廢水處理及回收的臭氧技術

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
http://www.airtreetech.com
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
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
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)
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
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)
Acetone
IPA
IPA ozone treatment
25
20
Concnetration (p
15
10
0
0 10 20 30 40 50 60 70
Ozone dosage (gram)
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)
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)
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)
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)
AMDI = 426
O one Formation b
Ozone by Micro
Micro-discharge
discharge
O2+ O3 O2
Dielectric media
AC voltage
The Design
g Structure of Ozone Generation
Double quartz tube
Ceramic Plate
AirTree Patent
Electrolysis Cell Single glass tube
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
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)
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))
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)
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
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)
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
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
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%.
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)
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
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
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
http://www.airtreetech.com30 1,000
Application of Air Sterilization
in Dr. S.N.Fu Library at Academia Sinica
After 5 days treatment
Untreated
T t d
Treated

廢水處理及回收的臭氧技術

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廢水處理及回收的臭氧技術

for O3, n = 2 K = 4.54 x 1044

160 AirTree treatment

Double quartz tube

Parameters of Ozone Generator

Power consumption (kw/kg ozone)

Cooling water – quality, flow rate , temperature

Pressure – inlet, outlet

7000 BE02 COD : Ozone = 1 : 1

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

10 kw/kg ozone generation

2 kw cooling water circulation

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

COD : Ozone = 1 : 0.54

Original processes Ozone treatment in the original process

Ozone treatment starting from Ozone treatment starting from the

Ozone and oxygen

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

The amount of organic calcium created

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

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

99.9% inactivity of O3, Cl2 and H2O2

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