R&D PROGRESS REPORT

*Dr. Junji Hirotsuji and Yoshitaka Kawaai are with the Advanced Technology R&D Center and Tetsuya Tamura is
with the Power & Industrial Systems Center.
R & D PROGRESS REPORT
Advonced Ozone
Woter-Ireotment
Iechno|ogy
by Dr. Junji Hirotsuji, Yoshitaka
Kawaai and Tetsuya Tamura*
Mi tsubi shi El ectri c has devel oped
commerci al ozone water-treatment technol o-
gi es that can provi de safe, odor-free dri nki ng
water, establ i sh envi ronmental l y sound
sewage-treatment processes and i mpl ement
hi gh-qual i ty water recl amati on systems. Thi s
arti cl e i ntroduces advanced ozoni zati on sys-
tems the corporati on has del i vered for treati ng
dri nki ng water and sewage, and a combi ned
process empl oyi ng ozone and hydrogen perox-
i de that i s currentl y under devel opment.
Advanced Ozonization Technology for
Treatment of Drinking Water
BENEFITS. Ozone treatment of dri nki ng water
benefi ts water qual i ty i n several ways.
It prevents formati on of tri hal omethanes and
other organochl ori ne compounds by decom-
posi ng humi c aci ds. Humi c aci ds react wi th
chl ori ne to produce thi s cl ass of substances.
It deodori zes dri nki ng water by breaki ng
down two major compounds that contri bute to
musty smel l , geosmi ne and 2-methyl i so-
borneol , whi ch other processes do not remove.
Combi ned wi th acti vated carbon fi l trati on, i t
serves to remove agri cul tural chemi cal s,
wastes from hi gh-tech i ndustri al processes and
other substances l i sted i n water-qual i ty regul a-
ti ons.
Japanese water-qual i ty regul ati ons requi re
that tri hal omethane, formed by the reacti on of
chl ori ne di si nfectants and humi c substances,
be present i n tap water at concentrati ons no
hi gher than 100g/l . Ozone has l ong been used
as a decol ori zi ng agent to decompose humi c
aci ds and other pi gmented compounds, and
therefore ozone removal of humi c substances
reduces the potenti al for tri hal omethane forma-
ti on.
A WATER-TREATMENT PLANT IN OKINAWA.
The corporati on has al ready del i vered 18 com-
merci al ozone and acti vated carbon water-
treatment systems. Here we i ntroduce an
Ozone reactor tank
Construction Reinforced concrete
No. of tanks 4 (2-stage x 2)
Capacity 194,000m
3
/day
Tank dimensions 3.85 x 8.8 x 5m (W x L x D*)
Contact time 10 min. (5 min./stage)
Treatment
Diffusion with simultaneous air and
water flow
Ozone generator
8.1kg/h x 4
capacities
Ozone injection rate 0~4mg/l
Additional equipment Catalytic ozone breakdown unit
*Effective depth
Activated charcoal absorption tank
Construction Reinforced concrete
No. of tanks 17 tanks (4 systems with 1 spare)
Capacity 219,800m
3
/day
Tank dimensions 5.05 x 10.85m (W x L)
Contact time 12min
Treatment
Fixed-layer, downward-flow activated
charcoal
Activated charcoal
2m
thickness
Cleaning method Blowback with air and water
Lower water collector Porous concrete
Additional equipment Activated charcoal supply
Tabl e 1 Mai n Speci fi cati ons of Ozone Treatment
Faci l i ty at Chatan Water-Treatment Pl ant
24
Mi tsubi shi El ectri c ADVANCE
Reservoir
Holding trough
Microbial oxidation tank
Mixing tank
Flocculation tank
Setting tank
Rapid filtering tank
Intermediate pumping station
Ozone reactor tank
Activated charcoal absorption tank
Purified water tank
Drinking water
Fig. 1 The water-treatment process at the Chatan
Water-Treatment Plant.
R&D PROGRESS REPORT
mi crobi ci dal effects. A porti on of the treated
wastewater can be recl ai med through ozone
processi ng to feed streams and fountai ns,
suppl ement ri vers, and for other recreati onal
purposes, as wel l as appl i cati ons i n the treat-
ment faci l i ty i tsel f.
Ozone processi ng can al so be adopted on a
l arger scal e to decol ori ze the enti re outfl ow of
sewage-treatment pl ants where pi gmented
compoundswhi ch the acti vated sl udge pro-
cess does not removeare present i n hi gh
concentrati ons. Ozone i s an effecti ve decol ori z-
i ng agent because i t sel ecti vel y attacks the
doubl e-bonds that gi ve pi gments thei r charac-
teri sti c col ors.
Chl ori nati on byproducts such as tri hal o-
methanes and other hazardous organochl ori ne
compounds i n treated-sewage outfl ows affect
ecosystems and can have a negati ve i mpact on
water qual i ty i f they enter water sources.
Ozone i s more l ethal to mi croorgani sms than
chl ori ne wi thout formi ng these substances.
Many sewage-treatment pl ants are expected
to i nstal l ozoni zati on faci l i ti es due to these
envi ronmental benefi ts.
A SEWAGE TREATMENT PLANT IN OSAKA.
The corporati on has del i vered 16 ozoni zati on
systems for sewage treatment. Here we wi l l
i ntroduce an i nstal l ati on at the Chubu Treat-
ment Pl ant of the South Osaka Central Coast
Sewage Di stri ct.
Industri al wastewater compri ses most of the
pl ants i nfl ow, however i t al so recei ves hi ghl y
col ored fi ber and food-processi ng pl ant wastes
that resul t i n di scol ored waters where the
pl ant di scharges i ts outfl ow to Osaka Bay
whi ch happens to be a hi ghl y vi si bl e l ocati on
near a popul ar beach area and the New Kansai
Internati onal Ai rport.
The pl ant had used sodi um hypochl ori te and
pol yal umi num chl ori de decol ori zi ng agents;
however, resi dual chl ori ne from these com-
pounds caused a vari ety of probl ems, i ncl udi ng
breakup of the acti vated sl udge fl oc, equi pment
ozoni zati on faci l i ty del i vered to the Chatan
Water-Treatment Pl ant of the Oki nawa Prefec-
ture Enterpri se Bureau.
The pl ant processes up to 194,000m
3
of water
per day, concl udi ng wi th ozoni zati on and acti ve
charcoal fi l trati on. Conventi onal treatment was
judged i ncapabl e of sati sfyi ng water qual i ty
requi rements because the ri vers used as a water
source were pol l uted wi th domesti c wastewater,
and the requi red chl ori nati on woul d have resul -
ted i n excessi ve tri hal omethane formati on.
We desi gned the ozoni zati on system to l i mi t
tri hal omethanes at the consumers faucet to
60g/l and chl oroform to 30g/l , based on Japa-
nese Mi ni stry of Heal th and Wel fare regul a-
ti ons, whi ch l i mi ts tri hal omethane-formi ng
potenti al to l ess than 100g/l , and WHO water-
qual i ty gui del i nes.
Tabl e 1 l i sts the faci l i ty speci fi cati ons. Four
ai r-fed gl ass-tube si l ent-di scharge ozone genera-
tors are used, each wi th an ozone producti on
capaci ty of 8.1kg/hr. The water i s ozonated by
mi xi ng ozonated ai r and water from opposi te
di recti ons i n a l arge tank, and repeati ng the
process i n a second tank. The tanks are 3.85 x
8.8m, wi th a 5m water depth. The water reten-
ti on ti me i s 10mi n.
PERFORMANCE. Tabl e 2 l i sts the water qual i ty
at each stage of treatment i n the faci l i ty. The
ozone treatment and acti vated charcoal fi l ter-
i ng accompl i sh the greatest reducti on i n
tri hal omethane formati on potenti al . These
processes both contri bute to l ower l evel s of
total organi c carbon (TOC) and methyl ene
bl ue acti ve substances (MBAS), and reduce
requi rements for chl ori ne and potassi um per-
manganate. The faci l i ty met the ori gi nal desi gn
objecti ves, and has contri buted to a safer and
better-tasti ng water suppl y.
Ozone Processing in Sewage Treatment
BENEFITS. Ozone processi ng i s used i n sewage
treatment for deodori zi ng, decol ori zi ng and
Stage of treatment
THM-FP TOC MBAS Chlorination KMnO
4
requirement
(g/l) (mg/l) (mg/l) requirement (mg/l) (mg/l)
Reservoir 59 1.9 0.08 2.2 7.6
After microbial treatment 57 (3) 1.75 (8) 0.05 (38) 1.0 (55) 6.8 (11)
After settling tank 44 (25) 1.43 (25) 0.05 (38) 0.5 (77) 4.5 (41)
After filtering 41 (31) 1.28 (33) 0.04 (50) 0.4 (82) 3.7 (51)
After ozonation 24 (59) 1.25 (34) 0.01 (88) 0.1 (95) 2.6 (66)
After activated charcoal
15 (75) 0.72 (62) 0.01 (88) 0.0 (100) 1.5 (80)
filtering
Note: Figures in parentheses list the cumulative removal of the substance in percent.
Tabl e 2 Operati on Resul ts of Chatan Water-Treatment Pl ant
March 1996
25
R&D PROGRESS REPORT
26
Mi tsubi shi El ectri c ADVANCE
Forced-air intake
Cooling
unit
Desiccation unit
Ozone generator
Cooling water
Refrigerated
air unit
Final setting tank
Ozone reactor tank
O
s
a
k
a

B
a
y
Ozone decomposer
Key
Water flow
Untreated water
Air or ozone flow
Treated water
Fig. 2 The ozonation process at the Chubu Treatment Plant.
generator and two 5kg/hr generators, al l of the
ai r-fed gl ass-tube si l ent-di scharge type. The
water and ozone are mi xed i n two si ngl e-stage
di ffuser-type reactor tanks that are 2.55 x 4.5m
wi th a 4.5m water depth. The retenti on ti me i s
14.9 mi nutes (Tabl e 3).
PERFORMANCE. Tabl e 4 shows the resul ts of the
ozone decol ori zati on treatment. Spectropho-
tometry was used to measure the decol ori zi ng
performance. In general the degree of col ori ng
was measured at under 10% (practi cal l y col or-
l ess), i ndi cati ng that the faci l i ty functi oned as
pl anned, al though the changi ng composi ti on
and col or degree of the effl uent from the fi nal
settl i ng tank resul ts i n some vari ati ons.
Runs 1~4 i n the tabl e show that even when
the retenti on ti me (the peri od of contact
between the water and ozone) was shortened
due to l arge throughput, constant decol ori zi ng
performance coul d be achi eved by boosti ng the
ozone-i njecti on rate. A si de benefi t of the pro-
cess i s that the chemi cal oxygen demand
(COD) of the effl uent dropped by 20~30%.
Item Type Number
Roots compressor,
Air blower 9.81N/cm
3
(1kgf/cm
3
), 6
4.94m
3
/min, 22kW
Air-fed glass-tube
Ozone generator silent-discharge, 3
4kg/h (1), 5kg/h (2)
Ozone injector Diffusion pipe 2
Reinforced concrete
Ozone reaction tank 2.55 x 4.5 x 4.5m 2
(W x L x D)
Activated charcoal
Ozone decomposer decomposer, 200m
3
/h 3
(standard state)
Tabl e 3 Mai n Speci fi cati ons of Ozone Treatment
Faci l i ty at Chubu Treatment Pl ant
corrosi on and hi gh operati ng costs.
We pl anned an ozone decol ori zi ng faci l i ty for
the pl ant to al l evi ate these probl ems. The pro-
ducti on system came onl i ne i n August 1992
fol l owi ng extensi ve testi ng.
The ozone faci l i ty consi sts of an ozone gen-
erator, ozone reacti on tank and catal yzer to
break down resi dual ozone i n the vented gas
(Fi g. 2). The faci l i ty empl oys one 4kg/hr ozone
R&D PROGRESS REPORT
Combined Ozone and Hydrogen Peroxide Water
Reclamation Technology
BACKGROUND. Advanced wastewater treat-
ments hol d the potenti al to i ncrease the water
suppl y and reduce water pol l uti on through ex-
tensi ve water recl amati on. Use of recl ai med
water i s al ready on the ri se, and further growth
i s expected.
Recl ai med wastewater needs to be suffi -
ci entl y pure to serve as a source for water-
suppl y systems or to use di rectl y i n agri cul ture
and i ndustry. The maxi mum total TOC for
these appl i cati ons i s 2~3mg/l , whi ch requi res
removal of refractory substances, such as the
products of bi ol ogi cal metabol i sm, and resi dual
organi c substances that remai n i n wastewater
even after ozone treatment.
Several new processes wi th hi gh oxi dati ve
potenti al have been studi ed for thi s purpose:
hi gh-pH ozoni zati on, UV ozoni zati on, and com-
bi ned ozone and hydrogen peroxi de treatment.
At Mi tsubi shi El ectri c, we i nvesti gated
combi ned ozone and hydrogen peroxi de treat-
Run No.
Inflow Reaction Injection rate Initial Final water Impurities Initial Final COD
rate (m
3
/h) time (min.) (mg/l) water purity(%) purity(%) reduction% COD(mg/l) COD(mg/l) reduction%
1 274 13.9 30.9 21.9 6.0 73 26.4 19.1 28
2 248 15.4 39.0 15.3 7.1 54 22.8 17.4 24
3 219 17.4 27.0 9.6 2.4 75 16.3 11.5 29
4 234 16.3 17.4 4.3 1.6 63 13.0 11.0 15
Avg.
244 15.6 28.6 12.8 4.3 66 19.6 14.8 24
(1~4)
5 138 27.6 29.1 23.7 7.6 68 21.3 15.7 26
6 164 23.2 23.9 20.4 6.6 68 20.9 14.5 31
7 165 23.1 22.2 20.1 6.9 66 21.6 17.4 19
8 162 23.5 20.2 14.7 3.7 75 17.9 14.1 21
Avg.
157 24.2 23.9 19.7 6.2 69 20.4 15.4 25
(5~8)
Note: Runs 1~4 employed two ozone generators, and runs 5~8 one ozone generator.
Tabl e 4 Operati on Resul ts of Ozone Treatment Faci l i ty at Chubu Treatment Pl ant
March 1996
27
Target
1
5 10 15
Tabl e 5 Water Qual i ty Level s and Appl i cati on
Requi rements
Total Organic Content (TOC) (mg/l)
Tap water
Reuse of
treated
sewage
Standards
Wastewater treatment
2
Agricultural water
2
Industrial water
2
Steel processing
Pulp processing
Tap water
2
Water quality
Note 1: Target for Mitsubishi water-reclamation technology
Note 2: Measured values
ment, wi th the goal of achi evi ng TOC l evel s of
3mg/l or l ower.
The combi ned process i s rel ati vel y si mpl e to
i mpl ement. Al l i t requi res i s that we suppl e-
ment a conventi onal ozone i njecti on process
wi th a smal l amount of hydrogen peroxi de.
REACTION MECHANISM. The hydrogen peroxi de
reacts wi th ozone to produce hydroxy free radi -
cal OH (Eq. 1). Even more hi ghl y oxi di zi ng
than ozone, thi s speci es i s capabl e of breaki ng
down refractory compounds and oxi di zi ng al -
most al l resi dual organi cs i nto carbon di oxi de
and water.
O
3
+ H
2
O
2
OH + O
2
H + O
2
OH + O
3
O
2
H + O
2
........(Eq. 1)
O
2
H + O
3
OH + O
2
Al though the hydroxy free radi cal easi l y
decomposes al cohol and other organi c com-
pounds i n l aboratory tests, we anti ci pate that
i norgani c i ons, such as carbonate i ons, present
i n wastewater woul d react wi th and consume
much of the speci es. Numerous other com-
pounds i n wastewater compl i cate the i ssue,
requi ri ng further i nvesti gati on.
RESEARCH AND DEVELOPMENT. Engi neers i n
Europe and the Uni ted States are studyi ng the
vari eti es of wastewater, preprocessi ng steps to
l i mi t the i neffecti ve consumpti on of hydroxy
free radi cal , and sui tabl e reactor vessel desi gns
for the radi cal reacti on. Treatment faci l i ti es
usi ng the combi ned process have al ready been
set up at several water-treatment pl ants. Japan
l ags the west i n the research and devel opment
of thi s technol ogy, wi th no commerci al systems
i mpl emented to date, but promi si ng resul ts
from i ni ti al studi es at Mi tsubi shi El ectri c sug-
R&D PROGRESS REPORT
28
Mi tsubi shi El ectri c ADVANCE
T
O
C

(
m
g
/
1
)
10
5
0
4 12 8 16
Reaction time (min)
Ozone only
10mg/I H
2
O
2
43mg/I H
2
O
2
Key
By suppl ementi ng exi sti ng ozoni zati on faci l i -
ti es wi th hydrogen peroxi de, we can expect to
rai se the absorpti on effi ci ency to 20~25% i n
tanks 4~5m deep, or convert processes to usi ng
compact, contact-type tanks wi thout l oss of
effi ci ency.
In summary, the combi ned ozone and hydro-
gen peroxi de treatment effecti vel y l owers the
TOC, al l ows constructi on of more compact
equi pment and i s wel l sui ted to water-recl ama-
ti on schemes.
WORK IN PROGRESS. Our current R&D i s ai med
at determi ni ng the best pretreatment processes
and condi ti ons, determi ni ng the opti mum
amount of hydrogen peroxi de and i ts best
method of i ntroducti on, and fi nal l y, the opti -
mum ozone i njecti on condi ti ons.
We are al so conducti ng desi gn studi es on a
practi cal water recl amati on system. A pi l ot
pl ant wi l l enter operati on by March 1996 to
hel p determi ne the technol ogys performance
under real -worl d condi ti ons, and we are
desi gni ng future systems that wi l l be si mpl e,
economi cal to run and easy to mai ntai n.
Thi s R&D project was conducted i n affi l i a-
ti on wi th the Publ i c Uti l i ty System Research
Project of the Engi neeri ng Advancement Asso-
ci ati on of Japan.
Water puri fi cati on technol ogy i s i ncreasi ngl y
i mportant as we face i ncreasi ng water pol l u-
ti on, growi ng urban popul ati ons and greater
water demand. Mi tsubi shi El ectri c bel i eves
that i ts work i n the fi el d of ozoni zati on tech-
nol ogy for water-suppl y puri fi cati on and sew-
age treatment wi l l contri bute to the heal th and
envi ronmental qual i ty of future generati ons. K
Fig. 3 TOC removal by H
2
O
2
/O
3
treatment after
pretreatment by PAC coagulation and fil-
tration.
gest that thi s process wi l l be sui tabl e for future
water recl amati on projects.
EXPERIMENTAL RESULTS. Fi g. 3 shows the
resul ts of a batch processi ng experi ment where
we subjected treated wastewater to PAC
coagul ati on and fi l trati on, and then used a
combi ned ozone and hydrogen peroxi de pro-
cess. Whi l e ozone al one does not si gni fi cantl y
reduce the TOC, the addi ti on of hydrogen per-
oxi de causes the TOC to decl i ne to as l ow as
1.5mg/l .
The combi ned process i s al so more effi ci ent:
the amount of ozone consumed per TOC re-
moved i s l ess than that requi red for conven-
ti onal ozoni zati on, and the ozone absorpti on
effi ci ency i s hi gher than that wi th conven-
ti onal ozoni zati on.
Fi g. 4 shows the resul ts of batch experi ments
i n water 30cm deep: absorpti on effi ci ency i s
10% under conventi onal ozoni zati on, whi l e i t
ri ses to 40% wi th the addi ti on of hydrogen
peroxi de. The absorpti on conti nues to remai n
hi gh even after the reacti on ti me has el apsed
and the hydrogen peroxi de has been consumed.
The hi gh absorpti on occurs because the di s-
sol ved ozone i s qui ckl y uti l i zed i n reacti ons
wi th hydrogen peroxi de and hydroxy free radi -
cal .
Key
Ozone only
43mg/I H2O2
10mg/I H
2
O
2
10
Reaction time (min)
A
b
s
o
r
b
e
d

o
z
o
n
e

(
s
u
p
p
l
i
e
d

o
z
o
n
e
%
)
50
100
0
Fig. 4 Ozone absorption characteristics.