Hatano Y., Katsumura Y., Mozumder A. (Eds.) Charged Particle and Photon Interactions with Matter - Recent Advances, Applications, and Interfaces

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930 Charged Particle and Photon Interactions with Matter

of 1000ppm was removed at 80% with a dose of 28 kGy. The Japan Atomic Energy Research

Institute and the Ebara Corporation have started collaborative research on electron-beam treatment

of NO

and SO

in ue gases from heavy oil combustion, where sufcient removal of NO

and SO

was simultaneously achieved at a dose of 40 kGy (Machi et al., 1977). In parallel, various basic

studies were conducted for the reduction of required dose, the effect of dose rate, and a dry process

(Tokunaga et al., 1978a; Tokunaga and Suzuki, 1984; Gentry et al., 1988). It is demonstrated that the

addition of ammonia enhanced the removal of NO

and SO

and produced ammonium nitrate and

ammonium sulfate as fertilizers (Tokunaga et al., 1978b). Various radicals produced by the electron-

beam irradiation of the ue gases react with nitric and sulfuric oxides to produce nitric and sulfuric

acids. These acids then react with the added ammonia and convert to the nal products, ammonium

nitrate

and ammonium sulfate, as follows:

NO SO HNO H SO

OH, O, HO

3 2X

, ,

 → (32.10)

HNO H SO H NO , NH SO

3 2 4

4 3 4

 →

( )

(32.11)

The enhancement of the removal of NO

and SO

in the presence of ammonia is important to reduce

the operation cost. The irradiation at a lower temperature led to a higher removal of NO

, because

is produced in an exothermic process (Machi et al., 1977). In addition to the effect of the gas

temperature, multi-stage irradiation improved NO

removal. Figure 32.5 shows the removal prole

for NO

at three different irradiation stages. The experiments were performed using a special irradia-

tion reactor having a few chambers for the multi-irradiation experiments (Tokunaga et al., 1993). In

the case of triple-stage irradiation, simulated ue gas was irradiated three times with electron beams,

when owing into each chamber in the irradiation reactor. There are non-irradiation zones between the

chambers. It was found that higher NO

removal was obtained from double- and triple-stage irradia-

tion. This is probably due to the effective consumption of OH radicals for reactions with intermediates.

It is very difcult to examine nitrogen balance before and after irradiation, because NO, N

, and

are the nitrogen sources in ue gases. Namba et al. (1990) have conducted the material bal-

ance of nitrogen and sulfur compounds using

N-labeled NO for the electron-beam treatment of

simulated ue gas (Namba et al., 1990). Electron beams were irradiated at 80°C to a mixture of gases

containing 250ppm

NO, 220 ppm SO

, 17.8% O

, and 82.1% N

in the presence of 690 ppm NH

100

0 4 8 12 16

Absorbed dose (kGy)

Removal eciency (%)

Triple-stage irradiation

Double-stage irradiation

Single-stage irradiation

Figure 32.5 Removal efciency of NO

at three different stage irradiations. (From Tokunaga, O. et al.,

Non-Thermal Plasma Techniques for Pollution Control, NATO ASI Series, Penetrante, B. M. and Schultheis,

E. (Eds.), Vol. 34, Part B, Springer-Verlag, Berlin Heidelberg, pp. 55–62, 1993. With permission.)

Applications of Ionizing Radiation to Environmental Conservation 931

The results show that about 55% of

NO was converted to

−

. Interestingly, other nitrogen

compounds such as

NO, and

N were also formed, indicating that

NO reacted

with

and/or

as follows:

15 14 15 14

NO N N N O+ → + (32.12)

15 14

NO NH N N H O+ → + (32.13)

15 14

NO NH N NO H O+ → + (32.14)

The

radicals of

N and

are produced by the radiolysis of nitrogen and ammonia.

As described earlier, SO

is removed through reaction with OH radicals produced by electron-

beam irradiation. This is a similar mechanism for the removal of NO

. However, in the electron-beam

treatment process, SO

can be removed through direct reactions with NH

in the absence of electron-

beam irradiation. The reactions, called thermal reactions, can also save the operation cost for the

electron-beam process. Laboratory-scale studies have been carried out for the reactions of SO

with

(Hirota et al., 1996). The results show that the reactions occur in a water layer formed on an inner

surface of reactor by water condensation out of the gas phase. The reactions were initiated by the dis-

solution of SO

and NH

into the water layer. The dissolution of SO

forms hydrogen sulte and sulte

ions, which are heterogeneously oxidized to hydrogen sulfate and sulfate ions by oxygen and NO in the

ue gas, respectively. The resulting hydrogen sulfate and sulfate ions in the aqueous layer react with

ammonium ions to form (NH

)

. Oxygen and NO play an oxidative role in SO

Many basic research studies on electron-beam treatment of NO

and SO

have opened up the chal-

lenge of application to real ue gases. Pilot-scale tests had started at Shin-Nagoya Power Plant of Chubu

Electric Power Company to treat an actual coal-red ue gas of 150–230ppm NO

and 650–950ppm

by an electron beam (Tokunaga, 1998a). Ammonia was added to a ue gas of 12,000m

/h, after

the reduction of gas temperature by 65°C. Then the ue gases were irradiated with electron beams

using an electron accelerator, operating at 800kV with a current of 135mA. Three irradiation heads

(45mA × 3) of the accelerator made it possible to do three stage irradiations for high performance of

removal. The results showed that a dose of 11kGy led to more than 90% removal of NO

and

. It is possible to obtain 90% removal of SO

using thermal reactions without irradiation.

On the basis of laboratory- and pilot-scale tests, industrial-scale processes have been constructed

in China, Poland, and Bulgaria. Half of the 600,000m

/h ue gases from a coal-red power genera-

tion boiler in China was treated using two electron accelerators (800kV 400 mA), where 1800ppm

was removed by 80% at about 4kGy (Tokunaga, 1998b). A test in an electron-beam facility

in Poland showed that removal performance of NO

is deeply related with its initial concentration,

temperature, ammonia stoichiometry, as well as dose and temperature (Chmielewski et al., 2004).

The accelerator used for the treatment of ue gases at the Shin-Nagoya Power Plant of Chubu

Electric

Power Company was delivered to the Maritsa East coal-red power plant for the treatment

of ue gas containing about 150ppm NO

and 5000ppm SO

. A dose of 4–5kGy achieved 90%

removal

of NO

and SO

and the test was successfully nished in 2003.

32.4 voCs in exhaust gases

The VOC-treatment method can be categorized into two technologies for recovering and destroying.

Recovering technology comprises adsorption (Ads), absorption (Abs), and condensation (Cnd).

Figure 32.6 shows the process capability of representative VOC-treatment methods. The adsorption

method can treat 1–100,000m

/h VOC stream at a concentration of 10–10,000ppm, where VOCs

are trapped by activated carbon or zeolites, and then stripped by steam for reuse. The replacement

of adsorbing materials is required in every 4–5 years to maintain the high adsorption performance.

In the absorption method, VOCs absorbed into water or organic liquid are separated by decantation

932 Charged Particle and Photon Interactions with Matter

or distillation. A higher concentrated VOC stream can be treated by the condensation method. The

destroying technologies comprise thermal incineration (TI), catalytic incineration (CI), and electron

beam (EB) treatment. Incineration is costly and generates a great amount of CO

due to the supple-

mentary fuel required for combustion of VOCs. Catalytic incineration cannot treat VOC stream

containing sulfur, phosphorous, halogens, etc., because they deactivate the catalysts. The electron

beam

method is the preferable method to treat VOCs at less than a few hundred ppm.

Hydrocarbons

are oxidized through reactions with hydroxyl radicals in electron processing. It indi-

cates that a higher decomposition is obtained from target chemicals having higher OH rate constants.

Figure 32.7 shows the decomposition prole for xylene mixture by an electron beam. Although the

reagent xylene liquid contained ethylbenzene, the decomposition proles for o-, m-, and p-xylenes,

and ethylbenzene were roughly in proportion to the OH rate constants of o- (14.7 × 10

−12

/mol/s),

m- (24.5×10

−12

), and p-xylenes (15.2 × 10

−12

), and ethylbenzene (7.5 × 10

−12

), respectively (Atkinson,

1986). In addition, mass balance in the xylene-irradiation demonstrated that the ring cleavage occurred

through reactions with OH radicals. Table 32.2 lists identied products in xylene-irradiation. The mass

–11

–12

–2

–1

Flow rate (m

/h)

Initial concentration of VOC (ppm)

Ads

Cnd

Abs

Figure 32.6 Characteristics of representative VOC-treatment technologies. (From Hirota, K. et al., Ind.

Eng. Chem. Res.,

43, 1185, 2004. With permission.)

100

0 2 4 6 8 10 12

Adsorbed dose (kGy)

Decomposition efficiency (%)

m & p-xylene

o-xylene

Ethylbenzene

Figure 32.7 Decomposition efciencies of xylene mixture by electron-beam irradiation. (From Hirota, K.

al., Radiat. Phys. Chem., 45, 649, 1995. With permission.)

Applications of Ionizing Radiation to Environmental Conservation 933

table 32.2

Carbon

ass

alance

ylene

rradiation

dose

gy)

hCooh

(mg

C/m

)

Cooh

(mg

C/m

)

Cooh

(mg

C/m

)

Cooh

(mg

C/m

)

(mgC/m

)

(mgC/m

)

aerosols

(mg C/m

)

unreacted

xylene

(mg C/m

)

input

(mgC/m

)

recovery

(%)

2 1.51 3.12 19.21 n.d. 2.52 0.11 22.20 49.01 93.75 104.2

5 3.41 6.80 26.59 n.d. 4.27 2.70 34.48 29.20 98.27 109.9

8 2.59 5.79 6.05 1.58 6.43 2.37 38.69 18.86 95.65 86.10

10 2.48 6.26 2.58 1.76 5.25 6.31 40.56 13.98 97.02 81.60

934 Charged Particle and Photon Interactions with Matter

balance in xylene-irradiation was examined on the basis of C-balance (mg C/m

) by comparison of

input xylene to irradiation products such as formic, acetic, propionic, and butyric acids, CO, CO

, and

aerosols (Hirota et al., 1995). Aerosols were formed by the coagulation of low volatile compounds

produced by the irradiation of VOCs. Lower recovery at higher dose was due to the increment of frag-

mentation that could not be detected. The highest concentrations of the carboxylic acids were obtained

at 5kGy, except for butyric acids, indicating that irradiation products were decomposed as the dose

was increased. Actually, the concentration of carbon dioxide increased with dose.

In the case of chlorobenzene, irradiation at an initial concentration of 20 ppm, mass balance of

chlorine was examined on the basis of absolute amount of chlorine (mg Cl) for a certain period at

doses of 4 and 8 kGy, and 4kGy in the presence of NH

. Excellent recoveries (100% ± 2%) were

obtained for the three runs and the majority of chlorine in the reacted chlorine was found in the gas-

eous products (Hirota et al., 1999). Figure 32.8a through c show the weight ratio of organic and inor-

ganic chlorine to reacted chlorine in the chlorobenzene molecule for gaseous products, aerosols, and

residues in the three runs. Inorganic and organic chlorine found in the gaseous products accounted

for more than 60% of the reacted chlorine. The addition of NH

reduced the organic-chlorine ratio

of the gaseous products, suggesting that the added ammonia reacted with chlorine dissociated from

carbon during irradiation. The reaction occurred before the recombination of dissociated chlorine

with carbon and NH

Cl particles formed, which increased the inorganic chlorine in aerosols, as

shown in Figure 32.8b. Ammonia played a role in the dechlorination of the gaseous products. On the

other hand, double energy input from 4 to 8kGy caused a little change in the inorganic and organic

chlorine ratios in the gaseous products, and not in the aerosols. The results indicate that the extra

energy cannot effectively enhance dechlorination. Abundant radicals generated by the extra energy

were consumed through reactions with chlorobenzene and intermediates. The extra energy input

0.0

0.2

0.4

0.6

0.8

1.0

4 kGy 8 kGy 4 kGy+ NH

Cl ratio

Organic Cl

Inorganic Cl

Gas products

0.0

0.2

0.4

0.6

0.8

1.0

4 kGy 8 kGy 4 kGy+NH

Cl ratio

Organic Cl

Inorganic Cl

Aerosols(a) (b)

0.0

0.2

0.4

0.6

0.8

1.0

4 kGy 8 kGy 4 kGy+ NH

Cl ratio

Organic Cl

Inorganic Cl

Residues(c)

Figure 32.8 Organic and inorganic chlorine found in (a) gas products, (b) aerosols, and (c) residues. (From

Hirota,

K. et al., Radiat. Phys. Chem., 57, 63, 1999. With permission.)

Applications of Ionizing Radiation to Environmental Conservation 935

increased decomposition ratio of chlorobenzene from 40% to 58%, with the aerosol concentration

from 17.8 to 34.3mg/m

. Dechlorination cannot take place during the rst attack of OH radical to

chlorobenzene. It was found that about 65% of reacted chlorobenzene was dechlorinated at doses of

and 8

kGy.

Ammonia enhanced the dechlorination up to about 80%.

commercialize the application of electron beam for the treatment of VOCs, the mineralization

of aerosols is the most challenging task. Manganese dioxide is a useful catalyst for the oxidation

of aerosols. It decomposes ozone produced by the irradiation of electron beams to target gases and

produces active oxygen and oxygen molecules on its surface. The active oxygen oxidizes aerosols

deposited on its surface (Hakoda et al., 2008), as shown in Figure 32.9. The Japan Atomic Energy

Agency has been developing the hybrid system of electron accelerator and manganese dioxide to

treat

VOC exhaust gas at a ow rate of 500–2000

/h.

32.5 dioxin in muniCipal waste inCinerator gases

As described previously, many municipal solid waste incinerators in Japan have replaced electric

precipitators with bag lters to meet a new regulation for PCDD/F emission. This is because dioxins

are synthesized at the temperature where electric precipitators can effectively trap y ash and acti-

vated carbon adsorbing PCDD/Fs. In the case of bag lters, the adsorbents are trapped by lters at

about 453 K. However, there still remains a concern of secondary treatment of PCDD/Fs adsorbed

on the surface of added activated carbons.

One of the alternative ways is to destroy dioxins in incinerator gases by an ionizing radiation.

Afew studies have been experimentally and theoretically carried out for the electron-beam treatment

of PCDD/Fs in Germany (Paur et al., 1991, 1998), where more than 90% decomposition was obtained

at 6kGy for PCDD and at 15kGy for PCDF at a temperature of 358K in the pilot plant. When con-

sidering the installation of the electron beam process to existing municipal solid waste incinerators,

an electron accelerator should be placed downstream of the electric precipitator, where the tempera-

ture of incinerator gases is about 473K in Japan. A pilot-scale facility for electron-beam treatment

for PCDD/Fs was constructed at a site of Takahama Clean Center treating 450t/day (150t/day × 3

furnaces) solid waste in Japan (Hirota et al., 2003). The schematic owchart of the facility is shown

in Figure 32.10. The incineration of 150t solid wastes emits about 40,000m

/h incinerator gases.

MnO

O CO

Aerosols

Figure 32.9 Oxidation of aerosols on the surface of MnO

catalyst.

40,000 m

1,000 m

Reactor

PCDD/F sampling

Electric

precipitator

Electron accelerator

Figure 32.10 Schematic ow of PCDD/F treatment facility with electron beams at the Takahama Clean Center.

936 Charged Particle and Photon Interactions with Matter

An incinerator gas of 1000m

/h was diverted for the test facility from the downstream of electric

precipitators and backed into the main stream incinerator after electron-beam treatment. Electron

beams were generated by an electron accelerator supplied at 300kV with a current of up to 40mA.

The incinerator gases containing PCDD/Fs were isokinetically and simultaneously sampled upstream

and downstream of the reactor during irradiation to evaluate the decomposition ratios of PCDD/Fs.

Although PCDD/F concentrations in the incinerator gases depended on the contents of garbage and

the incineration conditions, etc., the concentrations of PCDD/F before the electron-beam irradiation

were 0.22–0.88 and 0.35–1.24ng-TEQ/m

, respectively. Figure 32.11 shows the decomposition ef-

ciencies of PCDD/Fs in the incinerator gases with electron beams. The decomposition efciencies

increased with the dose. A dose of 12kGy led to 90% decomposition efciency of PCDDs. In the case

of PCDFs, decomposition efciency was about 10% lower than that of PCDD and reached 90% at a

dose of 16kGy. Totally, the TEQ concentration of PCDD/Fs was reduced by 90% at a dose of 14kGy.

Additional energy of electron beams is required to treat PCDD/Fs in incinerator gases at higher tem-

peratures than in the previous studies (Paur et al., 1998).

A kinetic approach of the decomposition of PCDD/F homologues allowed us to know if the

OH radical is the main oxidant. From the comparison of PCDD G-values obtained from the ini-

tial slopes of their plots of absorbed dose vs. decomposition efciency, the following relation was

obtained (Hirota et al., 2003):

12k k 1 4k 16k 2 2k

H8CDD H4CDD H5CDD H7CDD H6CDD

. . . .< < < <

(32.15)

This relation is roughly satised with the OH rate constants for reactions with PCDD homologues, where

the OH rate constant increases as the number of chlorine atoms on the aromatic rings decreases (Kwok

et al., 1995). However, the lower chlorinated homologues required much more energy to be decom-

posed in the case of PCDF. This is because the dechlorination as well as oxidation of PCDF homo-

logues occurred through reactions with activated species produced by the irradiation. The dechlorination

caused an increase in the concentration of PCDF homologues such as 2,4,6,7-TeCDF, 2,3,7,8-TeCDF,

and 1,2,3,4,9-PeCDF after irradiation at lower doses (Hirota et al., 2003; Hirota and Kojima, 2005).

Tsinghai University in China recently showed interest in electron-beam technology to treat diox-

ins emitted from medical waste incinerators. There are about 150 medical waste incinerators in

China, where a bag lter system reduces dioxin emission to 1–5ng-TEQ/m

. However, the Chinese

Government is planning to tighten the dioxin emission control to 0.1ng-TEQ/m

. More than 85% of

the existing medical waste incinerators cannot nd an avenue for coping with the new legislation. The

electron-beam technology is expected to reduce the dioxin emission to a legislation-satisfying level.

100

0 5 10 15 20 25 30

Absorbed dose (kGy)

Decomposition efficiency (%)

PCDDs

PCDFs

Figure 32.11 Decomposition efciency of PCDD/Fs by electron-beam irradiation.

Applications of Ionizing Radiation to Environmental Conservation 937

32.6 organiC pollutants in wastewater

Compared to the treatment of gaseous pollutants, there are many more research studies and devel-

opments analyzing ionizing radiation for aqueous pollutants. This is probably due to easier access

for analyzing reaction products after ionizing radiation treatment. An on-line system is necessary

to measure gaseous pollutants during irradiation. In contrast, irradiation and analysis can be sepa-

rately

done in the case of research on the treatment of wastewater.

general, household efuent is treated by activated sludge. In the case of industrial wastewater,

physicochemical methods such as precipitation, ltration, and adsorption are added to remove heavy

metals and inorganic compounds. The combination of biological and physicochemical methods is

necessary to treat industrial wastewaters. One of the methods for treating the contaminated water

is by ionizing radiation (Getoff, 1986; Gehringer et al., 1988; Cooper et al., 1993). The gamma-

ray irradiation of tri- and tetra-chloroethylene in the order of ppb showed that more than 99% of

the target chemicals were decomposed in drinking water at a dose of 1.6kGy (Gehringer et al.,

1985). In case of puried water, a dose of 0.1 kGy was enough to obtain the sufcient performance.

Ozone helped the decomposition efciency for tri- and tetra-chloroethylene (Gehringer et al., 1987).

Interestingly, the addition of metal ions also inuenced the treatment of the organics, where higher

decomposition efciency of trichloroethylene was obtained in the order of Fe

> Ni

> Cr

> only

gamma-ray > Co

> Zn

> Cu

> Mn

(Huang et al., 2009). A similar tendency was observed in

the

experiments on gamma-ray treatment of tetrachloroethylene.

recent years, people are paying much attention to the contamination of environment with

chemicals having biological effects on the body. Endocrine disrupting chemicals (EDCs) are very

detrimental to aquatic creatures because of their hormone mimicking and antagonizing action in

their organism. For example, 17 β-estradiol is a steroid hormone produced in female and male

reproductive

systems. However, once 17 β-estradiol is released to the environment and delivered to

the body, it interferes with the normal physiological process. To identify the crucial chemicals for

oxidizing EDCs, gamma-ray irradiation was carried under the condition of various atmospheres in

a laboratory scale. The sample solutions were saturated with air, oxygen, helium, and nitrous oxide

before irradiation. There was no difference in 17 β-estradiol decomposition except under N

O con-

dition (Kimura et al., 2004). The saturation of N

O in a sample solution accelerated the oxidation

of 17 β-estradiol because N

O reacts with the hydrated electron in the solution to produce hydroxyl

radicals

(Janata and Schuler, 1982):

N O e H O OH N OH

2 aq 2 2

+ + → + +

−

(32.16)

As described previously, G-values for generation of hydrated electron and hydroxyl radical are 2.7

and 2.8, respectively. Thus, the concentration of OH was double in the N

O-saturated solution,

where the higher decomposition efciency was obtained. It was found that the decomposition of

17 β-estradiol occurred through reaction with hydroxyl radicals. In general, hydrocarbons in N

O-

saturated water readily decomposed because the hydroxyl radical is a crucial chemical for their oxi-

dation. When hydroxyl radicals attack target pollutants in water, many intermediates are produced.

It should be noted that the toxicity of the intermediates may be higher than the target pollutants.

To examine the toxicity of solution before and after irradiation, chemical and biological decompo-

sition behavior of nonylphenol in water was investigated. Although a dose of 3kGy decomposed

nonylphenol completely, its estrogen activity still remained due to intermediates produced in the

γ-irradiation of nonylphenol (Kimura et al., 2006). However, the estrogen activity was eliminated

at irradiations over 5kGy. Ionizing radiation can eliminate chemical and biological inuence of

pollutants

in water.

Pilot-scale

tests for the treatment of wastewater were conducted using ionizing radiation in a

few countries, in which dyeing complex wastewater was treated with electron beams in combina-

tion with biological processes in Korea. An efuent of 1000m

/h was irradiated using an electron

938 Charged Particle and Photon Interactions with Matter

accelerator supplied with 1MV with a beam power of 40kW, followed by biological treatment. A dose

of 1–2kGy to the efuents before biological process enhanced the reduction of COD and BOD by

30%–40% compared to that of only biological processes (Han et al., 1998, 2002). Treatment period

was also reduced from 17 to 8h by an electron-beam irradiation. Brazil has treated wastewater using

an electron accelerator of 1.5MV with 25mA at a ow rate of 3–4m

/h (Sampa et al., 2001). The

results showed that about 80% decomposition efciency was achieved at a dose of 2kGy with aera-

tion for the major components of the wastewater such as chloroform, carbon tetrachloride, trichlo-

roethylene, etc. In contrast, chemical oxygen demand (COD) was reduced by 30% at the same dose.

With the increase of absorbed dose, COD increased by 5%–8% up to 15kGy and then decreased

again. Only 35% reduction of COD was obtained at a dose of 20kGy. Fragmentation of parent

pollutants

temporarily increased COD in the wastewater.

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