t i n g p e s t i c i d e i n c i n e r a t i o n . Some of the e a r l i e s t work on i n d u s t r i a l waste i n c i n e r a t i o n was performed on p e s t i c i d e s , and t h i s work became p a r t of the b a s i s f o r the current r e g u l a t i o n s f o r the i n c i n e r a t i o n of hazardous wastes. While e a r l i e r studies addressed the i n c i n e r a t i o n of p e s t i cides and p e s t i c i d e wastes as such, most current e f f o r t s are focused on the general area of hazardous waste, as defined by the Resource Conservation and Recovery Act of 1976. This ongoing work i s d i r e c t l y r e l a t e d to p e s t i c i d e d i s p o s a l , however, as p e s t i c i d e waste i s included i n the category of RCRA hazardous waste. In f a c t , the presence of p e s t i c i d e s i s a major considera t i o n i n a waste being designated as hazardous. S i g n i f i c a n t a c t i v i t y i s o c c u r r i n g i n assessing hazardous waste i n c i n e r a t i o n i n both the p r i v a t e and p u b l i c s e c t o r s . Much of the information gained from t h i s e f f o r t w i l l be d i r e c t l y a p p l i c a b l e to our knowledge of the i n c i n e r a t i o n of p e s t i c i d e s and p e s t i c i d e - c o n t a i n i n g wastes.


190

TREATMENT AND DISPOSAL OF PESTICIDE WASTES

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2.

3. C.


4.

5. 6.

7.

8.

9.

10.

11.

12.

Working Group on Pesticides. "Summary of Interim Guidelines for Disposal of Surplus or Waste Pesticides and Pesticide Containers," Report WGP-DS-1, 1970. U.S. Environmental Protection Agency. "Pesticides and Pes ticide Containers: Regulations for Acceptance and Recom mended Procedures for Disposal and Storage," Fed. Regist. 1974, 39(85), 15236. Ackerman, D. G.; Fisher, H. J.; Johnson, R. J.; Maddalone, R. F.; Matthews, B. J.; Moon, E. L.; Scheyer, Κ. H . ; Shih, C.; Tobias, R. F. "At-Sea Incineration of Herbicide Orange Onboard the M/T Vulcanus," EPA-600/2-78-086, 1978. Leighton, I. W.; Feldman, J. B. "Demonstration Test Burn of DDT in G.E. Liquid Injection Incinerator," U.S. Environmen t a l Protection Agency, 1975. Whitmore, F. C. "A Study of Pesticide Disposal in a Sewage Sludge Incinerator," EPA/530/SW-116c, 1975. Duvall, D. W.; Rubey, W. A. "Laboratory Evaluation of High Temperature Destruction of Kepone and Related Pesticides," EPA-600/2-76-299, 1976. Graham, J. L.; Rubey, W. Α . ; Dellinger, B. "Determination of Thermal Decomposition Properties of Toxic Organic Sub stances," Presented at the National Meeting of American In stitute of Chemical Engineers, Cleveland, Ohio, August 1982. Ferguson, T. L.; Bergman, F. J.; Cooper, G. R.; Li, R. T.; Honea, F. I. "Determination of Incinerator Operating Condi tions Necessary for Safe Disposal of Pesticides," EPA-600/ 2-75-041, 1975. Shih, C. C.; Tobias, R. F.; Clausen, J. F.; Johnson, R. J. "Thermal Degradation of Military Standard Pesticide Formu lations," TRW Systems, Inc., 1975. Johanson, J. G.; Yosim, S. J.; Kellogg, L. G.; Sudar, S. "Elimination of Hazardous Wastes by the Molten Salt De struction Process," Proc. 8th Annu. Res. Symp.: Incinera tion and Treatment of Hazardous Waste, EPA-600/9-83-003, 1983. Stretz, L. Α . ; Vavruska, J. S. "Controlled Air Incineration of PCP-Treated Wood," Los Alamos National Laboratory/U.S. Environmental Protection Agency IERL/CI Incineration Re search Branch, U.S. EPA Interagency Agreement AD-89-F1-539-0, undated. H a l l , F. D . ; Kemner, W. F.; Staley, L. J. "Evaluation of F e a s i b i l i t y of Incinerating Hazardous Wastes in High -Temperature Industrial Processes," Proc. 8th Annu. Res. Symp.: Incineration and Treatment of Hazardous Waste, EPA -600/9-83-003, 1983.


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Higgins, G. M.; Helmstetter, A. J. "Evaluation of Hazardous Waste Incineration in a Dry Process Cement K i l n , " Proc. 8th Annu. Res. Symp.: Incineration and Treatment of Hazardous Waste, EPA-600/9-83-003, 1983. Black, M. W.; Swanson, J. R. Pollut. Eng. 1983, 15(6), 50. Chadbourne, J. F. "Burning Hazardous Waste in Cement Kilns," Presented at the 76th Annual Meeting of the Air Pollution Control Association, Atlanta, Georgia, June 1983. Lauber, J. D. J. Air Pollut. Control Assoc. 1982, 32(7), 771. Keitz, E.; Boberschmidt, L . "A Profile of Existing Hazard ous Waste Incineration F a c i l i t i e s , " The MITRE Corp., November 1982. Ananth, K. P . ; Gorman, P . ; Hansen, E.; Oberacker, D. A. "Trial Burn Verification Program for Hazardous Waste Incin eration," Proc. 8th Annu. Res. Symp.: Incineration and Treatment of Hazardous Waste, EPA-600/9-83-003, 1983. Carnes, R. Α . ; Whitmore, F. C. "Siting and Design Consider ation for the Environmental Protection Agency Combustion Research F a c i l i t y , " Proc. 8th Annu. Res. Symp.: Incinera tion and Treatment of Hazardous Waste, EPA-600/9-83-003, 1983.

RECEIVED March 26, 1984


Incineration of Pesticide Wastes - ACS Symposium Series (ACS

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