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Radiation treatment of liquid wastes
Razdiaz. Phys. (.'hem. Vol. 2.1., N o 1. p p 77-97. 1984
0|4~572,~84 $3.00+,(N) Pergamon Press Lid
Pnnzcd in Great Bnzain.
RADIATI~ ~REA~M~T OF LIQUID WASTES
A.K. Fikaev, V.N. Shubin* Institute of I~Tslcal Chemistry of the A o a d e ~ of Solences of t h e U.S.S.R., Moscow, U.S.S.R. * I n s t i t u t e o f E l e c t r o c h e m i s t r y o f t h e Aoaden~ o f S c i e n c e s of the U.S.S.R., MOSOOW, U.S.S.R.
~BSTRACT The p a p e r i s t h e r e v i e w on r a d i a t i o n t r e a t m e n t o f n a t u r a l and p o l l u t e d wa~ers, x~latlo~ dcoomposltion of dyes, phenols, o~m~des eto., x~Li&tlon heterogeneous pu1~Ifioation (for ex~nple, radiation purifioation in the presenoe of sorben%s), radlation-flotation pul~fl~ation of aqueous wastes f~om mercury, l~iatlon-polymex-i~tlon puA-ifioatlon, x~tlatlon ~IsiDfeotlon of wastes. The s p e c i a l a t t e n t i o n i s p a i d t o t h e works o f S o v i e t a u t h o r s . KEY~ORDS Radiation treatment;
liquid wastes; natural
water; radiation
heterogeneous
purlfloatlon; radlatlon-flotatlon purification; radlatlon-polymeri~ation pu_~iftoation; radiation
disinfection.
~R~DUG~ION • ecauae o f f a s t development o f i x u l u a t z ~ and e~pmioult~ze the problem o f p u rification o f i n d u s t r i a l end m m ~ o i p ~ l wastes i s sharpened i n am~y c o u n t r i e s . One o f t h e p e r s p e c t i v e wa~s f o r t h e s o l u t i o n o f t h i s p r o b l e ~ i s t h e a p p l i c a t i o n of the energy of i o n i z i n g r a d i a t i o n .
During the aotio~ o f ioni~4-~ radiation on water h,yd..z'Lted eleo%zons ( e~q ), h~drogcn atoms and h~droxyl radloals which are very strong reducing and oxidi~ e~ents are formed. These species a~w cal~ble to anceRpiAah various radlolytlo t x ~ x s ~ o z ~ a t i o ~ s of solutes (redox reactlons, decaapoaltlon o f orga~Lc compounds, d i s o o l o ~ r a t i o n o f dyes, f c z ' ~ Z t i ~ o f p r e c i p i t a t e s e t c . ) . It is also well-M~si that ionizing z1~Li&tio~ bLs & stezili~bmg e~tlon. These e f f e c t s exe t h e ba~Ls fO~ t h e d e v e l o l m e ~ t o f x ~ L I A t £ = m e t h y l s o f p u zlfieati~ of aqueous wastes. At p r e s e n t t h e i n v e s t i g a t i o m . s i n t h e f i e l d RPC 24/1-F
77
of appll~tiom
of ioni~
z~lia-
tion for purification of liquid wastes are carried out in many laboratories. In this paper the most important results, which have been obtained in the direction under consideration in the U.S.S.R., are discussed. Some of these results were considered in books by Dolin and others (1970), Shubin and others (1979), Dzhagatspanyan end others (1979, 1981), Dmitriev end others (1981) end in review by Pikaev (1982). RADIATION TREAT~RNT OF NATURAL AND POLLUTED WATER In the 60-70s in the U.S.S.R. a lot of investigations (see e.g. Apel'zin and others (1973), Brusentseva end others (1975), Dolin and others (1970), Guteev and others (1978) on radiation treatment of natural water was carried out. The purpose of these studies was the improvement of characteristics of water purified by traditional methods or even their complete substitution. The important parameter of the quality of natural water is the color. It is due to the presence of different fractions of humus compounds: humic acids and colloidal and/or dissolved fulvic acids. Since the content of various fractions in the water of concrete reservoir was different, the experiments were performed with using both natural water and model solutions. The latter was necessary for the choice of optimal regime of radiation treatment (dose and dose rate) of any water with known content of humus compounds end also organic substances causing the taste end the odor. The radiation sources were 60Co installation and linear electron accelerator U-12 (electron energy is 5 MeV). Figure I shows the results of the study of radiation discolouration of aqueous solutions of humus compounds. The doses which are necessary for color removal from water of different reservoirs to 20 degrees (as it is required by respective State standard on drinking water) are given in Table I. From Table I it is seen that air bubbling favours the color removal from water of different sources. It is also necessary to mention that the doses required are the same in case of 6Oco
T-rays
and the fast electrons.
Research on radiation odor control was performed by using the solutions of 4 groups of organic substances isolated from natural waters. The results obtained are listed in Table 2. The efficiency of radiation removal of comparatively small amounts of o r g e ~ c impurities is confirmed by tertiary purification of wastes of the Baikal cellulose-paper plant after ch~mlcal s~Id biological purification. Figure 2 shows the respective results. It is seen that irradiation together
Radiation
~ t
8 6
of
Liquid
Wast~
t.0
7~
"--'~-x- g
" " - ' ~ C - -
'O
Z
t
Trcatmcnc
' X--4
f0
t5
P i ~ . 1. R a d i a t i o n d i s ¢ o l o u r a t i o n o f aqueous s o l u t i o n s o f humus oompoundsz 1 - s o l u t i o n o f humio a c i d s (pH 7 . 1 ) ; 2-solution of f u l v i c a c i d s (pH 7 , 1 ) ; >-colloidal solution of fulvlc acids (pH 7). Dose rate (Gys-1):
4.9(o); 3(x) end 0.58 (4). 1
R a d i a t i o ~ Dls00~o~umtion o f Water f,r~Sn Rese~To~rs o f 10800W D:~Stz~ot H .
II
Reservoir i
Inltlal color, deg
,,l
i
,,
~w~.z~d ~o= color r ~ t o 20 de8 Without a i r b u b b l i n g With a i r b u b b l ~
i
Uoha ~ e a l r v o i r
,,
Dose ( k ~ )
i lis
,
35
0.8
0.6
Eastern water treatment plant
33
0.5
0.35
K].yas e ~ voi.r
49
4.0
0.8
H,
reeler--
,
, IHI
,,
, ,,
TABLE 2
Radiation Odor Control
Raw water Odor inCOD, tensity,TON
Group of organic substances
Substances of the group
Neutral compounds
Hydrocarbons, ethers,esters, aldehydes, ketones,nitriles, sulfides etc.
140-100
110
Strong organic acids
Fatty acids
100-70
5
Weak organic acids
Phenols,substituted phenols, mercaptans, naphtenic acids et6.
70-50
10
6
Basic orgRn~c compounds
Amines,pyridine bases etc.
250-200
10
12
~02/dmJ
Irradiated water Odor in- COD, 3 tensity, mgO2/dm TON 17-12
15"
10
• Dose rate was 0.58 Gys-1; in other cases it was 3.6 Gys "I. with air b u b b 1 1 ~ decreases the color to 8-I0 degrees. In this case the decrease of the dose rate intensifies the process; already after irradiation to doses 0.1-0.3 kGy the color and COD of water correspond to the State standard on drinking water. Petryaev and others (1982) studied in detail the bactericidal effect of -radiation on biologically purified municipal and industrial wastes with increased content of org-n~c impurities (COD is up to 5 0 m ~ 02/dm3). The data of this study are shown in Table 3.
~
An~3 ogous investigations of municipal liquid wastes after 2 sta~es of biological purifioationwere performed by Mann (1971). sdm~lar.
The results obt,~ned are
Zolotova and others (1975), Woodbridge and others (1975) and Ryabchenko and others (1980) checked static system data at small flow-type pilot plants (output is up to 1.5 m 3 a day). The results were approximately the same. The irradiation to doses 0.6-0.8 kGy together with air bubbling gives the water which can be used for irrigation and drinking. In 1970 after prelimlnary tests the commercial plant with output of 38 m 3 a day was constructed in the U.S.A.(see Woodbridge and others(1975)). It was included in the
Radiatwon Trcatmenx of Liquid Wastes
81
I
D
Fig. 2.
f
2
3
R a d i a t i o n o o l o r ~wmoval f r ~ n w a s t e s o f t h e B a i k a l c e l l u l o s e - p a p e r p l a n t e ~ t e r obAm~oal and b i o l o g i c a l purification (dose rate 5.82 Gys-I):
1-wlthout air bubbling; 2-post-effeot after irradiation without air bubbli~;>-ai~ bubbling; 4 - a i r b u b b l i n g , dose r a t e 0.108 G~s -1 ,
Radiation ]~1.s1.~eo~:i.on
,,,
Dose, (}y
,
I
III
,
micro-
DlaCn:~ect:Lo~,%
,
0 90 300 500 800 1000
1.20 2.17 2.90 1.75 1.25 0.85 I
J
II
II
,
,
x 105 x 103
x x x x
oamplex of b l o l o ~ L e s l pumlfioa¢ion° dolle.rs/m 3
I
,
,
,,
H,
0 98ol 99.76 99.85 99.89 99.92
102 102 102 102
II
Itclti~i
,
Amount o f m ~ e d
,,i,,
~iol~~
of
IIIII
I
I
I
I
IIII
lIB
I
II
The ooet of puzl~loatim~ i s 0.38
The economical evaluation of the cost of complex purification of natural water was carried out by Guteev and others (1978). The evaluation was performed for radiation plants on the basis of electron accelerators with outputs of 100, 1000 and 5000 m 3 a day. It was calculated that the cost of purification of I m 3 was 2, 0.5 and 0.17 roubles. At present these values are comparable with the cost of purification by chemical method. Let us note that the cost of radiation purification should be lowered considerably after the increase of the power of used accelerators. RADIATION PURIFICATION OF INDUSTRIAL LIQUID WASTES In the preceding chapter it was shown compounds which were present in water fication were comparatively low. The tion contains the compounds which are dyes, phenol,
cyanides,
that in the case of simple chemical in small amounts the doses for purisituation is more complex when solupoisonous or hardly decomposed (e.g.
salts of mercury and bismuth etc.).
The radiation sensitivity of cotton-mills wastes, which are often coloured intensively because of residual dye concentrations, is enough high. It is clear since the radicals from water radiolysis attack in first turn the chromophoric groups which are responsible for the color of dye. Apparently, the results of irradiation are specific for dyes of different types. The main kinetic peculiarities for radiation discolouration of solutions of different azodyes both in the presence of oxygen and in its absence have been studied in detail by Khabarov and others (1981) and Takehisa and others (1982). It was found that disoolouration is a non-chain process ; the radiation-chemical yields do not exceed units or even tenth parts of unit. The doses required for discolouration depend on the type of dye; they are differed by almost two orders of magnitude. The process does not depend on the temperature. However, the yield depends on some additions (e.g. ions of transition metals). It was obtained by Case and others (1971) that the average dose for wastes taken from dye vats is 10-15 kGy. Case and others (1971), Dykhanov and others (1979), Tyutyukanova and others ( 1 9 8 0 ) f o u n d that approximately the same dose is necessary for the decomposition of pesticides. The other example of compounds, small amounts of which do not allow to use the water repeatedly and to throw off it the basin, are sulfides. Natroshvili and Nanobashvili (1967) and Natroshvili and others (1972) studied the radiolytic transformations in aqueous solutions of the compounds of sulfur in low valent states. It was found that the yields of oxidation of HS- to $20 ~- and SO~- were increased with the increase of acidity; they achieved 25 molecules/t00 eY, when the solution was bubbled by oxygen.
Radiation Trca~mem of Liquid W~stcs
83
G e r a ~ t m o v i c h and o t h e r s 41980) i n v e s t A g ~ t e d t h e a o t l ~ o f i o n i z i n g r a d i a t i o n on c o n d e ~ a t e s oZ e v a p o r a t e - s h o p s o f s u l f a t e c e l l u l o s e ~ o d u c t i o n p l a n t s . I t was e a t e ~ l A ~ h e d t h a t dome 1-2 kGy was s u f f i c i e n t f o r t h s dec~npoeition of s u l f i d e s oontaAnAn~ i n t h e w a s t e s t o 75-95 % ( a t p~ 4 - ~ ) . T h i o s u l f a t e s , s u l f t t e s and e l e m e n t a l s u l f u r which a ~ form ed d u r i ~ i X T a d i a t t o n a r e l e s s to
c
P h e n o l i s h a r d l y dec~npoeed d u r i n g i r r a d i a t i o n . I t i s p r e s e n t i n man~ w a ~ e s and i t i s ~,npossible t o us e t h e w a t e r w i t h p h e n o l c o n t e n t more t h a n 10 - 3 mg/~n 3. Because o f i t t h e r a d i a t i o n d e c o m p o s i t i o n o f p h e n o l i n aqueous s o l u t i o - - A was s ~ u d i e d t h o r o u g h l y by T o u h i l l and o t h e r s 41969), B r u s e n t e e v a and o t h e r s ( 1 9 7 1 ) , V y s o t s k a y a and o t h e r s 41980a). At low dose r a t e ( N O . 1 Gys-1 ) t h e c h a ~ t r a n s f o r m a t i o n o f p h e n o l w i t h t h e y i e l d o f 250-~00 m o l e o u l e s / q 0 0 eV t o o k p l a c e An a e r a t e d s o l u t i o n s . The main p r o c e s s o f p h e n o l t r a n s f o w , ~ t i o n se~ns t o be t h e c o n d e n s a t i o n . Y i g u ~ 3 shows t h e d e p e n d e n c e o f t h e y i e l d o f p h e n o l d e o ~ n p o ~ t ~ l o n on dose r a t e o f T - r a d i a t i o n . The i n c r e a s e o f t e m p e r a t u r e t o ~O°C g i v e s 2 t i m e i n o r e u e o f t h e y i e l d o f phenol dec~position, and t h e e f f i c i e n c y o f t h e p r o c e s s i s f a v o u r e d by o ~ Ken b u b b l i n g d u r i n g i r r a d A a t i o n . At h i g h dose r a t e s and a l s o i n t h e a b s e n c e o f o x y g en t h e p r o c e s s i s non-oheAn; i n thAs c a s e t h e p~oduot s a r e h i - and o t h e r p o l y a t ~ i ¢ p h e n o l s . ~h~ f i n a l p r o d u c t s o f m a ~ - s t e p t r a n s f o r m a t i o n a~e m ~ e i c a c i d end o t h e r n o n - a r o m a t i c c~apounds. However, t h e d o s e s f o r s u ch s t r a n s f o r m a t i o n a r e h i g h ( 0 . 2 - 0 . 2 5 MGy). T a k e h i s a and o t h e r s (1982) showed t h a t t h e dos e can be d e c r e a s e d c o n ~ i d e r a b l y ( t h e y i e l d o f t h e d e c r e a s e o f t o t a l o r g a n i c c a r b o n i s i n c x ~ a s e d by 20 t i m e s ) by t h e o ~ b i n ~ t i o n o f ~ation with osonation. I n t h i s combined p r o c e s s t h e o a r b o x ~ l a c i d s ( m a i n l y o x a l i c a c i d ) are f o ~ e d ; ~ h e ~ ~hey e~e d e c ~ a p o ~ d t o CO2 and ~20. V y s o t s k a ~ a and o t h e r s ( 1 9 8 0 a ) f o u ~ t h a t t h e r e s u l t o f i r ~ t i o n of i n d u s t r i a l w a s t e s oonte~in~u~ p h e n o l s , m e t h a n o l and for, ~al deh~ds i s t h e f o r mation of precipitates. L e t u s c o n s i d e r t h e reAiatlo~ pu_~Afloatlon o f ~qu~ous s o l u t i c m s o f one o f the moat poisonous s u b s t ~ c e s wb.i~h i s widely used in Kold i n d u s t ~ and i n g ~ l v a n i c c o a t i n g s s h o p s , namely - c y a n i d e s . ~ouhS.ll and o t h e r s (1969) s t u d i e d t h e i n ~ l u e n c e o f dos e r a t e , o ~ g e n o o n a e n t r a t i Q n , t e | a p e r a t u ~ , c o n c e n t r a t i o n o f oyanAdes (:~Xwm 26 ~ d m 3 t o 2 . 6 ~/dm 3) a~d ~ t a l y s t s ~ th~s i~ooess. I t was f o u n d t h a t u n d e r s t a t i c o o n d i t i ~ mad i n f l o w s y a t m t h e c ~ r p l e t e d e a a n p o s i t i o n o f c y a n i d e s i n t h e s o l u t i c ~ w 4t h c o n c e n t r a ~ i o n o f 2 6 ~ / d m 3 ~ S a t dose 1 . 8 - 2 kGy. ~ l~cooess i s a c c e l e r a t e d a t 100°C and
i n tho pr.. e of black, + ¢zO,, I n more oonoentx~_~ed i o l u t ¢ o n s t h e d o s e s r e q u l ~ e d f o r ~ e o o m ~ m i t i o n are incz~c.-ed t o 10-.104 k(~r (see D o l i n and o t h e r s 4 1 9 7 0 ) , ] i i t r o a i s v A l i and o t h e r s (1967), T ~ i l l and o t h e r s (1969) •
~-
A.K.
PIKAEV AND V, N. SHUBIN
3oo
~
~u
200
-/00
0 a.Of Pig. 3-
0,! /,0 ose zate ,
Dependence of yield of phenol decomposition on dose rate of T-radiation: l-aerated solution; 2-deaerated solution
Arshakuni and others (1971) obtained that cyanides in the solutions with concentration of 500-600 mg/dm 3 and at pH 6.5-7.0 are decomposed via chain mechanism. At dose rate 180 Gyh -1 the yield was 1200 ions/100 eV. On the basis of these results the pilot plant with 60Co source (output is 200 m 3 a day) for the decomposition of o y - ~ d e s was elaborated (see Kon'kov and others (1975)). Lju and others (1982) developed the radiation-flotation method of purification of industrial wastes from mercury. The wastes were from plants producing chlorine and alkali by electrolysis method with using the mercury as a cathode. The method developed consists of three stages:preliminary flotation in the presence of eurfactant (sodium alkylsulfonate), ~-irradiation and secondary flotation (also in the presence of sodium alkylsulfonate). The principal scheme of the method is shown in Pig. 4- By means of this method it is possible to purify the wastes from mercury presenting in different forms (dlssolved~as a metal and in precipitate) up to limiting permitted concentration ( ~ 5xiO -3 Optimum conditions for the purification are the following: I) at prellm~n-ry flotation the pH value of waste is 12-13, concentration of sodium alkylsulfonate is 50 mg/dm 3, the rate of air feed is 0.02-6.0 dm3/min; 2) at ~-irradiation the pH value is 12-13, dose is I kGy; 3) the conditions for secondary flotation are the same as for
mg/dm3).
Radiazion Treatmem of Lkt~d Waste5
~
85
~°
foam c o n d e n s a t e f o r b u r n i n g
. o d i u m ~ a l k y l s u l f o n a t e solution
"1
-1 compressed a i r
PiK. 4.
otator
','I
for neutralizetion
Principal scheme of purification of wastes frc~ mercury by ~adiation-flotation method.
The r e d u c t i o n o f i o n i c m e r c u r y t o m e t a l l i c one o c c u r s d u r i ~ i r r a d i a t i o n . At d o s e o f I kGy t h e ox~Een p.~eeenting i n w a s t e i s O ~ ~ . ~ p l e t e l y , and i n a l k a l i n e medium i o n i c m e r c u r y i s r e d u c e d by e - . I t i s o a ~ f i m e d by t h e d a t a o b t a i n e d by L j u and o t h e r s (1983a,19 8 3b ) d u r ~ the investigation of pu~me ~ o l ~ s l s of a l ~ 1 i n e solutio~I o f ionic and ~ l l o me~cau~y. ~ o e , the ~ l~sult of i~r~d~ation o f w~stes o o ~ t ~ m~T~y le ~he reaction of blv~Im~t mercury to me~alllo one and/or m m k l ~ soluble ImeU~meo~o~al4mt fern (H~(OH) 2 type) which are re~oved effectively by fl~ati~m, GETEROG~EOUS R A D I A T I ~ DESTRUCTION
F r ~ e o o n ~ - ~ o a l p o i n t o f view t h e r a d i a t i o n p u r i f i c a t i o n o f a q u e o ~ r u t h is perspective in the case of nh.~n process. Because of ~ effiolen~y of ter~watlon of c~-In- this process Is impossible for diluted 8queens solutions. However, the conditions promotlng to the .~.4. deeomposltlon of Or~hn£C pollutants can be obtained by the oombinatlo~ of ~ t i o n des~ruotlon with a~o~lon o f p o l l u t a n t s by a c t i v e c ~ r b o n . Aotlve m ~ b o n is ~ a d ~ useA durln~ ~ y yea~s f o r t ~ e ~ o f orKe~Ao pollutemts from different waa~es. However it loKts t h e sO~'pt£on O a l ~ l t y
8A~er same vox~Lug p e r i o d end t h i s c a p a c i t y s h o u l d be x s ~ e n o ~ t e d
pe~od~oally.
A. K. P:KAEV ,~,'~o V. N. SHUm~
The t r a d i t i o n a l method of regeneration is the treatment in special ovens at 900-1000oC. In 1972 the low tanperature method of destruction of organic s u b s t a n c e s a d s o r b e d a t t h e c a r b o n s u r f a c e by i r r a d i a t i o n was p r o p o s e d by Case and K e t c h e n ( 1 9 7 2 ) . U n f o r t , m a t e l y , t h e low t e m p e r a t u r e r e g e n e r a t i o n was n o t o o n t i n u o u s p r o c e s s ; t h e r e a s o n was t o o h i g h i n t t i a l concentrations of pollutants. Shubin and others (1980) found that considerably better results can be obtained by the c~nbination of radiation treatment with adsorption at the stage of tertiary purification. In this case industrial or municipal waste is filtered, then it is treated by generally accepted methods at biological purification plant, where the flocculating agent is added to water for the precipitation of suspended organic substances. The next stage is the filtration through the sand. After the removal of the main amount of organic pollutants the water containing the organic pollutants up to 250 mg 02/dm3 is passed through the capacity with active carbon which adsorbs the residual organic substances. Initially, the carbon adsorbs the organic substances very effectively, and the considerable decrease of COD and color of wastes occur. However, the high content of organic substances in the waste leads to the fast decrease of adsorption activity of the carbon. After passing about 10 volumes of liquid per I volume of carbon the color of waste and its COD value become the same as for initial waste, i.e. the purification stops completely. Shubin and others (1980) observed that for the mainten-nee of adsorption activity of the carbon at sufficiently high level the wastes were passed through the column under conditions of continuous irradiation of sorbent by 60Co ~-rays. The method under consideration was applied by Nikiforov and others (1982) and Shubin and others (1983) for the purification and disinfection of wastes of live-stock farms. At present there are no methods of their purification which correspond completely to the sanitary standards. Because of it the control of the possibility of long action of sorbent during simultaneous irradiation had a great importance. It was found that at linear flow rate of 1.1 m.h -1 and dose rate 0.35-0.5 Gys -I the dose required for purification was 1.5 kGy. Any deterioration of the work of respective unit was not obtained after its operation during 3 months, and the purification gave the water which can be used repeatedly in industrial cycle or thrown off to any reservoir. This is illustrated by the data of Table 4. The similar results were obtained by Hay (1975) at pilot plant for the purification of wastes of poultrY farm. The initial waste had yellow-brown color, high turbidity, intense odor and COD value of 10OmgO2/dm3. After radiationadsorption treatment the water became colorless and odorless; COD value and contents of bacteria were decreased by 90% and 95% respectively. The time
R ~ a ~ o n Tmatmem of Lkluicl Wa.~e5
8"7
of oo~t~t b e ~ e e e ~ ~oz~m~t e ~ d weJo~es we~ ~0 m 4 , a t d o s e r a t e ~he o ~ r t o f m ~ h a p u r ~ i o n i s 0 . O 7 - 0 . 0 8 d e l l a r s / m )• ~
~? u z - J ~ . m ~ t £ a n of~ gss~'~s o f I £ ~ t ~ k
4
l~netera
Initial wastes
200.4 Suspended mabetances,
0.047
Trsns~e~,
3.5
~/~3
cm
1~
24.4 0.03
30
800
40
BOD5 , ~ ' 0 2 / ~ 3
96
8
7.5
7.05
Total nltroeen, me/din3
23.2
7.7
p043-, e~,/'~3
75
0.11
K+, n~,/dm3 utcrobe
number
E.ooli
Stapb~loooocus
2.7
by
Wastes after tz~t~mt
COD, .~021dm3
pH
Of 1 k G y h - 1.
0.2
1.1 ~ L l l l o n / c ~ 3
41 ~ L o r o b e c e d e / c a 3
2 . 5 x 104
not isolated
2 x 103
not isolated
Ap~rently, the radiation-adsorption m e t h o d i s one o f t h e o h e l p e ~ r a d i a t i o n methods. I t i s due t o t h e s p e c i f i c s of real radiation deetruot£on prote~, wh~oh o c c u r s u n d e r c o n d i t i o n s o f r a d i a t i o n - a d s o r p t i o n equ~librium: at steadys t a t e o o = o e n t r a t i o n of' ~ n p u ~ t i e e and with constant z~te. Besides, concentrat~ the pollutants in the marf~ce layer et~&tes the chin destruction and the octurence of rad~ation-o&tslytto process. ~ r , the mechenism of the pur~ication is not clear. Indeed, the yield of deetruotion o f orsanio mabstanoes calculated fr~ t h e c h a ~ e o f COD v a l u e i s c ~ . 600 e q u i v . / 1 0 0 eY. At t h e ~ t~e the oonte~t of o~reen in ~Ltial w~te Is ~ 8 ~ 3 . As it follows from analyaee, thle is by 100 times leas than the amount r e q u i r e d f o r o x i d a t i o n o f a l l ozl~__ic m a b e t a n o e e t o 0 ~ ~ d ~ 0 (Shub~n a n d o t h e r s (19B0, 1 9 8 3 ) , N i k i f o r o v a n d o t h e r s ( 1 9 8 2 ) ) . Undoubtedly, only profound inweetl~atlons will help to develop the prinolplee of the choice of optimum oondltions for prolonged radiatlon-adsorptlon pul~floatlon.
The o t h e r m e t h o d u s i ~ the sorption at interface b e t w e e n a q u e o u s and g a s p h a s e s was d e v e l o p e d b y D z h ~ a t s p a n y a n a n d o t h e r s ( 1 9 7 9 , 1981) a n d M a k a r o o h kima and others (1969, 1974) for the purification of wastes c o n t a i ~ synthetic detergents (in first turn biologically nom-decomposable). The presence of such "hard" detergents in wastes leads to the foam formation during the aeration in aerotanks and prevents the application of other purification methods (especially biological method). The alkylarylsulfonates belong to the hard detergents. During irradiation of the solution containing "h,rd" detergents the following processes take place: the decay of alkylarylsulfonate because of sulfogroup detachment, the appearance of sulfate ions in equivalent amount, the decrease of the foam formation or the complete disappearance of it, the increase of surface tension up to the value equal to that for pure water and the increase of COD and BOb values. The yields of products do not depend on dose rate. The radiation destruction in a bulk of the solution is non-chain process; it is the oxidation of detergent molecules with the participation of air oxygen. The similar processes occur in the foam, but because of high concentration of detergent at the surface of foam bubbles and great accessibility of the oxygen the chain process of oxidation occurs. This is confirmed by high yields of desulfation and destruction of detergent (up to 50 molecules/lO0 eV) and oxygen consuming (up to 900 molecules/100 eV). As it is concluded by Dzhagatspanyan and others (1979, 1981), the use of economical low energy accelerators increases sharply the profitability of the process and makes it to be possible for industrial application. The process of adsorption purification was used as a first step of the purification of exhaust industrial gases from SO 2 . As it was found by Baranova and others (1981), in the solution containing bivalent m a ~ a n e s e ions as a catalyst SO~- ions are oxidized to sulfate ions under the action of iation. This radiation-catalytic process occurs via chain mechanism and can be used for the purification of sulfuric acid production exhaust gases
-rad-
with O.1-O.3% (in volume) content of SO 2. RADIATION-POLYmERIZATION
PURIFICATION
The formation of insoluble precipitate during irradiation of the solutions containing the substances which can be polymerized under the action of ionlz~ng radiation is used in radiation-polymerization method. The precipitate of polymer captures the pollutants and consequently purifies the solution. The formation of long nh--~ns of polymer takes place via opening the double bonds and cycles in molecules of organic compounds which is usually called by monomers. Such compounds can present in some wastes, but can be added also in it immediately before irradiation.
L~:liacion Trcam~nt o[ l.iqmd Waste5
~9
However, i t i s n e c e s s a r y t o s t r e s s t h a t t h e mean pArpose o f mW p u r i f i c a t i o n , which i s t h e s e p a r a t i o n o f p o l l u t a n t s ~-z~ pu~e sol~en%, i . e . w a t e r , can be d e c i d e d o~l~ by h e t e r o K e n e o u s p o l s ~ e ~ i ~ t i ~ n when t h e p o l ~ e r t o K e t h e r w i t h pollutants is p r e c i p i t a t e d and t h e n removed by known ~ e t h o d ~ 8 e t t l ~ , filtration o r c e n t r i f u g a t i o n . . From t h i s i t f o l l o w s t h a t t h e nm£n d i r e c t i o n o f
the development of redlatlom-poly~erlsatlon me%hod is the study of the possibility of captuzlmK the pollutants by insoluble polymer ~ c i ~ I t a t e e duzlnK l r r a d A & t l o n of w a s t e s w i t h a d d i t i o n o f monomers o r w i t h o u t added m ~ : e s (see S h u b l n a~d o t h e r s (1979), Nikonomov~ and othems (1976)). It is neee888zy to d A e t ~ a h the foll~win~ typical cases. I ). I n s o l u b l e p o l y m e r p r e c i p i t a t e formed by r a d i a t i o n p o l y ~ r i z ~ t i o n of s p e ~ l ~ l l ~ added monomer can remove t h e p o l l u t a n t s by t h e i r a d s o r p t i o n o r f o r a m t i o n o f e u t e c t i c mixture. 2 ). R a d i a t i o n t r e a t m e n t b e i n g t h e p o w e r f u l means o f ~ n ~ t i a t i o n can l e a d t o p o l y m e r i z a t i o n ( t h i s p r o c e s s i s o f t e n oeS.~ed by cmada~m~t~on s i n c e t h e h ~ d ~ e n is siumlteneously fozmed) of low-molecular c ~ WhiCh ~enezal-
ly do not belonK to mon~mers° 3)- N o n - p o l y m e r i z a b l e p o l l u t a n t s can be i n c l u d e d An rs&ti&tlon ~ - J t i a t e d polymeri~tion. Such an example i s t h e p u r i f i c a t i o n o f t h e w -e~es o f c e l l u l o m e - l m ~ ple,uta. These w a s t e s c o n t e £ n l i a m ~ e w hi ch iS OZ~m~O hamopolyn~r of c~aplex o~position. I t was f o u n d by Sh~bAn a n d o t h e r s (1979) t h a t r a d i a t i o n o x i d a t i o n o f t h i s c ~ p o u n d occur~uK v i a d e s t m a e t l o n o f p o l ~ e r i s n o t s u f f i c i e n t l y e f f e c t i v e , and t h e u t i ~ f ~ o t o r y p u l " i f i c a t i o n o f wastes requires the ~ d o s e s (up t o I MGy). ~ i t s e l f i s n o t cA-osalt--ka~, and t h e p r e ~ L p i t a t e i s n o t f a m e d . However, ~ n ~ o l u b l e p o ] ~ a r prec£1~it&te foz~An~ d u r i n K i r r a d i a t i o n o f t h e s o l u t i o n w i t h ~ o n m e r a d d i t i o n c a p t u r e s p o l l u t a n t s from t h e s o l u t i o n ( o b ~ o u s l ~ , b e o m a a e o f ~ r ~ t ~ t - o o p o l s ~ a e r i ~ t i o n ) (see N A k ~ o r o v a and o t h e r s (1976). 4). The p u r i f i c a t i o n o f p o l y m e r i n d u s t r y w a s t e s o o n t a A n £ ~ t h e r e m i n d e r s of the ayn'Pdaeaes- ollKomers, polymers which eze net pol~Rae~ised oaapletely e t c . i s lXWaible. A p p a r e n t l y , i n t h i s c a s e o p t ~ oondltio~ for the o~p l e t ~ o n o f t h e r e a c t i o n i n aqueous phase ca~ be c r e a t e d by t h e c h o i c e o f ~ l o n reg~, t e m p e r a t u r e , 1~ a n d a d d i t i o n o f s u b ~ 8 ualm~ i n t e e h noleSieal process.
The s p e e ~ o p e e u l i L r i t ¥ of r a d ~ a t i o n - ~ l ~ m e r i ~ i o n p ~ - l f l ~ t i ~ r e e l i ~ t i o n ~f h e t ~ o u s ~ol~mq~ up t o ~ (deathly de~ree of oonwersion. I t l a due t o the t o x i t ~ of z~E~hukl ~ r . To u ~
the r~Latic~
initiated
po~rir~tion
i s the v~ t o 1 0 ~ )
for the pu~if~ostion of stem
i s p o s s i b l e o n l y i n t h e c a s e when t h e p r e s e n c e o f p o l l u t a n t d o e s n o t l e a d t o effective c h a i n t e z ~ i n a t i o n and t h e c h a i n m e c h a n i s m o f p o l y m e r i z a t i o n i s k e p t t o h i g h (80-90%) d e g r e e o f monomer c o n v e r s i o n (1979), N i k o n o r o v a a n d o t h e r s (1976)).
( s e e S h u b i n and o t h e r s
In the studies under consideration methyl methacrylate, methyl acrylate, vinyl acetate and acrolein were used. The main part of the work was performed with 10 -I- 10 -2 mol dm -3 aqueous solutions of methyl methacrylate. It was established that the ch-~n mechanism of polymerization is kept up to 70-90% degree of monomer conversion. As it follows from the dependences on concentration and dose rate at high degrees of transformation the process is complicated with the growth of heterogeneity of the process; however, it keeps the main peculiarities of initial stages of conversion. The presence of oxygen lowers the polymerization rate; the decrease of pH increases the rate. At the next stage the regularities of radiation polymerizationwere studied in the presence of pollutants. For this the process was investigated with using the real wastes or model solutions. The real wastes were black waste of sulfate production of cellulose and waste of sulfite production of this material. The model solutions were solutions of dyes and urea. It was established that the irradiation of all the systems under consideration with methyl methacrylate addition (or other monomers) led to the formation of insoluble polymer precipitate. As in pure solutions of monomer, the c h a i n m e c h a n i e m o f t h e p r o c e s s was k e p t t o h i g h c o n v e r s i o n d e g r e e . For example, on polymerization of methyl methacrylate in black waste the yield o f monomer d e c r e a s e a t 15% c o n v e r s i o n was 3000 m o l e c u l e s / 1 0 0 e¥ and a t 55% c o n v e r s i o n i t was e q u a l t o 2000 m o l e c u l e s / 1 0 0 e ¥ . The d e g r e e o f p u r i f i c a t i o n was i n c r e a s e d w i t h t h e i n c r e a s e o f monomer c o n c e n t r a t i o n , the decrease of d o s e r a t e a n d pH a n d a t o p t i m a l c o n d i t i o n s i t c a n r e a c h 8 0 - 8 5 % a t d o s e s 0.1-1 kGy. The water purified from l i ~ i n e
can be returned to the plant for wm~h~mg
the cellulose, and the polymer precipitate with captured lignine after the dissolution i n monomer c a n be u s e d f o r t h e p r o d u c t i o n o f p o l y m e r i c g o o d s ( s e e P e t r y a e v and o t h e r s ( 1 9 7 8 ) ) . S u c h a s t u d y was p e r f o r m e d w i t h t h e w a s t e s of production of wood-fibrious plates mer. Developed technological scheme b i l i t y t o u s e wood r a w m a t e r i a l more precipitate for the treatment of the was shown by s p e c i a l c a l c u l a t i o n s the
c o n t a i n i n g l i g n i n e and r e s i d u a l m o n o of radiation purification gives a possic o m p l e t e l y and t o a p p l y t h e p o l y m e r murfaoe of wood-fibrious plates. As i t process is profitable.
The other perspective direction is the radiation treatment of the wastes of
Radiation Treatmenz of Liquid Waszes
91
polymer i n d u s t r y . For e ~ p l e , t h e w a s t e s o f one o f s u c h p l a n t s , p r o d u c i n g p o l y e s t e r s , have t h e f o l l o w i n g p e ~ m e t e r s : water-93%, ~ n e r a l s a l t s - l % , o r g a n i c s a l t s - l % , b y - p r o d u c t s (polymer p o l y ~ e r i z e d n o t c ~ p l e t e l y ) - ~ . 4 % , COD~10 ~ n~O2/dm3, pH 5 . 5 . I~ has i n , e n d i v e b l u e c o l o r and oontaAns t h e p r e c i p i t a t e (Ca. 20 ~'d~3)(eee Shubin and o t h e r s (1979), N~konor~va and o t h e r s
(~981)). R a d i a t i o n t r e & m e n t of s u c h & waste a f t e r a c i d i f i c a t A o n t o pH 4-4 by d o s e s 1-2 kGy d e c r e a s e s COD and c o l o r by 85-90% ( s e e F i g . 5 ) . ~ ThAs t r e a t m e n t leads ta the fo~tlon of c~pact, well-filtering prtcipita~e. Its htuidity i s 70~! i t can be d e c r e a s e d t o 3 0 ~ b y s ~ p l e p r e e s ~ .
.
~1-
L'--It-'-'~
O
t. !
0 ~.
o,s 5.
f,z
(6
10
Z7
0
Decrease o f COD (1) and f o r m a t i o n o f p r e ~ i p i t a t e (2) d u ~ i n & r a d l a t i o n t r e a t m e n t o f w a s t e o f p l a n t produci~ polyesters
At p r e s e n t t h e w a s t e s o f p l a n t s p r o d u c ~ p o l y e s t e r s a r e b u r n t . The c o s t o f thAs p r o c e s s i s 10-15 r o u b l e s / m 3 . F r ~ p r e l ~ : ~ y data it follows that the c o s t o f r a d X a t i c ~ p u r i f i c a t i o n i s c o n s i d e r a b l y l o w e r ( 2 - 4 r o u b l e e / m 3) • ~he polymer formed can be u s e d i n t e c h n o l o g y . As i t was f o u n d by Bondarenko s ~ l O~l~trS (1980), 1114m4111~m~13.te ~ x ~ o b t - 4 ~ d ~ ~ t ~ o n ptt~oation of the wastes of p l a n t s px,~duei~ v l ~ l a c e t a t e p l a ~ t i c s .
RADIATION DISINFECTION OF WASTES A lot of papers are devoted to disinfecting action of radiation. The studies have been carried out with bacteria, viruses and spores. It was established that radiation sensitivity of microorganisms is different. Bacteria are most sensitive, viruses are less sensitive, spores are most resistant to irradiation. For example, it was found by Touhill and others (1969) that disinfecting action of ionizing radiation on 4 m a i n groups of microorganisms, o c c u r i n g m o s t often in wastes: E.coli, enterococcus, spores and p~-g-coli, depends only on dose. At dose 2.5 kGy the amount of lost microorganisms was (in %): total amount of bacteria-99.995; coliforms-1OO; enterococcus-100; phag-coli-100; spores-92. The change of pH from 5 to 8 had no effect on radiation dislnfection (see Touhill and others (1969)). The dose of ~-and X-radiation which is necessary for the damage of definite number of E.coli cells in the absence of air is more by 10-12 times than in the presence of oxygen. It was also shovm that the presence of organic pollutants increases the dose required for disinfection. The detection of synergistic effect by Sidorenko and others (1963) is very important for radiation disinfection. The effect is that the results of combined action of radiation and other biologically active agent (for example, chlorine, heating etc.) are considerably better than the results of their separate actions. It decreases the ~n-ctivation dose for different bacteria by 5-10 times (see Woodbridge and others (1975)). The regularities obtained on model systems gave rise to construction of pilot and industrial plants. Since 1970 in the U.S.A. there is the large scale plant on radiation purification of mlm~cipal wastes in which the disinfection after biological purification is performed by ~-radiation treatment (see ~ - ~ (1971)). The output is 37.8 m 3 a day. The plant experience showed that the dose 0.5 kGy decreased the number of coliforms by 104 times and was sufficient for the dis~ection of wastes. Besides, the irradiation to such a dose improved noticeably the chemical, physical and biological parameters of wastes. In the paper by Mikhailova and others (1974) the results obtained d u r ~ the study of radiation disinfection of wastes of large live-stock breeding farm were published. The laboratory scale investigation on disinfection of such wastes by ~ - r a y s with consequent using as a fertilizer was carried out. The radiation sources were 60Co and 137Cs. The degree of disinfection was controlled by microbe number and coli-titre before and after irradiation. The determinations were performed through 2 hours, I, 2, 5 and 10 days after
~la~on
Tcea~rncnt of Liquid Wa-,~tc-~
93
irrsdiation. T ~ t i a l w a s t e had o o l i - t i t r e o f 10-7 and m i c r o b e number o f ~" 109. The d o s e was changed from 0.3 t o 6 . 6 kGy. Zt was show~ t h a t d i , ~ n f e o t i o n by ~ - r a y s was i r r e v e r s i b l e . The s t e r i l i z a t i o n ( t o m i c r o b e number o f O) was a c h i e v e d a t dose 2 . 5 - 4 . 0 kGy. I n t h e U . S . S . R . t h e problem o f r a d i a t i o n d i s i n f e c t i o n h a s now v e r y i m p o r t a n t si~nlfloanoe be¢ause of the p~sss~e to industrial methods of production of meat-dalry products via large live-stock breeding farms. Since the existing methods of biological purification and disinfection of without-lltter :~.nu.re d i d n o t s e c t t r e t h e c o m p l e t e d e s t r u c t i o n o f m i c r o o r g a n i s m s and h e l ~ n t eggs, t h e works on u s i ~ t h e t o w - e n e r ~ a c c e l e r a t o r s , p r o d u c i n g i n t h e S o v i e t Union, f o r t h e d i s i n ~ e c t i o n o f w a s t e s o f l i v e - s t o c k b r e e d i n g farms began. At present there is the information on 2 pilot plants. The plant in the All-Unlon Scientific Research Institute for Cattle-Breed~n~ Meo~-~-~zation has low-energy electron &ccelerator EOL-400 N(two contrary horizontal beams with energy 400 keY) as a s o ~ e of radlation. P ~ 6 demonstrates the view o f w o r k i n g r e a c t o r o f t h i s p l a n t . As i t was f o u n d by B r u s e n t s e v a and o t h e r s ( 1 9 8 0 ) , G r i s h a e v and o t h e r s ( 1 9 8 3 ) , t h e a d d i t i o n o f 0.2% o f e=monia to irradiati=E waste insured 10~ disinfection of liquid fraction of waste a t d o s e 5 kGy.
Fig. 6.
RPC 24/1-Q
View of w o r k ~ reactor of ~ d l a t l o n plant at AllUnion $clentlflo Roses.rob Y.uJtitute of Cattle-Bree~ Mechanlzation
At radiation plant "Borovlyany" two types of sources (60Co with activity of 0.5 MCi and 1.5-2.5 ~eV electron accelerator produced by the Institute of Nuclear Physics) are used. The general view of the plant building is shown in Fig. 7. It was found by Dmitriev and others (1981), C h u d i n a n d others (1982) that the use of sensibilizing additions of KC1 and CuS04 and of bubbl~ng the ozone-oxygen mixture secured the complete disinfection of livestock breeding farm waste at dose 2.5 kGy without preliminary separation into fractions.
Pig. 7.
Building of radiation plant "Borovlyany"
The similar studies are being carried out by working group "Waste Irradiation" of the Europlan Society of Nuclear Methods in Agriculture. From materials of annual conferences it is possible to note that the studies in the U.S.S.R. and other countries are being performed in near directions, and they are similar on results, conclusions and practical r e c ~ e n d a t i o n s (see Dolin and others (1970), Dzhagatspanyan and others (1981), ~mitriev and others (1981), Mann (1971), Woodbridge and others (1975), Plyustcheva (1971), Sidorenko and others (1980), Grishaev and others (1983), Chudin and others (1982), Gagen-Torn and others (1979), Vysotskaya and others (1980 b). CONCLUSION The performed discussion of various problems of radiation treatment of wastes shows that the radiation methods have some advantages in comparison with the conventional methods. The most perspective direction in this field is the
Radiation Trca¢mcnt of Liquid Waslcs
g5
a p p l i c a t i o n o f o ~ b i n e d methods o f p u r i f i c a t i o n ( t h e ~ b i n a t i o n of irradia t i o n w i t h f l o t a t i o n , a d s o r p t i o n , ozone t r e a t m e n t e t c . )° I n t h i s c a s e t h e dose f o r w a s t e p u r i f i c a t £ o n i s o~u~Lderably l o w e r e d ; t h i s makes r a d i a t i o n methods e o o n ~ o a l l y profitable. EEPERE~OES
Apal'tsyn, I.E., V.A. V.N. Shubin, S.A. i saa£t, tekhnika, A~sh_-~bUnl, R.G., S.S. L.~.MlJco.Toohkina,
~ ,
Kl~acJcko, E.F. Zolotova, Z.N. Makarenko, P.I. Dolin, B r u s e n t s e v a , and V.A. ~ o v (1973). Vodosn~b~e N 5, 8-12. Chlrkin~an, I.A. Gambaz~an, E.Go Butanyan, P.Z.Dolln, and R.V. Dzhagatspanyan (1971). ~ a v~.~
5, 5~6-537.
Baranov&, R , B . , L.T.Buga~ako, V.H. Byakov, V . I . L a z a r e v , and E . P . l ~ t r y a e v (1981). ~ eaA 2he~r R a d i ~ t < L o n - ~ 0 ~ t ' l~.,d.fica~tion. Energ o i z d a t , Moscow ( i n Russian). B ~ o , S°G., A.F. Nikolaev, L.I. Duvaklna, T.A. Schmldt, T°A. Antonova, S°A° Brusentseva, and P.I. Dolin (1980). Pl&st° ma nY , N 2, 47-48. Bruaentseva, S.A., A.G. /Tibush, V.N. 3hubin, and P°I° Dolin (1971)o
~
m~=~,
Khtmiya
5, 83.
Eruaentseva, S.A°, P.I. Dolin, V.A. 7.hlgunov, G.K. Nikonorova, V.N. Shubin, I.E. Apel'tsFn, E.F. Zolotova, V.A. Klyachko, and Z°N. Makarenko (1975).
V
~
,
N 3, 157-159.
Case, P.N., D.L. Kin, D°E. Smlley, and A.W. Garrison (1971). S~m~oli~ on t ~ use of ,,~.cleez ~ - ~ s ~ the ~ = ~ = ~ , m t = ~ ~=troZ of ~nv~r~tal Pollution (Salzburg). IAEA, Vienna, 755-761. Case, P.N., ~nd E,E. Ketchen (1973). Prenoh patent 2179129 (A). Chudin, A.A., and V.N. Shubin (1982). w h t ~ y a i tepJu~loLtya voctT, 4, 304-306. r ~ - t t r i e v , A.M., V.N. K a l i n i n , and V.S. Yetrov (1981). ~ a t i o n Tz~=tnent of WMt~e of Ltve-StO~k ~"ee~J,*-~ ]~u==. U ~ = ~ / , ~ ( i n Russ±sin). D o l i n , P ° I . , V.N° ~aubin, and S°A° Bz~asentseva (1970)o ~ t i o n Pu~fi~,tion gf W~te¢. Nsu~m, ilosoow ( i n Russian). ~Fkhlnov, N°No, IoDo Bondar, and S°A° Bz~sentseva (1979)° / T o b l ~ o ~ ~ , N 10, 10-15. D~tSl~inyan, R.V., V . I . Kosorotov, and M.T. F i l i p p o v (1979). I n t z ~ 4 u e t i ¢ = ~9 a~J~tJ.an..(~m.t.o~ Tee~=~losy. Atcmisdat, Mcaoow ( i n Rassian). D ~ t ~ , R,V., V.A. ~k~l,A1-~ M,T. Pilippov, and E.L. Me~teltson (1981). ~ e l ~ of EwLtat~on: Puwi~un~e~ o¢ w-.=te~. ~ w ~ o A ~ t , ~osoo~ ( i n Russian). ~ n - ~ , V.K., T.A. I~pow~, mad G,~. ~ed~wdev ( 1 ~ 9 ) . On t h e p o s s i b i l i t y o f a p ~ e m ¢ ¢ o n of ele
Accelerators of C h ~ e d PaFticles , Leningrad, 172-180 (in Russian). Gerasimovich, O.A., E.P. Petryaev, A.~. Kovalevskaya, and O.B. Stebunov (1980). Izv.AN BSSR.Ser.fiz.-ener~.nauk, N I, 41-43. Grishaev, I.D., S.A. Brusentseva, P.I. Dolin, G.A. Vinogradov, and V.E. Dubinskii (1983). Sbornik trudov ~IIVS. Moscow (in press). Guteev, V.P., B.M. Vanyushkin, N.G. Kon'kov, Yu.A. Pa~n, P.I. Dolin, S.A. Brusentseva, E.P.Zolotova, and Z.N.~akarenko (1978), ¥odn2e resursy, N 5, 205-206. Hay, W.C. (1975). Radiation for a Clean Envirolmment. Proceedings of Symposium (~unich). IAEA, Vienna, 433-444. kqlabarov, V.N., L.L. Kozlov, and G.~. Panchenkov (1981). Khimiya Vysokikh energii, 15, 218-222. Kon'kov, N.G., S.P. Buslaeva, V.B. 0sipov, Yu.A. Panin, L.D. Solodikhina, L.B. Upadyshev, ¥.P. Karpukhin, and I.F. Faingold (1975). Radiatipn .for a Clean Environment. P r o q e e d ~ s of Symposium (~unich). IAEA, Vienna, 419-431 • Lju, E., I.E. ~ a r o v , Yu.I. Kuryatr~ikov, A.P. ~-zanko, R.V. Dzhagatspanyan, and A.K. Pikaev (1982). Radiation-flotation purification of aqueous wastes from mercury. Book of Abstracts. IV International Meetin~ on Radiation ProcessinK, Dubrovnik, Yugoslavia, 43 Lju, E., I.E. Nakarov, and A.K.Pikaev (1983 a). Khimiya v y s o ~ k h enerEii, 17, 50-55Lju, E., I.E. Nakarov, and A.K.Pikaev (1983 b). ProoeedinEs of V T i h ~ S2mposium on Radiation Chemistr?/. Akademiai Kiado, Budapest (in press). Nakarochkina, L.M., A.K. Mikhailova, ~.T. Pilippov, A.I. Gershenovich, and R.V. Dzhagatspanyan (1969). ~ c h e s k a y a promyah!ennost, N 12, 905-909. ~akarochkina, L.M., A.K. N/khailova, ~.T. Filippov, A.I. Gershenovich, and R.V. Dzhagatspanyan (1974). Khim.icheskaya p r ~ s ~ o s t , N 7, 501-504. Mann, L.A. (1971). Isotopes and Radiation TechnoloF~7, 8, 439-444. N/~-~lova, A.,S. Naohev, and A. Andreeva (1974). Trud~ vodo~abzhenlya, k~izats~i i ~n~t~i te~ki, 10, 191-197. Natroahvili, G.R., and E.M. Nanobashvili (1967). Trud2 TbiliskoKo ped~Eo~icheskogo instituta ira. A.S.Puahkina, 20, 15-20. Natroshvili, G.R., ~.V.Panchvidze, and E.M. Nanobaahvili (1972). P r o c 0 e d ~ s of III Tihan~ Symposium o.n R@diation Chemistry, Akademiai K.iado, Budapest, 1281-1291. Nikiforov, N.N., V.N. Shubin, S.A. Brusentseva, D.~. Zorin, P.I. Dolin, and I.D. Griahaev (1982). ¥ o d o ~ b z h e n i e i sanitarnaya t e k ~ k a , N 6, 6-8. Nikonorova, G.K., V.N. Shubin, S.A. Brusentsevaand P.I. Dolin (1976). Vodn~e resurs~, N 3, 149-155. Nikonorova, G.K., V.N. Shubin, S.A. Brusentseva, P.I. Dolin, G.N. Koleboshin, Yu.I. S h ~ , Yu.N. Sorokin, E.P. Petryaev, A.~. Kovalevskaya, V.P. Burtsev, and M.M. Khokhlova (1980), Kh~micheska2a prom~shlennost, N 9,
Radia[ion Trcutmcnt of Liqmd V~'a~tcs
97
533-534. Petrya~v, E.P., A.M. Kovalevmkaya, V.G. 3chlyk, Y u . L V~-~uskaya, G.A. Zhal e i k o , and O.B. Steb~uov (1978). I z v . A~ B S ~ . 3 e r ~ f l z ~ m ~ r K . ~ , N 1, 21-25 I ~ t r y a e v , E . P . , V.I. Vlasova, T.A. Ryabushko, N.N. 3ubbotina, and R.N. Tschekaleva (1982). Ts~etn~e mete~l~, N 4, 105-106. Flkaev, A.K. (1982). I n v i t e d Papers.TV I n t e r n a t i o n a l ~ e e t l ~ on Radiat£on Procemmln~, Dubrovnlk, Yugoslavla, 261-280 Irlustcheva, G.L. (1971)° M e d i t s y n s k ~ a p a r u i t o l o ~ l y a i p a r a s l t a r n y e b o l e z nl. 40, 461-465. Ryabchenko, V.A., E.L. Mendel 'son, N°A. Arbuzova, and V.A. Gol'din (1980). Vod~snlbmhen!e I kanallzatslya, N 3(46), 42-44. Shubln, V.N., S.A. Brusentseva, and G°K. Nikonorova (1979). -Polvmerizatlon Purlfioat~0n 9f Industrial Wastes° At~nizdat, Moscow (in Russian). Shubin, V.N., S.A. Brusentseva, and G.K. Nikonorova (9180). ~ . ~ i = . k ~ , , 54, 2557-2560. Shubln, V.N., I.D. Grlshaev, N.S. Fel', S.A. Brusentseva, P.I. Dolin, S.P. ~ova, L.A. Zaozerskaya, and D.M. Zorin (1983). Radimt.Phys.Chem, (in press). Sidorenko, G.I., M.A. Pin, gin, and V.T. Savenkova (1963). GiE£ena i s a ~ t ariga, 28, N 9, 97-98. Takehisa, M., and A. Sakumoto (1982). Industrial ADDllcation of Radioisotopes epld R~diatlon ~ech~olo~y. l~ooeediz~s 9~ Conference ~Gren0ble ) • IAEA, Vienna, 217-233. Touhill, C.I., E.C. uA1.tin, M.P. Pujihara, D.E. Obsen, I.E. Stein, and G.IcDonnel (1969). J.Water Pollution Control Peder~ion. Dart 2. 41, N 2, 44-60. Tyutyukanova, G.K., N.D. ~neu'yeva, M.S. Sokolov, and V.N. Primak-~irolyuboy (1980). Khlmi~a v sel'skom k~ozyaistve , 18, 51-54. Vinogradov, G.A. (1980). Tezisy dokladov sove stchanlya Do radzLatsionnol k h ~ m t i orEanicheskikh s o e d i n e n i i . Moskva, 25. Vysotskayaj N.A., L.G. Shevohuk, and G.P.Alieva (1980 a ) . t e c h n o l o = i y a , N 1, 53-55. Vysotskaya, N.A., A.P. Rekasheva, and L.G. Shevchuk (1980 b). R a d i a t i o n Tr~atn~nt of Sewage S!u~es. Tekhnika, Kiev (in Russian) Woodbrldge, D.D., P.C. Cooper, A.J. van der Berg, H.D. ~usselman, and H.N. Lowe (1975). Radiatign for a Clean Environment. ~r0c~edim~s of S~Doslum { ~ o h ~ . IAEA, Vienna, 169-188. Zolotova, E.P., Z.N. Makarenko, and S.A. Brusentseva (197~). Trudy VODGEO. vy=. 49 • ~er. V0d.0snab~,henie, 22-24. •
0|4~572,~84 $3.00+,(N) Pergamon Press Lid
Pnnzcd in Great Bnzain.
RADIATI~ ~REA~M~T OF LIQUID WASTES
A.K. Fikaev, V.N. Shubin* Institute of I~Tslcal Chemistry of the A o a d e ~ of Solences of t h e U.S.S.R., Moscow, U.S.S.R. * I n s t i t u t e o f E l e c t r o c h e m i s t r y o f t h e Aoaden~ o f S c i e n c e s of the U.S.S.R., MOSOOW, U.S.S.R.
~BSTRACT The p a p e r i s t h e r e v i e w on r a d i a t i o n t r e a t m e n t o f n a t u r a l and p o l l u t e d wa~ers, x~latlo~ dcoomposltion of dyes, phenols, o~m~des eto., x~Li&tlon heterogeneous pu1~Ifioation (for ex~nple, radiation purifioation in the presenoe of sorben%s), radlation-flotation pul~fl~ation of aqueous wastes f~om mercury, l~iatlon-polymex-i~tlon puA-ifioatlon, x~tlatlon ~IsiDfeotlon of wastes. The s p e c i a l a t t e n t i o n i s p a i d t o t h e works o f S o v i e t a u t h o r s . KEY~ORDS Radiation treatment;
liquid wastes; natural
water; radiation
heterogeneous
purlfloatlon; radlatlon-flotatlon purification; radlatlon-polymeri~ation pu_~iftoation; radiation
disinfection.
~R~DUG~ION • ecauae o f f a s t development o f i x u l u a t z ~ and e~pmioult~ze the problem o f p u rification o f i n d u s t r i a l end m m ~ o i p ~ l wastes i s sharpened i n am~y c o u n t r i e s . One o f t h e p e r s p e c t i v e wa~s f o r t h e s o l u t i o n o f t h i s p r o b l e ~ i s t h e a p p l i c a t i o n of the energy of i o n i z i n g r a d i a t i o n .
During the aotio~ o f ioni~4-~ radiation on water h,yd..z'Lted eleo%zons ( e~q ), h~drogcn atoms and h~droxyl radloals which are very strong reducing and oxidi~ e~ents are formed. These species a~w cal~ble to anceRpiAah various radlolytlo t x ~ x s ~ o z ~ a t i o ~ s of solutes (redox reactlons, decaapoaltlon o f orga~Lc compounds, d i s o o l o ~ r a t i o n o f dyes, f c z ' ~ Z t i ~ o f p r e c i p i t a t e s e t c . ) . It is also well-M~si that ionizing z1~Li&tio~ bLs & stezili~bmg e~tlon. These e f f e c t s exe t h e ba~Ls fO~ t h e d e v e l o l m e ~ t o f x ~ L I A t £ = m e t h y l s o f p u zlfieati~ of aqueous wastes. At p r e s e n t t h e i n v e s t i g a t i o m . s i n t h e f i e l d RPC 24/1-F
77
of appll~tiom
of ioni~
z~lia-
tion for purification of liquid wastes are carried out in many laboratories. In this paper the most important results, which have been obtained in the direction under consideration in the U.S.S.R., are discussed. Some of these results were considered in books by Dolin and others (1970), Shubin and others (1979), Dzhagatspanyan end others (1979, 1981), Dmitriev end others (1981) end in review by Pikaev (1982). RADIATION TREAT~RNT OF NATURAL AND POLLUTED WATER In the 60-70s in the U.S.S.R. a lot of investigations (see e.g. Apel'zin and others (1973), Brusentseva end others (1975), Dolin and others (1970), Guteev and others (1978) on radiation treatment of natural water was carried out. The purpose of these studies was the improvement of characteristics of water purified by traditional methods or even their complete substitution. The important parameter of the quality of natural water is the color. It is due to the presence of different fractions of humus compounds: humic acids and colloidal and/or dissolved fulvic acids. Since the content of various fractions in the water of concrete reservoir was different, the experiments were performed with using both natural water and model solutions. The latter was necessary for the choice of optimal regime of radiation treatment (dose and dose rate) of any water with known content of humus compounds end also organic substances causing the taste end the odor. The radiation sources were 60Co installation and linear electron accelerator U-12 (electron energy is 5 MeV). Figure I shows the results of the study of radiation discolouration of aqueous solutions of humus compounds. The doses which are necessary for color removal from water of different reservoirs to 20 degrees (as it is required by respective State standard on drinking water) are given in Table I. From Table I it is seen that air bubbling favours the color removal from water of different sources. It is also necessary to mention that the doses required are the same in case of 6Oco
T-rays
and the fast electrons.
Research on radiation odor control was performed by using the solutions of 4 groups of organic substances isolated from natural waters. The results obtained are listed in Table 2. The efficiency of radiation removal of comparatively small amounts of o r g e ~ c impurities is confirmed by tertiary purification of wastes of the Baikal cellulose-paper plant after ch~mlcal s~Id biological purification. Figure 2 shows the respective results. It is seen that irradiation together
Radiation
~ t
8 6
of
Liquid
Wast~
t.0
7~
"--'~-x- g
" " - ' ~ C - -
'O
Z
t
Trcatmcnc
' X--4
f0
t5
P i ~ . 1. R a d i a t i o n d i s ¢ o l o u r a t i o n o f aqueous s o l u t i o n s o f humus oompoundsz 1 - s o l u t i o n o f humio a c i d s (pH 7 . 1 ) ; 2-solution of f u l v i c a c i d s (pH 7 , 1 ) ; >-colloidal solution of fulvlc acids (pH 7). Dose rate (Gys-1):
4.9(o); 3(x) end 0.58 (4). 1
R a d i a t i o ~ Dls00~o~umtion o f Water f,r~Sn Rese~To~rs o f 10800W D:~Stz~ot H .
II
Reservoir i
Inltlal color, deg
,,l
i
,,
~w~.z~d ~o= color r ~ t o 20 de8 Without a i r b u b b l i n g With a i r b u b b l ~
i
Uoha ~ e a l r v o i r
,,
Dose ( k ~ )
i lis
,
35
0.8
0.6
Eastern water treatment plant
33
0.5
0.35
K].yas e ~ voi.r
49
4.0
0.8
H,
reeler--
,
, IHI
,,
, ,,
TABLE 2
Radiation Odor Control
Raw water Odor inCOD, tensity,TON
Group of organic substances
Substances of the group
Neutral compounds
Hydrocarbons, ethers,esters, aldehydes, ketones,nitriles, sulfides etc.
140-100
110
Strong organic acids
Fatty acids
100-70
5
Weak organic acids
Phenols,substituted phenols, mercaptans, naphtenic acids et6.
70-50
10
6
Basic orgRn~c compounds
Amines,pyridine bases etc.
250-200
10
12
~02/dmJ
Irradiated water Odor in- COD, 3 tensity, mgO2/dm TON 17-12
15"
10
• Dose rate was 0.58 Gys-1; in other cases it was 3.6 Gys "I. with air b u b b 1 1 ~ decreases the color to 8-I0 degrees. In this case the decrease of the dose rate intensifies the process; already after irradiation to doses 0.1-0.3 kGy the color and COD of water correspond to the State standard on drinking water. Petryaev and others (1982) studied in detail the bactericidal effect of -radiation on biologically purified municipal and industrial wastes with increased content of org-n~c impurities (COD is up to 5 0 m ~ 02/dm3). The data of this study are shown in Table 3.
~
An~3 ogous investigations of municipal liquid wastes after 2 sta~es of biological purifioationwere performed by Mann (1971). sdm~lar.
The results obt,~ned are
Zolotova and others (1975), Woodbridge and others (1975) and Ryabchenko and others (1980) checked static system data at small flow-type pilot plants (output is up to 1.5 m 3 a day). The results were approximately the same. The irradiation to doses 0.6-0.8 kGy together with air bubbling gives the water which can be used for irrigation and drinking. In 1970 after prelimlnary tests the commercial plant with output of 38 m 3 a day was constructed in the U.S.A.(see Woodbridge and others(1975)). It was included in the
Radiatwon Trcatmenx of Liquid Wastes
81
I
D
Fig. 2.
f
2
3
R a d i a t i o n o o l o r ~wmoval f r ~ n w a s t e s o f t h e B a i k a l c e l l u l o s e - p a p e r p l a n t e ~ t e r obAm~oal and b i o l o g i c a l purification (dose rate 5.82 Gys-I):
1-wlthout air bubbling; 2-post-effeot after irradiation without air bubbli~;>-ai~ bubbling; 4 - a i r b u b b l i n g , dose r a t e 0.108 G~s -1 ,
Radiation ]~1.s1.~eo~:i.on
,,,
Dose, (}y
,
I
III
,
micro-
DlaCn:~ect:Lo~,%
,
0 90 300 500 800 1000
1.20 2.17 2.90 1.75 1.25 0.85 I
J
II
II
,
,
x 105 x 103
x x x x
oamplex of b l o l o ~ L e s l pumlfioa¢ion° dolle.rs/m 3
I
,
,
,,
H,
0 98ol 99.76 99.85 99.89 99.92
102 102 102 102
II
Itclti~i
,
Amount o f m ~ e d
,,i,,
~iol~~
of
IIIII
I
I
I
I
IIII
lIB
I
II
The ooet of puzl~loatim~ i s 0.38
The economical evaluation of the cost of complex purification of natural water was carried out by Guteev and others (1978). The evaluation was performed for radiation plants on the basis of electron accelerators with outputs of 100, 1000 and 5000 m 3 a day. It was calculated that the cost of purification of I m 3 was 2, 0.5 and 0.17 roubles. At present these values are comparable with the cost of purification by chemical method. Let us note that the cost of radiation purification should be lowered considerably after the increase of the power of used accelerators. RADIATION PURIFICATION OF INDUSTRIAL LIQUID WASTES In the preceding chapter it was shown compounds which were present in water fication were comparatively low. The tion contains the compounds which are dyes, phenol,
cyanides,
that in the case of simple chemical in small amounts the doses for purisituation is more complex when solupoisonous or hardly decomposed (e.g.
salts of mercury and bismuth etc.).
The radiation sensitivity of cotton-mills wastes, which are often coloured intensively because of residual dye concentrations, is enough high. It is clear since the radicals from water radiolysis attack in first turn the chromophoric groups which are responsible for the color of dye. Apparently, the results of irradiation are specific for dyes of different types. The main kinetic peculiarities for radiation discolouration of solutions of different azodyes both in the presence of oxygen and in its absence have been studied in detail by Khabarov and others (1981) and Takehisa and others (1982). It was found that disoolouration is a non-chain process ; the radiation-chemical yields do not exceed units or even tenth parts of unit. The doses required for discolouration depend on the type of dye; they are differed by almost two orders of magnitude. The process does not depend on the temperature. However, the yield depends on some additions (e.g. ions of transition metals). It was obtained by Case and others (1971) that the average dose for wastes taken from dye vats is 10-15 kGy. Case and others (1971), Dykhanov and others (1979), Tyutyukanova and others ( 1 9 8 0 ) f o u n d that approximately the same dose is necessary for the decomposition of pesticides. The other example of compounds, small amounts of which do not allow to use the water repeatedly and to throw off it the basin, are sulfides. Natroshvili and Nanobashvili (1967) and Natroshvili and others (1972) studied the radiolytic transformations in aqueous solutions of the compounds of sulfur in low valent states. It was found that the yields of oxidation of HS- to $20 ~- and SO~- were increased with the increase of acidity; they achieved 25 molecules/t00 eY, when the solution was bubbled by oxygen.
Radiation Trca~mem of Liquid W~stcs
83
G e r a ~ t m o v i c h and o t h e r s 41980) i n v e s t A g ~ t e d t h e a o t l ~ o f i o n i z i n g r a d i a t i o n on c o n d e ~ a t e s oZ e v a p o r a t e - s h o p s o f s u l f a t e c e l l u l o s e ~ o d u c t i o n p l a n t s . I t was e a t e ~ l A ~ h e d t h a t dome 1-2 kGy was s u f f i c i e n t f o r t h s dec~npoeition of s u l f i d e s oontaAnAn~ i n t h e w a s t e s t o 75-95 % ( a t p~ 4 - ~ ) . T h i o s u l f a t e s , s u l f t t e s and e l e m e n t a l s u l f u r which a ~ form ed d u r i ~ i X T a d i a t t o n a r e l e s s to
c
P h e n o l i s h a r d l y dec~npoeed d u r i n g i r r a d i a t i o n . I t i s p r e s e n t i n man~ w a ~ e s and i t i s ~,npossible t o us e t h e w a t e r w i t h p h e n o l c o n t e n t more t h a n 10 - 3 mg/~n 3. Because o f i t t h e r a d i a t i o n d e c o m p o s i t i o n o f p h e n o l i n aqueous s o l u t i o - - A was s ~ u d i e d t h o r o u g h l y by T o u h i l l and o t h e r s 41969), B r u s e n t e e v a and o t h e r s ( 1 9 7 1 ) , V y s o t s k a y a and o t h e r s 41980a). At low dose r a t e ( N O . 1 Gys-1 ) t h e c h a ~ t r a n s f o r m a t i o n o f p h e n o l w i t h t h e y i e l d o f 250-~00 m o l e o u l e s / q 0 0 eV t o o k p l a c e An a e r a t e d s o l u t i o n s . The main p r o c e s s o f p h e n o l t r a n s f o w , ~ t i o n se~ns t o be t h e c o n d e n s a t i o n . Y i g u ~ 3 shows t h e d e p e n d e n c e o f t h e y i e l d o f p h e n o l d e o ~ n p o ~ t ~ l o n on dose r a t e o f T - r a d i a t i o n . The i n c r e a s e o f t e m p e r a t u r e t o ~O°C g i v e s 2 t i m e i n o r e u e o f t h e y i e l d o f phenol dec~position, and t h e e f f i c i e n c y o f t h e p r o c e s s i s f a v o u r e d by o ~ Ken b u b b l i n g d u r i n g i r r a d A a t i o n . At h i g h dose r a t e s and a l s o i n t h e a b s e n c e o f o x y g en t h e p r o c e s s i s non-oheAn; i n thAs c a s e t h e p~oduot s a r e h i - and o t h e r p o l y a t ~ i ¢ p h e n o l s . ~h~ f i n a l p r o d u c t s o f m a ~ - s t e p t r a n s f o r m a t i o n a~e m ~ e i c a c i d end o t h e r n o n - a r o m a t i c c~apounds. However, t h e d o s e s f o r s u ch s t r a n s f o r m a t i o n a r e h i g h ( 0 . 2 - 0 . 2 5 MGy). T a k e h i s a and o t h e r s (1982) showed t h a t t h e dos e can be d e c r e a s e d c o n ~ i d e r a b l y ( t h e y i e l d o f t h e d e c r e a s e o f t o t a l o r g a n i c c a r b o n i s i n c x ~ a s e d by 20 t i m e s ) by t h e o ~ b i n ~ t i o n o f ~ation with osonation. I n t h i s combined p r o c e s s t h e o a r b o x ~ l a c i d s ( m a i n l y o x a l i c a c i d ) are f o ~ e d ; ~ h e ~ ~hey e~e d e c ~ a p o ~ d t o CO2 and ~20. V y s o t s k a ~ a and o t h e r s ( 1 9 8 0 a ) f o u ~ t h a t t h e r e s u l t o f i r ~ t i o n of i n d u s t r i a l w a s t e s oonte~in~u~ p h e n o l s , m e t h a n o l and for, ~al deh~ds i s t h e f o r mation of precipitates. L e t u s c o n s i d e r t h e reAiatlo~ pu_~Afloatlon o f ~qu~ous s o l u t i c m s o f one o f the moat poisonous s u b s t ~ c e s wb.i~h i s widely used in Kold i n d u s t ~ and i n g ~ l v a n i c c o a t i n g s s h o p s , namely - c y a n i d e s . ~ouhS.ll and o t h e r s (1969) s t u d i e d t h e i n ~ l u e n c e o f dos e r a t e , o ~ g e n o o n a e n t r a t i Q n , t e | a p e r a t u ~ , c o n c e n t r a t i o n o f oyanAdes (:~Xwm 26 ~ d m 3 t o 2 . 6 ~/dm 3) a~d ~ t a l y s t s ~ th~s i~ooess. I t was f o u n d t h a t u n d e r s t a t i c o o n d i t i ~ mad i n f l o w s y a t m t h e c ~ r p l e t e d e a a n p o s i t i o n o f c y a n i d e s i n t h e s o l u t i c ~ w 4t h c o n c e n t r a ~ i o n o f 2 6 ~ / d m 3 ~ S a t dose 1 . 8 - 2 kGy. ~ l~cooess i s a c c e l e r a t e d a t 100°C and
i n tho pr.. e of black, + ¢zO,, I n more oonoentx~_~ed i o l u t ¢ o n s t h e d o s e s r e q u l ~ e d f o r ~ e o o m ~ m i t i o n are incz~c.-ed t o 10-.104 k(~r (see D o l i n and o t h e r s 4 1 9 7 0 ) , ] i i t r o a i s v A l i and o t h e r s (1967), T ~ i l l and o t h e r s (1969) •
~-
A.K.
PIKAEV AND V, N. SHUBIN
3oo
~
~u
200
-/00
0 a.Of Pig. 3-
0,! /,0 ose zate ,
Dependence of yield of phenol decomposition on dose rate of T-radiation: l-aerated solution; 2-deaerated solution
Arshakuni and others (1971) obtained that cyanides in the solutions with concentration of 500-600 mg/dm 3 and at pH 6.5-7.0 are decomposed via chain mechanism. At dose rate 180 Gyh -1 the yield was 1200 ions/100 eV. On the basis of these results the pilot plant with 60Co source (output is 200 m 3 a day) for the decomposition of o y - ~ d e s was elaborated (see Kon'kov and others (1975)). Lju and others (1982) developed the radiation-flotation method of purification of industrial wastes from mercury. The wastes were from plants producing chlorine and alkali by electrolysis method with using the mercury as a cathode. The method developed consists of three stages:preliminary flotation in the presence of eurfactant (sodium alkylsulfonate), ~-irradiation and secondary flotation (also in the presence of sodium alkylsulfonate). The principal scheme of the method is shown in Pig. 4- By means of this method it is possible to purify the wastes from mercury presenting in different forms (dlssolved~as a metal and in precipitate) up to limiting permitted concentration ( ~ 5xiO -3 Optimum conditions for the purification are the following: I) at prellm~n-ry flotation the pH value of waste is 12-13, concentration of sodium alkylsulfonate is 50 mg/dm 3, the rate of air feed is 0.02-6.0 dm3/min; 2) at ~-irradiation the pH value is 12-13, dose is I kGy; 3) the conditions for secondary flotation are the same as for
mg/dm3).
Radiazion Treatmem of Lkt~d Waste5
~
85
~°
foam c o n d e n s a t e f o r b u r n i n g
. o d i u m ~ a l k y l s u l f o n a t e solution
"1
-1 compressed a i r
PiK. 4.
otator
','I
for neutralizetion
Principal scheme of purification of wastes frc~ mercury by ~adiation-flotation method.
The r e d u c t i o n o f i o n i c m e r c u r y t o m e t a l l i c one o c c u r s d u r i ~ i r r a d i a t i o n . At d o s e o f I kGy t h e ox~Een p.~eeenting i n w a s t e i s O ~ ~ . ~ p l e t e l y , and i n a l k a l i n e medium i o n i c m e r c u r y i s r e d u c e d by e - . I t i s o a ~ f i m e d by t h e d a t a o b t a i n e d by L j u and o t h e r s (1983a,19 8 3b ) d u r ~ the investigation of pu~me ~ o l ~ s l s of a l ~ 1 i n e solutio~I o f ionic and ~ l l o me~cau~y. ~ o e , the ~ l~sult of i~r~d~ation o f w~stes o o ~ t ~ m~T~y le ~he reaction of blv~Im~t mercury to me~alllo one and/or m m k l ~ soluble ImeU~meo~o~al4mt fern (H~(OH) 2 type) which are re~oved effectively by fl~ati~m, GETEROG~EOUS R A D I A T I ~ DESTRUCTION
F r ~ e o o n ~ - ~ o a l p o i n t o f view t h e r a d i a t i o n p u r i f i c a t i o n o f a q u e o ~ r u t h is perspective in the case of nh.~n process. Because of ~ effiolen~y of ter~watlon of c~-In- this process Is impossible for diluted 8queens solutions. However, the conditions promotlng to the .~.4. deeomposltlon of Or~hn£C pollutants can be obtained by the oombinatlo~ of ~ t i o n des~ruotlon with a~o~lon o f p o l l u t a n t s by a c t i v e c ~ r b o n . Aotlve m ~ b o n is ~ a d ~ useA durln~ ~ y yea~s f o r t ~ e ~ o f orKe~Ao pollutemts from different waa~es. However it loKts t h e sO~'pt£on O a l ~ l t y
8A~er same vox~Lug p e r i o d end t h i s c a p a c i t y s h o u l d be x s ~ e n o ~ t e d
pe~od~oally.
A. K. P:KAEV ,~,'~o V. N. SHUm~
The t r a d i t i o n a l method of regeneration is the treatment in special ovens at 900-1000oC. In 1972 the low tanperature method of destruction of organic s u b s t a n c e s a d s o r b e d a t t h e c a r b o n s u r f a c e by i r r a d i a t i o n was p r o p o s e d by Case and K e t c h e n ( 1 9 7 2 ) . U n f o r t , m a t e l y , t h e low t e m p e r a t u r e r e g e n e r a t i o n was n o t o o n t i n u o u s p r o c e s s ; t h e r e a s o n was t o o h i g h i n t t i a l concentrations of pollutants. Shubin and others (1980) found that considerably better results can be obtained by the c~nbination of radiation treatment with adsorption at the stage of tertiary purification. In this case industrial or municipal waste is filtered, then it is treated by generally accepted methods at biological purification plant, where the flocculating agent is added to water for the precipitation of suspended organic substances. The next stage is the filtration through the sand. After the removal of the main amount of organic pollutants the water containing the organic pollutants up to 250 mg 02/dm3 is passed through the capacity with active carbon which adsorbs the residual organic substances. Initially, the carbon adsorbs the organic substances very effectively, and the considerable decrease of COD and color of wastes occur. However, the high content of organic substances in the waste leads to the fast decrease of adsorption activity of the carbon. After passing about 10 volumes of liquid per I volume of carbon the color of waste and its COD value become the same as for initial waste, i.e. the purification stops completely. Shubin and others (1980) observed that for the mainten-nee of adsorption activity of the carbon at sufficiently high level the wastes were passed through the column under conditions of continuous irradiation of sorbent by 60Co ~-rays. The method under consideration was applied by Nikiforov and others (1982) and Shubin and others (1983) for the purification and disinfection of wastes of live-stock farms. At present there are no methods of their purification which correspond completely to the sanitary standards. Because of it the control of the possibility of long action of sorbent during simultaneous irradiation had a great importance. It was found that at linear flow rate of 1.1 m.h -1 and dose rate 0.35-0.5 Gys -I the dose required for purification was 1.5 kGy. Any deterioration of the work of respective unit was not obtained after its operation during 3 months, and the purification gave the water which can be used repeatedly in industrial cycle or thrown off to any reservoir. This is illustrated by the data of Table 4. The similar results were obtained by Hay (1975) at pilot plant for the purification of wastes of poultrY farm. The initial waste had yellow-brown color, high turbidity, intense odor and COD value of 10OmgO2/dm3. After radiationadsorption treatment the water became colorless and odorless; COD value and contents of bacteria were decreased by 90% and 95% respectively. The time
R ~ a ~ o n Tmatmem of Lkluicl Wa.~e5
8"7
of oo~t~t b e ~ e e e ~ ~oz~m~t e ~ d weJo~es we~ ~0 m 4 , a t d o s e r a t e ~he o ~ r t o f m ~ h a p u r ~ i o n i s 0 . O 7 - 0 . 0 8 d e l l a r s / m )• ~
~? u z - J ~ . m ~ t £ a n of~ gss~'~s o f I £ ~ t ~ k
4
l~netera
Initial wastes
200.4 Suspended mabetances,
0.047
Trsns~e~,
3.5
~/~3
cm
1~
24.4 0.03
30
800
40
BOD5 , ~ ' 0 2 / ~ 3
96
8
7.5
7.05
Total nltroeen, me/din3
23.2
7.7
p043-, e~,/'~3
75
0.11
K+, n~,/dm3 utcrobe
number
E.ooli
Stapb~loooocus
2.7
by
Wastes after tz~t~mt
COD, .~021dm3
pH
Of 1 k G y h - 1.
0.2
1.1 ~ L l l l o n / c ~ 3
41 ~ L o r o b e c e d e / c a 3
2 . 5 x 104
not isolated
2 x 103
not isolated
Ap~rently, the radiation-adsorption m e t h o d i s one o f t h e o h e l p e ~ r a d i a t i o n methods. I t i s due t o t h e s p e c i f i c s of real radiation deetruot£on prote~, wh~oh o c c u r s u n d e r c o n d i t i o n s o f r a d i a t i o n - a d s o r p t i o n equ~librium: at steadys t a t e o o = o e n t r a t i o n of' ~ n p u ~ t i e e and with constant z~te. Besides, concentrat~ the pollutants in the marf~ce layer et~&tes the chin destruction and the octurence of rad~ation-o&tslytto process. ~ r , the mechenism of the pur~ication is not clear. Indeed, the yield of deetruotion o f orsanio mabstanoes calculated fr~ t h e c h a ~ e o f COD v a l u e i s c ~ . 600 e q u i v . / 1 0 0 eY. At t h e ~ t~e the oonte~t of o~reen in ~Ltial w~te Is ~ 8 ~ 3 . As it follows from analyaee, thle is by 100 times leas than the amount r e q u i r e d f o r o x i d a t i o n o f a l l ozl~__ic m a b e t a n o e e t o 0 ~ ~ d ~ 0 (Shub~n a n d o t h e r s (19B0, 1 9 8 3 ) , N i k i f o r o v a n d o t h e r s ( 1 9 8 2 ) ) . Undoubtedly, only profound inweetl~atlons will help to develop the prinolplee of the choice of optimum oondltions for prolonged radiatlon-adsorptlon pul~floatlon.
The o t h e r m e t h o d u s i ~ the sorption at interface b e t w e e n a q u e o u s and g a s p h a s e s was d e v e l o p e d b y D z h ~ a t s p a n y a n a n d o t h e r s ( 1 9 7 9 , 1981) a n d M a k a r o o h kima and others (1969, 1974) for the purification of wastes c o n t a i ~ synthetic detergents (in first turn biologically nom-decomposable). The presence of such "hard" detergents in wastes leads to the foam formation during the aeration in aerotanks and prevents the application of other purification methods (especially biological method). The alkylarylsulfonates belong to the hard detergents. During irradiation of the solution containing "h,rd" detergents the following processes take place: the decay of alkylarylsulfonate because of sulfogroup detachment, the appearance of sulfate ions in equivalent amount, the decrease of the foam formation or the complete disappearance of it, the increase of surface tension up to the value equal to that for pure water and the increase of COD and BOb values. The yields of products do not depend on dose rate. The radiation destruction in a bulk of the solution is non-chain process; it is the oxidation of detergent molecules with the participation of air oxygen. The similar processes occur in the foam, but because of high concentration of detergent at the surface of foam bubbles and great accessibility of the oxygen the chain process of oxidation occurs. This is confirmed by high yields of desulfation and destruction of detergent (up to 50 molecules/lO0 eV) and oxygen consuming (up to 900 molecules/100 eV). As it is concluded by Dzhagatspanyan and others (1979, 1981), the use of economical low energy accelerators increases sharply the profitability of the process and makes it to be possible for industrial application. The process of adsorption purification was used as a first step of the purification of exhaust industrial gases from SO 2 . As it was found by Baranova and others (1981), in the solution containing bivalent m a ~ a n e s e ions as a catalyst SO~- ions are oxidized to sulfate ions under the action of iation. This radiation-catalytic process occurs via chain mechanism and can be used for the purification of sulfuric acid production exhaust gases
-rad-
with O.1-O.3% (in volume) content of SO 2. RADIATION-POLYmERIZATION
PURIFICATION
The formation of insoluble precipitate during irradiation of the solutions containing the substances which can be polymerized under the action of ionlz~ng radiation is used in radiation-polymerization method. The precipitate of polymer captures the pollutants and consequently purifies the solution. The formation of long nh--~ns of polymer takes place via opening the double bonds and cycles in molecules of organic compounds which is usually called by monomers. Such compounds can present in some wastes, but can be added also in it immediately before irradiation.
L~:liacion Trcam~nt o[ l.iqmd Waste5
~9
However, i t i s n e c e s s a r y t o s t r e s s t h a t t h e mean pArpose o f mW p u r i f i c a t i o n , which i s t h e s e p a r a t i o n o f p o l l u t a n t s ~-z~ pu~e sol~en%, i . e . w a t e r , can be d e c i d e d o~l~ by h e t e r o K e n e o u s p o l s ~ e ~ i ~ t i ~ n when t h e p o l ~ e r t o K e t h e r w i t h pollutants is p r e c i p i t a t e d and t h e n removed by known ~ e t h o d ~ 8 e t t l ~ , filtration o r c e n t r i f u g a t i o n . . From t h i s i t f o l l o w s t h a t t h e nm£n d i r e c t i o n o f
the development of redlatlom-poly~erlsatlon me%hod is the study of the possibility of captuzlmK the pollutants by insoluble polymer ~ c i ~ I t a t e e duzlnK l r r a d A & t l o n of w a s t e s w i t h a d d i t i o n o f monomers o r w i t h o u t added m ~ : e s (see S h u b l n a~d o t h e r s (1979), Nikonomov~ and othems (1976)). It is neee888zy to d A e t ~ a h the foll~win~ typical cases. I ). I n s o l u b l e p o l y m e r p r e c i p i t a t e formed by r a d i a t i o n p o l y ~ r i z ~ t i o n of s p e ~ l ~ l l ~ added monomer can remove t h e p o l l u t a n t s by t h e i r a d s o r p t i o n o r f o r a m t i o n o f e u t e c t i c mixture. 2 ). R a d i a t i o n t r e a t m e n t b e i n g t h e p o w e r f u l means o f ~ n ~ t i a t i o n can l e a d t o p o l y m e r i z a t i o n ( t h i s p r o c e s s i s o f t e n oeS.~ed by cmada~m~t~on s i n c e t h e h ~ d ~ e n is siumlteneously fozmed) of low-molecular c ~ WhiCh ~enezal-
ly do not belonK to mon~mers° 3)- N o n - p o l y m e r i z a b l e p o l l u t a n t s can be i n c l u d e d An rs&ti&tlon ~ - J t i a t e d polymeri~tion. Such an example i s t h e p u r i f i c a t i o n o f t h e w -e~es o f c e l l u l o m e - l m ~ ple,uta. These w a s t e s c o n t e £ n l i a m ~ e w hi ch iS OZ~m~O hamopolyn~r of c~aplex o~position. I t was f o u n d by Sh~bAn a n d o t h e r s (1979) t h a t r a d i a t i o n o x i d a t i o n o f t h i s c ~ p o u n d occur~uK v i a d e s t m a e t l o n o f p o l ~ e r i s n o t s u f f i c i e n t l y e f f e c t i v e , and t h e u t i ~ f ~ o t o r y p u l " i f i c a t i o n o f wastes requires the ~ d o s e s (up t o I MGy). ~ i t s e l f i s n o t cA-osalt--ka~, and t h e p r e ~ L p i t a t e i s n o t f a m e d . However, ~ n ~ o l u b l e p o ] ~ a r prec£1~it&te foz~An~ d u r i n K i r r a d i a t i o n o f t h e s o l u t i o n w i t h ~ o n m e r a d d i t i o n c a p t u r e s p o l l u t a n t s from t h e s o l u t i o n ( o b ~ o u s l ~ , b e o m a a e o f ~ r ~ t ~ t - o o p o l s ~ a e r i ~ t i o n ) (see N A k ~ o r o v a and o t h e r s (1976). 4). The p u r i f i c a t i o n o f p o l y m e r i n d u s t r y w a s t e s o o n t a A n £ ~ t h e r e m i n d e r s of the ayn'Pdaeaes- ollKomers, polymers which eze net pol~Rae~ised oaapletely e t c . i s lXWaible. A p p a r e n t l y , i n t h i s c a s e o p t ~ oondltio~ for the o~p l e t ~ o n o f t h e r e a c t i o n i n aqueous phase ca~ be c r e a t e d by t h e c h o i c e o f ~ l o n reg~, t e m p e r a t u r e , 1~ a n d a d d i t i o n o f s u b ~ 8 ualm~ i n t e e h noleSieal process.
The s p e e ~ o p e e u l i L r i t ¥ of r a d ~ a t i o n - ~ l ~ m e r i ~ i o n p ~ - l f l ~ t i ~ r e e l i ~ t i o n ~f h e t ~ o u s ~ol~mq~ up t o ~ (deathly de~ree of oonwersion. I t l a due t o the t o x i t ~ of z~E~hukl ~ r . To u ~
the r~Latic~
initiated
po~rir~tion
i s the v~ t o 1 0 ~ )
for the pu~if~ostion of stem
i s p o s s i b l e o n l y i n t h e c a s e when t h e p r e s e n c e o f p o l l u t a n t d o e s n o t l e a d t o effective c h a i n t e z ~ i n a t i o n and t h e c h a i n m e c h a n i s m o f p o l y m e r i z a t i o n i s k e p t t o h i g h (80-90%) d e g r e e o f monomer c o n v e r s i o n (1979), N i k o n o r o v a a n d o t h e r s (1976)).
( s e e S h u b i n and o t h e r s
In the studies under consideration methyl methacrylate, methyl acrylate, vinyl acetate and acrolein were used. The main part of the work was performed with 10 -I- 10 -2 mol dm -3 aqueous solutions of methyl methacrylate. It was established that the ch-~n mechanism of polymerization is kept up to 70-90% degree of monomer conversion. As it follows from the dependences on concentration and dose rate at high degrees of transformation the process is complicated with the growth of heterogeneity of the process; however, it keeps the main peculiarities of initial stages of conversion. The presence of oxygen lowers the polymerization rate; the decrease of pH increases the rate. At the next stage the regularities of radiation polymerizationwere studied in the presence of pollutants. For this the process was investigated with using the real wastes or model solutions. The real wastes were black waste of sulfate production of cellulose and waste of sulfite production of this material. The model solutions were solutions of dyes and urea. It was established that the irradiation of all the systems under consideration with methyl methacrylate addition (or other monomers) led to the formation of insoluble polymer precipitate. As in pure solutions of monomer, the c h a i n m e c h a n i e m o f t h e p r o c e s s was k e p t t o h i g h c o n v e r s i o n d e g r e e . For example, on polymerization of methyl methacrylate in black waste the yield o f monomer d e c r e a s e a t 15% c o n v e r s i o n was 3000 m o l e c u l e s / 1 0 0 e¥ and a t 55% c o n v e r s i o n i t was e q u a l t o 2000 m o l e c u l e s / 1 0 0 e ¥ . The d e g r e e o f p u r i f i c a t i o n was i n c r e a s e d w i t h t h e i n c r e a s e o f monomer c o n c e n t r a t i o n , the decrease of d o s e r a t e a n d pH a n d a t o p t i m a l c o n d i t i o n s i t c a n r e a c h 8 0 - 8 5 % a t d o s e s 0.1-1 kGy. The water purified from l i ~ i n e
can be returned to the plant for wm~h~mg
the cellulose, and the polymer precipitate with captured lignine after the dissolution i n monomer c a n be u s e d f o r t h e p r o d u c t i o n o f p o l y m e r i c g o o d s ( s e e P e t r y a e v and o t h e r s ( 1 9 7 8 ) ) . S u c h a s t u d y was p e r f o r m e d w i t h t h e w a s t e s of production of wood-fibrious plates mer. Developed technological scheme b i l i t y t o u s e wood r a w m a t e r i a l more precipitate for the treatment of the was shown by s p e c i a l c a l c u l a t i o n s the
c o n t a i n i n g l i g n i n e and r e s i d u a l m o n o of radiation purification gives a possic o m p l e t e l y and t o a p p l y t h e p o l y m e r murfaoe of wood-fibrious plates. As i t process is profitable.
The other perspective direction is the radiation treatment of the wastes of
Radiation Treatmenz of Liquid Waszes
91
polymer i n d u s t r y . For e ~ p l e , t h e w a s t e s o f one o f s u c h p l a n t s , p r o d u c i n g p o l y e s t e r s , have t h e f o l l o w i n g p e ~ m e t e r s : water-93%, ~ n e r a l s a l t s - l % , o r g a n i c s a l t s - l % , b y - p r o d u c t s (polymer p o l y ~ e r i z e d n o t c ~ p l e t e l y ) - ~ . 4 % , COD~10 ~ n~O2/dm3, pH 5 . 5 . I~ has i n , e n d i v e b l u e c o l o r and oontaAns t h e p r e c i p i t a t e (Ca. 20 ~'d~3)(eee Shubin and o t h e r s (1979), N~konor~va and o t h e r s
(~981)). R a d i a t i o n t r e & m e n t of s u c h & waste a f t e r a c i d i f i c a t A o n t o pH 4-4 by d o s e s 1-2 kGy d e c r e a s e s COD and c o l o r by 85-90% ( s e e F i g . 5 ) . ~ ThAs t r e a t m e n t leads ta the fo~tlon of c~pact, well-filtering prtcipita~e. Its htuidity i s 70~! i t can be d e c r e a s e d t o 3 0 ~ b y s ~ p l e p r e e s ~ .
.
~1-
L'--It-'-'~
O
t. !
0 ~.
o,s 5.
f,z
(6
10
Z7
0
Decrease o f COD (1) and f o r m a t i o n o f p r e ~ i p i t a t e (2) d u ~ i n & r a d l a t i o n t r e a t m e n t o f w a s t e o f p l a n t produci~ polyesters
At p r e s e n t t h e w a s t e s o f p l a n t s p r o d u c ~ p o l y e s t e r s a r e b u r n t . The c o s t o f thAs p r o c e s s i s 10-15 r o u b l e s / m 3 . F r ~ p r e l ~ : ~ y data it follows that the c o s t o f r a d X a t i c ~ p u r i f i c a t i o n i s c o n s i d e r a b l y l o w e r ( 2 - 4 r o u b l e e / m 3) • ~he polymer formed can be u s e d i n t e c h n o l o g y . As i t was f o u n d by Bondarenko s ~ l O~l~trS (1980), 1114m4111~m~13.te ~ x ~ o b t - 4 ~ d ~ ~ t ~ o n ptt~oation of the wastes of p l a n t s px,~duei~ v l ~ l a c e t a t e p l a ~ t i c s .
RADIATION DISINFECTION OF WASTES A lot of papers are devoted to disinfecting action of radiation. The studies have been carried out with bacteria, viruses and spores. It was established that radiation sensitivity of microorganisms is different. Bacteria are most sensitive, viruses are less sensitive, spores are most resistant to irradiation. For example, it was found by Touhill and others (1969) that disinfecting action of ionizing radiation on 4 m a i n groups of microorganisms, o c c u r i n g m o s t often in wastes: E.coli, enterococcus, spores and p~-g-coli, depends only on dose. At dose 2.5 kGy the amount of lost microorganisms was (in %): total amount of bacteria-99.995; coliforms-1OO; enterococcus-100; phag-coli-100; spores-92. The change of pH from 5 to 8 had no effect on radiation dislnfection (see Touhill and others (1969)). The dose of ~-and X-radiation which is necessary for the damage of definite number of E.coli cells in the absence of air is more by 10-12 times than in the presence of oxygen. It was also shovm that the presence of organic pollutants increases the dose required for disinfection. The detection of synergistic effect by Sidorenko and others (1963) is very important for radiation disinfection. The effect is that the results of combined action of radiation and other biologically active agent (for example, chlorine, heating etc.) are considerably better than the results of their separate actions. It decreases the ~n-ctivation dose for different bacteria by 5-10 times (see Woodbridge and others (1975)). The regularities obtained on model systems gave rise to construction of pilot and industrial plants. Since 1970 in the U.S.A. there is the large scale plant on radiation purification of mlm~cipal wastes in which the disinfection after biological purification is performed by ~-radiation treatment (see ~ - ~ (1971)). The output is 37.8 m 3 a day. The plant experience showed that the dose 0.5 kGy decreased the number of coliforms by 104 times and was sufficient for the dis~ection of wastes. Besides, the irradiation to such a dose improved noticeably the chemical, physical and biological parameters of wastes. In the paper by Mikhailova and others (1974) the results obtained d u r ~ the study of radiation disinfection of wastes of large live-stock breeding farm were published. The laboratory scale investigation on disinfection of such wastes by ~ - r a y s with consequent using as a fertilizer was carried out. The radiation sources were 60Co and 137Cs. The degree of disinfection was controlled by microbe number and coli-titre before and after irradiation. The determinations were performed through 2 hours, I, 2, 5 and 10 days after
~la~on
Tcea~rncnt of Liquid Wa-,~tc-~
93
irrsdiation. T ~ t i a l w a s t e had o o l i - t i t r e o f 10-7 and m i c r o b e number o f ~" 109. The d o s e was changed from 0.3 t o 6 . 6 kGy. Zt was show~ t h a t d i , ~ n f e o t i o n by ~ - r a y s was i r r e v e r s i b l e . The s t e r i l i z a t i o n ( t o m i c r o b e number o f O) was a c h i e v e d a t dose 2 . 5 - 4 . 0 kGy. I n t h e U . S . S . R . t h e problem o f r a d i a t i o n d i s i n f e c t i o n h a s now v e r y i m p o r t a n t si~nlfloanoe be¢ause of the p~sss~e to industrial methods of production of meat-dalry products via large live-stock breeding farms. Since the existing methods of biological purification and disinfection of without-lltter :~.nu.re d i d n o t s e c t t r e t h e c o m p l e t e d e s t r u c t i o n o f m i c r o o r g a n i s m s and h e l ~ n t eggs, t h e works on u s i ~ t h e t o w - e n e r ~ a c c e l e r a t o r s , p r o d u c i n g i n t h e S o v i e t Union, f o r t h e d i s i n ~ e c t i o n o f w a s t e s o f l i v e - s t o c k b r e e d i n g farms began. At present there is the information on 2 pilot plants. The plant in the All-Unlon Scientific Research Institute for Cattle-Breed~n~ Meo~-~-~zation has low-energy electron &ccelerator EOL-400 N(two contrary horizontal beams with energy 400 keY) as a s o ~ e of radlation. P ~ 6 demonstrates the view o f w o r k i n g r e a c t o r o f t h i s p l a n t . As i t was f o u n d by B r u s e n t s e v a and o t h e r s ( 1 9 8 0 ) , G r i s h a e v and o t h e r s ( 1 9 8 3 ) , t h e a d d i t i o n o f 0.2% o f e=monia to irradiati=E waste insured 10~ disinfection of liquid fraction of waste a t d o s e 5 kGy.
Fig. 6.
RPC 24/1-Q
View of w o r k ~ reactor of ~ d l a t l o n plant at AllUnion $clentlflo Roses.rob Y.uJtitute of Cattle-Bree~ Mechanlzation
At radiation plant "Borovlyany" two types of sources (60Co with activity of 0.5 MCi and 1.5-2.5 ~eV electron accelerator produced by the Institute of Nuclear Physics) are used. The general view of the plant building is shown in Fig. 7. It was found by Dmitriev and others (1981), C h u d i n a n d others (1982) that the use of sensibilizing additions of KC1 and CuS04 and of bubbl~ng the ozone-oxygen mixture secured the complete disinfection of livestock breeding farm waste at dose 2.5 kGy without preliminary separation into fractions.
Pig. 7.
Building of radiation plant "Borovlyany"
The similar studies are being carried out by working group "Waste Irradiation" of the Europlan Society of Nuclear Methods in Agriculture. From materials of annual conferences it is possible to note that the studies in the U.S.S.R. and other countries are being performed in near directions, and they are similar on results, conclusions and practical r e c ~ e n d a t i o n s (see Dolin and others (1970), Dzhagatspanyan and others (1981), ~mitriev and others (1981), Mann (1971), Woodbridge and others (1975), Plyustcheva (1971), Sidorenko and others (1980), Grishaev and others (1983), Chudin and others (1982), Gagen-Torn and others (1979), Vysotskaya and others (1980 b). CONCLUSION The performed discussion of various problems of radiation treatment of wastes shows that the radiation methods have some advantages in comparison with the conventional methods. The most perspective direction in this field is the
Radiation Trca¢mcnt of Liquid Waslcs
g5
a p p l i c a t i o n o f o ~ b i n e d methods o f p u r i f i c a t i o n ( t h e ~ b i n a t i o n of irradia t i o n w i t h f l o t a t i o n , a d s o r p t i o n , ozone t r e a t m e n t e t c . )° I n t h i s c a s e t h e dose f o r w a s t e p u r i f i c a t £ o n i s o~u~Lderably l o w e r e d ; t h i s makes r a d i a t i o n methods e o o n ~ o a l l y profitable. EEPERE~OES
Apal'tsyn, I.E., V.A. V.N. Shubin, S.A. i saa£t, tekhnika, A~sh_-~bUnl, R.G., S.S. L.~.MlJco.Toohkina,
~ ,
Kl~acJcko, E.F. Zolotova, Z.N. Makarenko, P.I. Dolin, B r u s e n t s e v a , and V.A. ~ o v (1973). Vodosn~b~e N 5, 8-12. Chlrkin~an, I.A. Gambaz~an, E.Go Butanyan, P.Z.Dolln, and R.V. Dzhagatspanyan (1971). ~ a v~.~
5, 5~6-537.
Baranov&, R , B . , L.T.Buga~ako, V.H. Byakov, V . I . L a z a r e v , and E . P . l ~ t r y a e v (1981). ~ eaA 2he~r R a d i ~ t < L o n - ~ 0 ~ t ' l~.,d.fica~tion. Energ o i z d a t , Moscow ( i n Russian). B ~ o , S°G., A.F. Nikolaev, L.I. Duvaklna, T.A. Schmldt, T°A. Antonova, S°A° Brusentseva, and P.I. Dolin (1980). Pl&st° ma nY , N 2, 47-48. Bruaentseva, S.A., A.G. /Tibush, V.N. 3hubin, and P°I° Dolin (1971)o
~
m~=~,
Khtmiya
5, 83.
Eruaentseva, S.A°, P.I. Dolin, V.A. 7.hlgunov, G.K. Nikonorova, V.N. Shubin, I.E. Apel'tsFn, E.F. Zolotova, V.A. Klyachko, and Z°N. Makarenko (1975).
V
~
,
N 3, 157-159.
Case, P.N., D.L. Kin, D°E. Smlley, and A.W. Garrison (1971). S~m~oli~ on t ~ use of ,,~.cleez ~ - ~ s ~ the ~ = ~ = ~ , m t = ~ ~=troZ of ~nv~r~tal Pollution (Salzburg). IAEA, Vienna, 755-761. Case, P.N., ~nd E,E. Ketchen (1973). Prenoh patent 2179129 (A). Chudin, A.A., and V.N. Shubin (1982). w h t ~ y a i tepJu~loLtya voctT, 4, 304-306. r ~ - t t r i e v , A.M., V.N. K a l i n i n , and V.S. Yetrov (1981). ~ a t i o n Tz~=tnent of WMt~e of Ltve-StO~k ~"ee~J,*-~ ]~u==. U ~ = ~ / , ~ ( i n Russ±sin). D o l i n , P ° I . , V.N° ~aubin, and S°A° Bz~asentseva (1970)o ~ t i o n Pu~fi~,tion gf W~te¢. Nsu~m, ilosoow ( i n Russian). ~Fkhlnov, N°No, IoDo Bondar, and S°A° Bz~sentseva (1979)° / T o b l ~ o ~ ~ , N 10, 10-15. D~tSl~inyan, R.V., V . I . Kosorotov, and M.T. F i l i p p o v (1979). I n t z ~ 4 u e t i ¢ = ~9 a~J~tJ.an..(~m.t.o~ Tee~=~losy. Atcmisdat, Mcaoow ( i n Rassian). D ~ t ~ , R,V., V.A. ~k~l,A1-~ M,T. Pilippov, and E.L. Me~teltson (1981). ~ e l ~ of EwLtat~on: Puwi~un~e~ o¢ w-.=te~. ~ w ~ o A ~ t , ~osoo~ ( i n Russian). ~ n - ~ , V.K., T.A. I~pow~, mad G,~. ~ed~wdev ( 1 ~ 9 ) . On t h e p o s s i b i l i t y o f a p ~ e m ¢ ¢ o n of ele
Accelerators of C h ~ e d PaFticles , Leningrad, 172-180 (in Russian). Gerasimovich, O.A., E.P. Petryaev, A.~. Kovalevskaya, and O.B. Stebunov (1980). Izv.AN BSSR.Ser.fiz.-ener~.nauk, N I, 41-43. Grishaev, I.D., S.A. Brusentseva, P.I. Dolin, G.A. Vinogradov, and V.E. Dubinskii (1983). Sbornik trudov ~IIVS. Moscow (in press). Guteev, V.P., B.M. Vanyushkin, N.G. Kon'kov, Yu.A. Pa~n, P.I. Dolin, S.A. Brusentseva, E.P.Zolotova, and Z.N.~akarenko (1978), ¥odn2e resursy, N 5, 205-206. Hay, W.C. (1975). Radiation for a Clean Envirolmment. Proceedings of Symposium (~unich). IAEA, Vienna, 433-444. kqlabarov, V.N., L.L. Kozlov, and G.~. Panchenkov (1981). Khimiya Vysokikh energii, 15, 218-222. Kon'kov, N.G., S.P. Buslaeva, V.B. 0sipov, Yu.A. Panin, L.D. Solodikhina, L.B. Upadyshev, ¥.P. Karpukhin, and I.F. Faingold (1975). Radiatipn .for a Clean Environment. P r o q e e d ~ s of Symposium (~unich). IAEA, Vienna, 419-431 • Lju, E., I.E. ~ a r o v , Yu.I. Kuryatr~ikov, A.P. ~-zanko, R.V. Dzhagatspanyan, and A.K. Pikaev (1982). Radiation-flotation purification of aqueous wastes from mercury. Book of Abstracts. IV International Meetin~ on Radiation ProcessinK, Dubrovnik, Yugoslavia, 43 Lju, E., I.E. Nakarov, and A.K.Pikaev (1983 a). Khimiya v y s o ~ k h enerEii, 17, 50-55Lju, E., I.E. Nakarov, and A.K.Pikaev (1983 b). ProoeedinEs of V T i h ~ S2mposium on Radiation Chemistr?/. Akademiai Kiado, Budapest (in press). Nakarochkina, L.M., A.K. Mikhailova, ~.T. Pilippov, A.I. Gershenovich, and R.V. Dzhagatspanyan (1969). ~ c h e s k a y a promyah!ennost, N 12, 905-909. ~akarochkina, L.M., A.K. N/khailova, ~.T. Filippov, A.I. Gershenovich, and R.V. Dzhagatspanyan (1974). Khim.icheskaya p r ~ s ~ o s t , N 7, 501-504. Mann, L.A. (1971). Isotopes and Radiation TechnoloF~7, 8, 439-444. N/~-~lova, A.,S. Naohev, and A. Andreeva (1974). Trud~ vodo~abzhenlya, k~izats~i i ~n~t~i te~ki, 10, 191-197. Natroahvili, G.R., and E.M. Nanobashvili (1967). Trud2 TbiliskoKo ped~Eo~icheskogo instituta ira. A.S.Puahkina, 20, 15-20. Natroshvili, G.R., ~.V.Panchvidze, and E.M. Nanobaahvili (1972). P r o c 0 e d ~ s of III Tihan~ Symposium o.n R@diation Chemistry, Akademiai K.iado, Budapest, 1281-1291. Nikiforov, N.N., V.N. Shubin, S.A. Brusentseva, D.~. Zorin, P.I. Dolin, and I.D. Griahaev (1982). ¥ o d o ~ b z h e n i e i sanitarnaya t e k ~ k a , N 6, 6-8. Nikonorova, G.K., V.N. Shubin, S.A. Brusentsevaand P.I. Dolin (1976). Vodn~e resurs~, N 3, 149-155. Nikonorova, G.K., V.N. Shubin, S.A. Brusentseva, P.I. Dolin, G.N. Koleboshin, Yu.I. S h ~ , Yu.N. Sorokin, E.P. Petryaev, A.~. Kovalevskaya, V.P. Burtsev, and M.M. Khokhlova (1980), Kh~micheska2a prom~shlennost, N 9,
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533-534. Petrya~v, E.P., A.M. Kovalevmkaya, V.G. 3chlyk, Y u . L V~-~uskaya, G.A. Zhal e i k o , and O.B. Steb~uov (1978). I z v . A~ B S ~ . 3 e r ~ f l z ~ m ~ r K . ~ , N 1, 21-25 I ~ t r y a e v , E . P . , V.I. Vlasova, T.A. Ryabushko, N.N. 3ubbotina, and R.N. Tschekaleva (1982). Ts~etn~e mete~l~, N 4, 105-106. Flkaev, A.K. (1982). I n v i t e d Papers.TV I n t e r n a t i o n a l ~ e e t l ~ on Radiat£on Procemmln~, Dubrovnlk, Yugoslavla, 261-280 Irlustcheva, G.L. (1971)° M e d i t s y n s k ~ a p a r u i t o l o ~ l y a i p a r a s l t a r n y e b o l e z nl. 40, 461-465. Ryabchenko, V.A., E.L. Mendel 'son, N°A. Arbuzova, and V.A. Gol'din (1980). Vod~snlbmhen!e I kanallzatslya, N 3(46), 42-44. Shubln, V.N., S.A. Brusentseva, and G°K. Nikonorova (1979). -Polvmerizatlon Purlfioat~0n 9f Industrial Wastes° At~nizdat, Moscow (in Russian). Shubin, V.N., S.A. Brusentseva, and G.K. Nikonorova (9180). ~ . ~ i = . k ~ , , 54, 2557-2560. Shubln, V.N., I.D. Grlshaev, N.S. Fel', S.A. Brusentseva, P.I. Dolin, S.P. ~ova, L.A. Zaozerskaya, and D.M. Zorin (1983). Radimt.Phys.Chem, (in press). Sidorenko, G.I., M.A. Pin, gin, and V.T. Savenkova (1963). GiE£ena i s a ~ t ariga, 28, N 9, 97-98. Takehisa, M., and A. Sakumoto (1982). Industrial ADDllcation of Radioisotopes epld R~diatlon ~ech~olo~y. l~ooeediz~s 9~ Conference ~Gren0ble ) • IAEA, Vienna, 217-233. Touhill, C.I., E.C. uA1.tin, M.P. Pujihara, D.E. Obsen, I.E. Stein, and G.IcDonnel (1969). J.Water Pollution Control Peder~ion. Dart 2. 41, N 2, 44-60. Tyutyukanova, G.K., N.D. ~neu'yeva, M.S. Sokolov, and V.N. Primak-~irolyuboy (1980). Khlmi~a v sel'skom k~ozyaistve , 18, 51-54. Vinogradov, G.A. (1980). Tezisy dokladov sove stchanlya Do radzLatsionnol k h ~ m t i orEanicheskikh s o e d i n e n i i . Moskva, 25. Vysotskayaj N.A., L.G. Shevohuk, and G.P.Alieva (1980 a ) . t e c h n o l o = i y a , N 1, 53-55. Vysotskaya, N.A., A.P. Rekasheva, and L.G. Shevchuk (1980 b). R a d i a t i o n Tr~atn~nt of Sewage S!u~es. Tekhnika, Kiev (in Russian) Woodbrldge, D.D., P.C. Cooper, A.J. van der Berg, H.D. ~usselman, and H.N. Lowe (1975). Radiatign for a Clean Environment. ~r0c~edim~s of S~Doslum { ~ o h ~ . IAEA, Vienna, 169-188. Zolotova, E.P., Z.N. Makarenko, and S.A. Brusentseva (197~). Trudy VODGEO. vy=. 49 • ~er. V0d.0snab~,henie, 22-24. •