廢水處理及回收的臭氧技術

臭氧應用於廢水回收 20111007

◆ 臭氧在廢水回收的應用
◆應用的方法：臭氧注入、反應槽的設計
◆ 選擇臭氧機的注意事項：穩定性、耗能
◆ 設備費用及操作費用

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 Waste water treatment processes
pH = ???, COD =??? ppm,
Chemicals/formula ??? ppm
CMD = ???
Primary Secondary Tertiary
Chemical and Bio-treatment Advanced
physical id i
oxidation
treatments
Disinfection
pH
H adjustment
dj t t
Aerobic UV
Precipitation Ozone
Anaerobic
Filtration H2O2

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What can ozone do ?
Disinfection
bacteria < spore < virus < cysts
Oxidation (eV)
F2 (3.0) > OH ( 2.8) > O (2.4) > O3 (2.09)
> H2O2 (1.77) > HOCl (1.5) > Cl2 (1.3)

B ki chemicals
Breaking h i l into
i t small
ll molecules
l l
Reduce COD BOD
Decolor
Deodor
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 In acid solution pH adjusted

O2

O3 (wt%)

4.5%

6%

8%

10%

0 4 6 8 10 12 (min) 0 4 6 8 10 12 (min)
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 Fe 3+ + e − → Fe +2 ∆E = 0.77eV
O3 + 2 H + + 2e − → O2 + H 2O ∆E = 2.09eV
O2 + 4 H + + 4e − → 2 H 2O ∆E = 1.229eV
4 Fe 2+ + O2 + 4 H + → 4 Fe +3 + 2 H 2O
2 Fe 2+ + O3 + 2 H + → 2 Fe +3 + H 2O + O2

nF∆E = RTLn
F∆ RTL (K )

F 96500, R = 8.314,
F=96500 8 314 T = temperature in K
for O2, n = 4 K = 1.14 x 1031

for O3, n = 2 K = 4.54 x 1044

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 CN − + O3 → CNO − + O2 (1.846 O 3 / 1.0
1 0 CN - )
−
2CNO − + 3O3 + H 2O → N 2 + 2 HCO3 + 3O2
−
2CN − + 5O3 + H 2O → 2 HCO3 + N 2 + 5O2 ( 4.64 O 3 / 1.0 CN - )

CN vs Ozone

20
CN (gram/lit)

15
10
5
0
0 50 100 150
ozone (gram/lit)

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 Acetone

IPA

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 IPA ozone treatment
25

20
Concnetration (p

15

10

0
0 10 20 30 40 50 60 70
Ozone dosage (gram)

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 waste water treatment (Acetone&IPA)
180

160 AirTree treatment

140 Optimal ozone treatment
120
CO D ((ppm)

100

80

60

40

20

0
0 5 10 15 20 25
Ozone dosage (arb.unit)

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4500
4000 分餾後廢水20040608, 1L
3500 ADMI
3000 COD/10
2500
2000
1500
1000
500
0
0 50 100 150 200 250 300
Ozone dosage (g/ton)

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Phenol treated by ozone

Phenol treatment
1600

1400
ozone treatment
1200 AirTree treatment

1000

COD (ppm)
800

600

400

200

0
0 10 20 30 40 50 60 70
Ozone dosage (arb. unit)

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 20000
18000

COD (ppm
LR COD : Ozone = 1 : 1
16000
14000
m)

12000
10000
8000
6000
4000
2000
0
0 50 100 150 200
Ozone dosage (gram)

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AMDI = 426

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O one Formation b
Ozone by Micro
Micro-discharge
discharge

O2+ O3 O2

Dielectric media

AC voltage

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 The Design
g Structure of Ozone Generation

Double quartz tube

Ceramic Plate

AirTree Patent
Electrolysis Cell Single glass tube

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Structure of Ozone Generator
Production (gram/hr)

100 g/h
/h 2k /h
2kg/h 60 kkg/h
/h

Parameters of Ozone Generator

Concentration (mg/l)

Power consumption (kw/kg ozone)

Cooling water – quality, flow rate , temperature

energy consumption (kw/kg ozone)

Pressure – inlet, outlet

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 8000

7000 BE02 COD : Ozone = 1 : 1

COD (pp
6000

5000
pm)

4000

3000

2000

1000

0
0 20 40 60 80
ozone dosage (gram)

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 16000
BE10 COD : Ozone = 1 : 2
14000
COD (ppm) 12000
10000
8000
6000
4000
2000
0
0 50 100 150
Ozone dosage
g (g
(gram))

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Energy cost for ozone treating one kg of COD

Taking ozone : COD = 1 : 1 (in weight)

10 kw/kg ozone generation

4 kkw reacting
ti tank
t k

2 kw cooling water circulation

close loop chiller cooling water
10 x 0.6/0.4 = 15 kw

29 kw /kg ( 10% by weight, PSA oxygen)

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 30000

高濃度IPA, 1L
25000

20000
COD (ppm)

15000

10000

5000

0
0 1000 2000 3000 4000 5000 6000 7000
Ozone dosage (g/ton)

COD : Ozone = 1 : 0.54

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 Semiconductor water reuse

8
6
T O C (ppm

4
2
0
0 50 100 150 200 250 300 350 400 450
ozone dosage (g/m3)

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 Chemicals

Bio-treatm

Bio-treatm

Chemicals

Ozone trreatment
Activve carbon
Dye waste water

ment

ment
Un-treated

Original processes Ozone treatment in the original process

Ozone treatment starting from Ozone treatment starting from the

second chemical treatment
un-treated waste water

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Pre-ozone treatment (before aerobic treatment)
1. Fragment big molecule and poisonous molecule
2. Supply oxygen

Ozone and oxygen

yg

anaerobic aerobic

Purpose：
Increase the ability of aerobic treatment by
1. Break down big
g molecule into small molecule
2. Oxide molecule to for bacteria favor acid molecule

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Improvement proposal : pre-ozone treatment to increase the
ability of aerobic treatment
1. Ozone dosage (50 ppm ~ 100 ppm) up to decolor achieved
Th ability
The bili isi expected
d to be
b increased
i d 30% ~ 50%
2. Ozone dosage (10 ppm ~ 20ppm) up to break down
molecule
The ability is expected to be increased 10% ~ 30%.

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The
h barrier
b i for waste water ozone treatment
RUNNING COST

COD : Ozone = 1 : X

O3 (kg) x power consumption (kw/kg) x 3

3 = 1 + 2 (1 /electricity + 2/oxygen)

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 Rg
臭氧機的氧氣回收
氧氣機/A 2kw/kg
需求規格:
C 臭氧輸出濃度 (% by we weight)
g ) RA
P 臭氧產量 (g/h)
G 原始氧氣需求量 (m3/h)
A 氧氣機濃度 (per cent assuming 90%,
臭氧機/R 10kw/kg
0.9))

氧氣回收效能
R 臭氧機濃度 (% by weight) Rp
X 氧氣回收率
Y 臭氧機的損耗率 XZ
Z 氧的回收濃度 (per cent) 氧氣回收

氧氣機及臭氧機的實際操作值

臭氧機的規格
臭氧機的氧氣濃度 臭氧需求 P/C
RA = X Z + ((1-X)) A
臭氧機的產量
Rp = P (1 +Y)

氧氣機的規格
氧氣機的需求量
Rg = (1-X) G + G P Y C/R
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 CaO is used to adjust pH and forms calcium ion

The amount of organic calcium created

One phenol molecule contributes two CODs

COD 50 ppm formed by phenol contains 25 phenol molecules

Each calcium ion can chelate two phenol molecules

Adding CO2 to remove calcium and adjust pH

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 Legionnaires’ Disease Bacterium, LDB

Oak Ridge National Laboratory, :The Effect of Three Oxidizing Biocides on Legionella
Pneumophils Serogroup I”:

Ozone concentration 0.24ppm，contact time 5min， 99.9% inactivity (pH7.2, 25℃)

99.9% inactivity of O3, Cl2 and H2O2

L. Pneumophils Serogroup I

Contact Concent.
chemicals pH Temp. (℃)
time (min) (ppm)
7.2 25 <5 0.24
7.2 35 <5 0.13
O3 7.2 45 <5 0.13
8.0 25 <5 0.20
8.9 25 <5 0.14
7.2 25 30-45 0.30
Cl2

H2O2 7.2 25
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Application of Air Sterilization
in Dr. S.N.Fu Library at Academia Sinica
After 5 days treatment
Untreated

T t d
Treated
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