2000 7

550 ADMI3

NB-FBN
yellow-HE4R pH3-8
5-60 mg Cl2/L
pH
pH dC / dt
dC / dt = kC
k pH
HOCl
1200
ADMI 400 ADMI pH = 4.0
= 14 mg Cl2/L 12 % NaOClH2SO4
pH 6.0 NaOH NT$ 3.04 /m3
NT$ 0.07 /m3 NT$ 3.11 /m3
26 1000 CMD 8 9

Abstract
Almost all dyestuffs used for textile processing impose heavy colors
on effluents such that they cant meet effluent regulations.

Sodium

hypochlorite (NaOCl) has long been used for effluent decoloration by

most textile plants. However, despite by the operators experience, there
is still no scientific method for controlling the dosing rate of sodium
hypochlorite.

An insufficient dosage may result in an aesthetically and

legally unacceptable effluent. Whereas an excessive one may lead to the

formation of chlorine-containing organic compounds which are harmful
to the aquatic life and may limit the water utilization.

It is necessary to

develop a control technique for chlorination decoloration of textile

wastewaters.
In this study, secondary effluent samples from a textile wastewater
plant and synthetic wastewater samples prepared by two azo-type
dyestuffs were used for chlorination decoloration tests in a batch reactor
with a residual chlorine indicator.
Experimental results indicate that the most economic and effective
reaction conditions for decoloration of the test wastewaters were pH = 4
and residual chlorine = 14 mg/L. In the conditions, wastewaters with
true color intensity = 1,200 ADMI could be reduced to values less than
400 ADMI within 60 min. Results also confirm that on-line monitoring
of residual chlorine concentration in the reacting liquid can be used to
achieve a better control of chlorine addition.
Experimental data also indicate that the color removal rate (-dC/dt)
was linearly proportional to the color intensity (C) and free hypochlorous
acid (HOCl) concentration.


1.1

400 ADMIAmerican Dyestuff Manufacting

Industry 3 550
ADMI4PAC
13 Al2O3 12
1.15
PAC 1000 mg/L

 1.2

1.1

1.1

1.2

1.3
1
2

3 NB-FBN 40 mg/L4 Yellow-HE4R

30 mg/L
pH3-85-60 mg Cl2/L
pH

1.4

1. NaOCl
2.
3. pH
4. HOClOCl

 1.1 5

6 ml/L 35

2 g/L

1 g/L

1 g/L

sequestrants

1.5 g/L

Sequestrant

0.5 g/L Sodium heptonate 34

90

 1.2 5

pH

pH

COD
COD


2.1
2.1.1
300
pure state

2.16

2.1

2.1.2

pH

BODCODSS

 2.1 6

CMCPVA

BOD
COD

pH
BOD

pH

COD

NaOH

NaOH

NaOH

2.1 6
9

2.2

3000

2.2.1 6
1.
l

l SO3
NH2
2.
l

l -OH-SO3
3.
l
l -OH-COOH

10


4.
l

l -NH2 -NHR-NR2

5.
l

6.
l

7.
l

11

8.
l

l
9.
l

12

2.2.2

2.2 6

13

 2.2 6

14

2.3
NaOCl
Fenton ROUV H2O2
O3

6 , 9

36

2.3.1

2.1

8H+ + 8e- 4H2

4Fe 4Fe2++8e4Fe2++10H2O+O2 4Fe(OH)3+8H+

15

 40 mg/L PACPoly Aluminum

Chloride 12 % Al2O3 pH = 7
8-10 4
15 25

9 , 10

H2O2100 mg/L
83 % 92 %
H2O2 H2O2/FeSO4 (Fentons reagent)
H2O2 FeSO4( 100 mg/L)

11

12

H2

Fe+2

Fe+2

Fe+2

Fe+2

OH-

OH

Fe+2

OH-

OH

OH-

2.2

16

2.3.2 NaOCl

13

NaOCl

ORP NaOCl NaOCl 14 ,

15

ORP NaOCl pH 16 , 17

2.3.3

trap

disperse
dyes

13

17

2.3.4 Fenton
Fenton H2O2 FeSO4 Fe+2
H2O2 OH
Fe+2 H2O2 Haber-Weiss
18

H2O2 + Fe+2 Fe+3 + OH- +OH

H2O2 + Fe+3 Fe+2 + H+ +HO2

HO2 O2 +H

2 H2O2 O2 +2H2O

RH OH

H2O2 + Fe+2 Fe+3 + OH- +OH

RH +OH R+ H2O

R+ Fe+3 R+ + Fe+2
R+ OH- ROH

2 H2O2 + RH ROH + H2O

Fenton

pH23 19

18

 pH 3.5
25 97 20 H2O2/
FeSO4 (100 mg/L)pH = 4 PAC
Fentons reagent 5
20 21 Fe+2 Fe+2 H2O2
1.1-1.9

22

Fentons reagent
23

2.3.5 (RO)
(RO) NaCl
O3
(permeation rate)

24

SS

2.3.6 UV H2O2/UV
UV
UV

25

UV
UV

19

 26
H2O2 + UV 2HO
HO+ H2O2 H2O + HO2
HO2 H+ + O2-
HO2+ HO2 H2O2 + O2
HO2+ O2-+ H2O H2O2 + O2 + OH RH OH

RH +OH R+ H2O
R+ OH- ROH

UV/H2O2 (HO)
H2O2/UV
Acid Black 1 Direct Yellow 4
H2O2 pH
H2O2

27

H2O2

13 UV H2O2 acid red 1

acid yellow 23 29

2.3.7

20


12

30

13

0.3 g/L 85

1
11

31

2.3.8
chitinchitosan
Acid red
1
32

2.3.9 O3

21

23

OH
33
O3 + H2O H3O+ + OHH3O+ + OH- 2H2O
O3 + HO2 HO+ 2O2
HO+ 2O2 H2O + O2
RH OH

RH +OH R+ H2O
R+ O2 RO2
RO2+ RH ROOH + R

O3
SS

2.3

34

22

 2.3 O3 34

O3mg/L

39.4

34.3

10

29.9

15

25.9

25

13.9

30

7.7

40

4.2

50

0.6

60

0.0

2.3.10
catalytic wet air oxidation

35

2.3.11

23

36

TiO2

2.3.12

2.4

24

 2.4

l
l

l
l

l
l

NaOCl

l
l
l

l
l

l
disperse

dyes

Fenton

l H2O2 l

l
l

RO

l NaCl l

(permeation rate)
l

25

 2.3

UV

H2O2

l H2O2
l

l
l

l
l

12 l

l l

11

l l

O3

l
l

l
l O3
l

l
l

l
l

26

 2.3

l TiO2

BOD/COD
l l

l
l
l

27

2.4
2.4.1 Chlorine residuals

gaseous
chlorine
hypochlorite
hypochloriteous acid
HOClhypochloriteous ionsOCl
free available chlorine
pH
2.337

chlorine demand

pH /
pH 4.5
combined available
chlorine
total
available chlorine38

2.4.2

28

ammonia
amino acids
proteins

total organic carbonTOC

nitrites
iron

manganese
hygrogen sulfidecyanides
organic nitrogen39

methylketone groupchloroform 40
trihalomethanes, THMs
haloketones, HKs

haloacetonitriles, HANs
haloacetic acids, HAAs

chlorophenols

2.4.3

Total Residual ChlorineTRCtrihalomethanesTHMs

41

mosquitofish
LC5042 2.5

pH pH
total residual
chlorine pH=7 pH=8 2.4
42

29

 247 508
43

2.5 mosquitofish
LC5042

LC50mg/L

NHCl2

0.37

HOCl

0.46

NH2Cl

1.31

OCl-

2.21

Ethanolchloramine

HOCH2CH2NHCl

15.4

N-chloroglycin

COOHCH2NHCl

575

30

HOCl(%)

90

10

80

20

70

30

60

40

50

50

40

60

30

70

20

80

10

90

10

11

OCl- (%)

100

100

pH

2.3 pH HOCl OCl- 37

1.4

1.2
1.0
0.8

mg/L TRC

0.6
0.4
0.2
0.0

5.5

6.0

6.5

7.0

7.5

8.0

8.5

9.0

pH

2.4 pH TRC 53

31

2.4.4
THM
RBC THM
98

44

anilineazo compounds

chloroanilines chloronitrobenzennes
chlorophenols O3Ca(OH)2
Ca(OH)2
4.6

45

32

 2.6 O3Ca(OH)2

O3

mg/L mg/L

O3
Ca(OH)2

mg/L

Aniline derivatives

Aniline

2.0178

0.224

-89

3.624

-179

o-Chloroaniline

0.088

0.014

-84

0.208

+236

p- Chloroaniline

0.062

0.019

-69

0.499

+805

2,5-Dichloroaniline

0.055

0.000

-100

0.000

N,N-dimethylaniline

0.008

0.002

-75

0.000

-100

N,N-diethylaniline

0.029

0.00

-100

0.000

p-Nitroaniline

0.650

0.136

-79

0.000

-100

Benzenamine, 2-chloro-4-nitro

0.026

0.019

-27

0.000

-100

Benzenamine, 2-chloro-N,N-diethyl-4-nitro

0.012

0.000

-100

0.000

Benzenamine, 2,4-dinitro

0.018

0.000

-100

0.000

Benzoic acid, 3-amino-2,5-dichloro

0.060

0.000

-100

0.000

Acetamide, N-(2-chlorophenyl)

0.085

0.050

-41

0.000

Acetamide, N-(4-chlorophenyl)

0.061

0.062

0.00

0.000

-100

Acetamide, N-(2,5-dichlorophenyl)

0.017

0.000

-100

0.000

1-(N,N-dimethylaniline)-5-pyrazolone

235.8

145.6

-38

0.076

-99.9

1-(N,N-dimethylaniline)-3-ethoxy-5pyrazolone

0.146

0.049

-66

0.000

-100

Benzene, nitro-

0.179

0.320

+78

0.053

-70

o-Chloronitrobenzene

0.000

0.037

0.022

-40

m-Chloronitrobenzene

0.016

0.017

0.00

0.000

-100

p-Chloronitrobenzene

0.944

0.751

-20

0.133

-86

Benzene, 1.4-dichloro-2-nitro

0.021

0.020

0.00

0.000

-100

Benzene, dinitro-

0.012

0.036

+300

0.000

-100

Benzene, 1,3-dimethyl-2-nitro

0.010

0.000

-100

0.000

Benzeneethanol, 2-nitro

0.042

0.016

-62

0.000

-100

Ethanone, 1-(4-nitrophenyl)

0.106

0.661

+624

0.491

-25

Nitrobenzene derivatives

33

 2.6 O3Ca(OH)2

O3

mg/L mg/L

O3
Ca(OH)2

mg/L

Azobenzene derivatives

1-(n-chloro-n-amino-phenylazo)-5pyrazolone(#1628)
1-(n-chloro-n-amino-phenylazo)-5pyrazolone(#1824)
1-(n-chloro-n-amino-phenylazo)-5pyrazolone(#1807)
1-(n-chloro-n-amino-phenylazo)-5pyrazolone(#1778)
1-(n-chloro-n-amino-phenylazo)-5pyrazolone(#1979)

17.930

11.437

-36

0.635

-96

16.082

9.551

-41

0.076

-99.5

0.297

0.012

-96

0.000

-100

0.112

0.092

-17

0.000

-100

0.652

0.274

-58

0.000

-100

Diazene, (4-nitriphenyl)phenyl

0.036

0.000

-100

0.000

Diazene, bis(4-nitrophenyl)

0.068

0.000

-100

0.000

Phenol, 2,4-dichloro-

0.020

0.000

-100

0.000

Phenol, 2,4,6-trichloro-

0.054

0.000

-100

0.000

Phenol, tetrachloro-

0.097

0.000

-100

0.000

Benzoxazole

0.236

0.167

-29

0.000

-100

Benzene, isocyanato-

0.081

0.070

-13

0.000

-100

Benzene, 1-chloro-2-isocyanato

0.165

0.140

-15

0.000

-100

Benzene, 1-chloro-3-isocyanato

0.039

0.000

-100

0.000

Benzene, 1-chloro-4-isocyanato

0.279

0.212

-24

0.000

-100

1H, 3H-Benzoxazole, 2-one

1.648

1.672

0.00

0.251

-85

Benzene, chloro-

0.035

0.021

-40

0.000

-100

Acetic acid, dichloro-

0.027

0.197

+630

0.026

0.00

Benzoic acid

0.030

0.059

+197

0.046

-21

Benzoic acid, 2-formyl

0.022

0.117

+531

0.083

-29

3-buten-2one, 3,4-dichloro

0.006

0.027

+459

0.011

259

2,5-cyclohexadiene-1,4-dione, 2,6-dimethyl

0.017

0.000

-100

0.000

1-naphthalene-carboxaldehyde

0.070

0.000

-100

0.000

Phenol derivatives

N-compounds

Miscellaneous

34


3.1
3.1.1

1. 1
2.
3. Model CF-610
4. Model PC-310
5. pH Model PC-310
6. ( Model MP-3 )
pH
7.
8.
3.1

3.1.2
3.1.2.1

( 3.2) 13 % Al2O3
1000 mg/L 2 mg/L

35

 NaOCl

CF-610
MP-3
pH

PC-310

ORP

pH
PC-310

MP-3

3.1

3.1.2.2

( 3.3) 13 % Al2O3
1000 mg/L 2 mg/L

36

3.1.2.3 NB-FBN
NB-FBN
40 mg/L COD 18.7 mg/L

3.1.2.4 Yellow-HE4R
Yellow-HE4R 3.4
30 mg/L COD 16.7 mg/L

37

pH

3.2

pH1

pH2

3.3

38

H
S

S
S

Cl

C
H

S
N

Cl

H
S

C
O

3.4 Yellow-HE4R

3.1.3
1. NaOClRiedel-deHanGermany
2. H2SO4 pH Riedel-deHanGermany
3. NaOH pH Riedel-deHanGermany
4. K2Cr2O7
COD Merck CoGermany
5. 10 g/L
COD Riedel-deHan
Germany
6. H2SO9597
COD Riedel-deHan
4
Germany
7. NH4
FeSO42
6H2O
COD
Riedel-deHanGermany
8. HgSO4
COD Riedel-deHanGermany
39

3.2
pH 345678

510142030 60 mg Cl2/L
25

1. pH
2. 25

3. 1 pH
1 % H2SO4
4. pH
5.
(NaOCl )
20
6. pH pH pH ( 1 %
H2SO4 ) pH pH 0.1
7. 5 pHNaOCl
1 % H2SO4 ORP
< 400 ADMI
pH

40

3.3
3.3.1
ADMIAmerican Dyestaff Manufacturers
Institute 3 0.45 m
HACH DR/4000 U 590540438 nm
3 Tristimulus value
Munsell Values -
Adams-Nickerson chromatic value formula DE
ADMI

3.3.2 ORP
ORP controllerModel PC-310

3.3.3 pH
pH pH meterModel PC-310
pH pH

3.3.4
Chlorine transmitter Model CF-610

41

3.3.5 COD
NIEA W515.50A

42


4.1
pH
4.1a4.1b4.2a4.2d4.3a
4.3c4.4a4.4c
4.1a4.1b 40 mg/L NB-FBN
pH
3 14 mg Cl2/L 10 mg
Cl2/L 5 mg Cl2/L pH 3.3
14 mg Cl2/L 10 mg Cl2/L
4.2a4.2d 30 mg/L Yellow-HE4R

pH 3 5 10 14 mg Cl2/L
pH 3.34 5

4.3a4.3c
pH 3
5 10 14 mg Cl2/L
6143 26 400 ADMI pH 4
5 10 14 mg Cl2/L
14787 48 400 ADMI pH 6
43

 5 7.5 10 mg Cl2/L
512262 200 400 ADMI
4.4a4.4c
pH 33.3 4

pH

pH

44

NB-FBNpH=3

NB-FBNpH=3.3

1.4

1.4
=5 mg/L
=10 mg/L
=14 mg/L

=10 mg/L

1.2

1.0

1.0

0.8

0.8
C/C0

C/C0

1.2

0.6

=14 mg/L

0.6

0.4

0.4

0.2

0.2
0.0

0.0
0

200

400

200

time (min)

4.1a NB-FBN pH3

600

4.1b NB-FBN pH3.3

yellow-HE4RpH=3

yellow-HE4RpH=3.3

1.4

1.4
=5 mg/L
=10 mg/L

1.2

=5 mg/L
=10 mg/L
=14 mg/L

1.2

=14 mg/L

1.0

1.0

0.8

0.8
C/C0

C/C0

400
time (min)

0.6

0.6

0.4

0.4

0.2

0.2

0.0

0.0
0

20

40

60

time (min)

20

40

60

time (min)

4.2a yellow-HE4R pH3

4.2b yellow-HE4R pH3.3

45

yellow-HE4RpH=4

yellow-HE4RpH=5

1.4

1.4
=5 mg/L
=10 mg/L
=14 mg/L

1.0

1.0

0.8

0.8

0.6

0.6

0.4

0.4

0.2

0.2

0.0

0.0
0

50

100

=5 mg/L
=10 mg/L
=14 mg/L

1.2

C/C0

C/C0

1.2

150

100

4.2c yellow-HE4R pH4

pH=4

1.4

1.4

=5 mg/L
=14 mg/L

C/C0

C/C0

0.6

0.6
0.4

0.2

0.2

0.0
40

=14 mg/L

0.8

0.4

20

=10 mg/L

1.0

0.8

=5 mg/L

1.2

=10 mg/L

1.0

300

4.2d yellow-HE4R pH5

pH=3

1.2

200
time (min)

time (min)

0.0

60

time (min)

100

200

time (min)

4.3a pH3

46

4.3b pH4

pH=6
=5 mg/L

1.2

=5 mg/L
=10 mg/L
=14 mg/L
=20 mg/L
=30 mg/L
=60 mg/L

1.4

=7.5 mg/L

1.2

=10 mg/L

1.0

1.0
C/C0

0.8
C/C0

pH=3

1.6

1.4

0.6

0.8
0.6

0.4

0.4

0.2

0.2

0.0

0.0

200

400

time (min)

4.3c pH6

40
time (min)

60

80

4.4a pH3

pH=4

pH=3.3

1.4

1.4
=14 mg/L

1.2

=14 mg/L

1.2

=30 mg/L
=60 mg/L

1.0

=20 mg/L
=60 mg/L

1.0
C/C0

0.8
C/C0

20

0.6

0.8
0.6

0.4

0.4

0.2

0.2

0.0

0.0
0

20

40

60

time (min)

50

100

time (min)

4.4b pH3.3

47

4.4c pH4

48

4.2 pH

pH 13
13.537 pH
HOClOCl

pH pH
pH 4.5a
4.5b4.6a4.6c4.7a4.7c4.8a4.8c
pH
4.5a4.5b 40 mg/L NB-FBN
pH
10 mg Cl2/L pH 3 pH 3.3
14 mg Cl2/L pH 3 pH 4
4.6a4.6c 30 mg/L Yellow-HE4R
5 mg Cl2/L pH
1014 mg Cl2/L
pH 3 pH 3.3 pH 4 pH 5
4.7a4.7c
pH 5 mg
Cl2/LpH 3 61 400 ADMI pH
46 7 147512 619 400 ADMI

48

 10 mg Cl2/L pH3456 8
400 ADMI 4387149200 193
14 mg Cl2/LpH 34 7
2648 257
4.8a4.8c
1420 60 mg Cl2/L pH

pH

pH pH

49

NB-FBN14 mg/L

NB-FBN10 mg/L

1.4

1.4
pH=3

pH=3

1.2

pH=3.3

1.0

1.0

0.8

0.8

C/C0

C/C0

1.2

0.6

pH=4

0.6

0.4

0.4

0.2

0.2

0.0

0.0
0

50

100

150

time (min)

4.5a NB-FBN
10 mg Cl2/L

200

4.5b NB-FBN
14 mg Cl2/L

yellow-HE4R10 mg/L

yellow-HE4R5 mg/L
1.4

1.4
pH=3

pH=3

1.2

1.2

pH=3.3
pH=4

1.0

pH=3.3
pH=4

1.0

pH=5

0.8

C/C0

C/C0

100
time (min)

0.6

0.8
0.6

0.4

0.4

0.2

0.2

0.0

pH=5

0.0
0

100

200
time (min)

300

50

100

time (min)

4.6a yellow-HE4R
5 mg Cl2/L

50

4.6b yellow-HE4R
10 mg Cl2/L

5 mg/L

yellow-HE4R14 mg/L
1.4

1.4

pH=3

1.2

pH=4

1.0

pH=4
pH=6

1.0

pH=5

C/C0

0.8

C/C0

pH=3

1.2

pH=3.3

0.6

0.6

0.4

0.4

0.2

0.2

0.0

pH=7

0.8

0.0
0

50

100

200

time (min)

600

time (min)

4.6c yellow-HE4R
14 mg Cl2/L

4.7a
5 mg Cl2/L

10 mg/L

14 mg/L

1.4

1.4
pH=3

1.2

pH=5

pH=4
pH=7

1.0

pH=6
pH=8

C/C0

0.8

pH=3

1.2

pH=4

1.0
C/C0

400

0.6

0.8
0.6

0.4

0.4

0.2

0.2

0.0

0.0
0

100

200

time (min)

50

100

150

200

250

time (min)

4.7b
10 mg Cl2/L

51

4.7c
14 mg Cl2/L

14 mg/L
pH=3

1.2

pH=4

C/C0

C/C0

pH=4
pH=5

1.0

0.8
0.6

0.8
0.6

0.4

0.4

0.2

0.2

0.0

0.0
0

50

100

time (min)

60 mg/L
pH=3
pH=3.3
pH=4

1.0

pH=5

0.8
0.6
0.4
0.2
0.0
0

20

40

40

60

80

4.8b
20 mg Cl2/L

1.4
1.2

20

time (min)

4.8a
14 mg Cl2/L

C/C0

pH=3

1.2

pH=3.3

1.0

20 mg/L

1.4

1.4

60

time (min)

4.8c
60 mg Cl2/L

52

53

4.3
4.3.1 NB-FBN
NB-FBN - dC / dt
first order reaction
a. Cl2 H+
pH
d C / dt

kC

4.1

C ADMI

t min
k min-1
b. lnC0/C t

k R2 4.1

4.104.11 k H+

4.3.2 Yellow-HE4R
4.2a4.2d4.4a4.4c Yellow-HE4R

- dC / dt first order reaction

Cu C(t)
Cu
Yellow-HE4R
53


a. Cl2
H
pH
dCCu/ dt

kCCu

4.2

C ADMI

t min
k min1
Cu ADMI
Cu differential method
k Cu
dCCu/ dt kCCu

4.3

d C / dt kCCu

4.4

d C / dt k Ck Cu

4.5

C d C / dtd C / dt C 4.9

k k Cu
Cu
b. ln
C0Cu /CCu t
k R2 (
) 4.2
4.114.12 k [H+]

54

dC/dt
k

Cu N

4.9 C d C / dt
4.1 NB-FBN
k R2
NB-FBN

pH

3.3

7
8

(mg Cl2/L)

k (1/min)

R2

k (1/min)

R2

0.0072

0.9946

0.0172

0.9557

10

0.0129

0.9839

0.0216

0.9738

14

0.0477

0.9668

0.0317

0.9097

10

0.0028

0.9930

14

0.0351

0.9823

0.0077

0.9660

10

0.0162

0.9354

14

0.0128

0.9718

0.0250

0.9577

10

0.0079

0.9746

14

0.0046

0.8706

0.0029

0.9715

7.5

0.0040

0.9837

10

0.0076

0.9529

0.0015

0.9870

14

0.0039

0.9990

10

0.0022

0.9502

55

 4.2 yellow-HE4R
kCu R2
yellow H-E4R

pH

3.3

(mg Cl2/L)

k
(1/min)

R2

ADMI

k
(1/min)

R2

ADMI

0.0853

0.9127

405.2

0.0074

0.9769

1284.2

10

0.0985

0.9180

397.1

0.0387

0.9384

1231.7

14

0.1232

0.9724

371.2

0.0959

0.8714

877.2

20

0.1000

0.9684

430.6

30

0.1695

0.9670

412.6

60

0.2052

0.8890

343.5

0.0834

0.9124

510.6

10

0.1079

0.9397

381.6

14

0.2263

0.9145

336.5

0.0547

0.9393

1233.9

30

0.1011

0.9748

399.9

60

0.1543

0.9557

406.0

0.0274

0.9932

461.8

10

0.0484

0.9947

474.4

14

0.0672

0.9314

387.2

0.0171

0.9956

1429.7

20

0.0521

0.9942

458.2

60

0.0620

0.9103

447.0

0.0046

0.9550

689.3

10

0.0215

0.9576

287.3

14

0.0210

0.9991

311.1

20

0.0295

0.9849

835.0

60

0.0489

0.9584

620.7

Cu

56

Cu

NB-FBN

[H ]k

[H ]k

0.05

0.07
5 mg/L
10 mg/L
14 mg/L

0.06

5 mg/L
10 mg/L
14 mg/L

0.04

0.03

0.04

0.05

0.03

0.02

0.02

0.01
0.01

0.00

0.00
0

10

10

[H+]10000

[H+]10000

4.10 NB-FBN
k [H+]

4.11
k [H+]

Yellow H-E4R

[H ] k

[H ] k
0.35
5 mg/L
10 mg/L
14 mg/L

5
10
14
20
30
60

0.30
0.25

0.12

0.20

k 1/min

0.16

0.08

mg/L
mg/L
mg/L
mg/L
mg/L
mg/L

0.15
0.10

0.04

0.05
0.00

0.00
0

10

10

[H ] 10000

[H ] 10000

4.12 yellow-HE4R
k [H+]

4.13
k [H+]

57

4.3.3 k pH
k pH
pH HOCl
HOCl

k HOCl
HOCl [OCl - ] + [ H + ]

4.6

[OCl - ] [ H + ]
Ke =
[ HOCl ]

4.7

Ke Ke = 3.2 10-8 at 25
[ HOCl ] =

[OCl - ] [ H + ]
Ke

4.8

[Cl 2 ] = [ HOCl ] + [OCl - ]

[ HOCl ] =

[Cl 2 ] [ H + ]
Ke + [ H + ]

4.9

k HOClOCl
k = k1 [ HOCl ] + k2 [OCl - ]

4.10

4.9
k = k1

[Cl2 ] [ H + ]
[Cl2 ] [ H + ] Ke
+ k2

+
Ke + [ H ]
Ke + [ H + ] [ H + ]

58

4.11

[Cl 2 ] [ H + ]
[Cl 2 ] K e
+ k2
+
Ke + [ H ]
Ke + [H + ]

4.12

[Cl 2 ]
(k1[ H + ] + k2 Ke )
+
Ke + [ H ]

4.13

k (Ke + [ H + ])
= k1 [ H + ] + k2 Ke
[Cl 2 ]

4.14

k = k1

k=

y=

k (Ke + [ H + ])
[Cl 2 ]

4.15

y 4.3H
4.144.17
4.144.17 HOCl k1
4.4 OCl k2 k1

k2 HOCl OCl
HOCl pH
HOClOCl pH
pH

59

dC / d t k1H
Cl2C

4.16

H 10-810-3 M pH38
Cl2 560 mg Cl2/L
C

3004000 ADMI

4.4 k1

k1

NB-FBN

0.0106

0.0156

Yellow-HE4R

0.0660
0.0376

60

 4.3 y
y=

pH

3.3

7
8

k (Ke + [H + ])
[Cl2 ]

(mg Cl2/L)

NB-FBN

0.1022

1.2113*

0.24425*

0.1051*

10

0.0916

0.6994

0.15336

0.2748*

14

0.2419*

0.6248

0.16077

0.4864

20

0.3550

30

0.4012

60

0.2428*

0.5936*

10

0.0100

0.3840

14

0.0892*

0.2888

0.1390

30

0.1199

60

0.0915

0.0389

0.01094

10

0.0344

0.01151

14

0.0065

0.0341

0.01283

0.0087

20

0.0185

60

0.0073

0.0007

10

0.0015

0.00056

14

0.0044

0.0011

20

0.0011

60

0.0006

0.00004

7.5

0.00004

10

0.00006

0.00000

14

0.00000

10

0.00000

Yellow-HE4R

* 4.144.17

61

0.14

y = 0.0106x
2
R = 0.8045

0.12

0.10
0.08
0.06
0.04
0.02
0.00
0

10

[H ]x10000

4.14 NB-FBN
y [H+]

0.80
0.70

y = 0.066x
R 2 = 0.9847

0.60

0.50
0.40
0.30
0.20
0.10
0.00
0

10

[H ]x10000

4.15 yellow-HE4R
y [H+]

62

0.18
0.16

y = 0.0156x
R 2 = 0.9981

0.14

0.12
0.10
0.08
0.06
0.04
0.02
0.00
0

10

[H ]x10000

4.16 y
[H+]

0.60
y = 0.0376x
2
R = 0.9017

0.50

0.40
0.30
0.20
0.10
0.00
0

10

[H ]x10000

4.17 y
[H+]

63

64

4.4
4.4.1
4.3 k
continuously-stirred-tankreactor,CSTR

C / C0 1 / 1k

4.17

n CSTR
C / C0 1 / 1knn
n1 11 1 C0/C1/k

4.18
4.19

n2 22 2
C0/C1/21/k 4.20
n3 33 3
C0/C1/31/k 4.21

4.174.21

C ADMI

C0 ADMI
h

n h

64

 4.5 pH ADMI
400 pH4.014 mg/L
2-CSTR 3-CSTR 60 min

4.5 pH
ADMI 400
400 ADMI
min

pH

4
5
6

7
8

mg Cl2/L

C0(ADMI)

2CSTR

3CSTR

1005

61

66

61

10

1005

43

53

49

14

942

26

33

31

1179

147

165

150

10

1161

87

119

108

14

1056

48

62

57

10

1053

149

201

184

1128

512

769

619

7.5

987

262

317

293

10

1116

200

268

245

1017

619

793

730

14

1050

257

326

300

10

936

193

241

223

65

4.4.2
4.4.2.1
4.6
12 %NaOCl NT$ 3.6 /98 %H2SO4
NT$ 1.82 /NaOH NT$ 9.12 /
4.6
kg/

pH

4
5
6

7
8

12%NaOCl
mg Cl2/L

H2SO4

NaOH

NT$

0.262

0.422

0.1435

3.0200

10

0.336

0.453

0.1750

3.6301

14

0.326

0.425

0.2390

4.1268

0.403

0.297

0.0225

2.1965

10

0.490

0.351

0.0400

2.7676

14

0.555

0.370

0.0400

3.0362

10

0.601

0.342

0.0235

3.0004

0.455

0.279

2.1458

7.5

0.686

0.245

2.9155

10

0.612

0.238

2.6364

0.581

0.294

2.6267

14

0.515

0.210

2.2362

10

0.532

0.079

2.0590

66

4.4.2.2
4.4.1 2CSTR 3CSTR
m3 1000 m3
m3
NT$ 5,000
4.7
4.7 2CSTR 3CSTR
m3

m3NT$

2CSTR
3CSTR

pH
mg Cl2/L

7
8

(m3/)

(NT$)

(m3/)

(NT$/2 )

(m3/)

(NT$/3 )

42.4

211,806

23.0

229,554

14.1

211,551

10

29.9

149,306

18.4

183,851

11.3

169,432

14

18.1

90,278

11.6

116,016

7.2

107,567

102.1

510,417

57.2

572,181

34.6

519,381

10

60.4

302,083

41.4

414,120

25.1

376,459

14

33.3

166,667

21.6

215,868

13.2

198,012

10

103.5

517,361

69.7

697,242

42.6

639,742

355.6

1,777,778

235.9

2,358,630

143.3

2,150,040

7.5

181.9

909,722

110.1

1,101,134

67.8

1,016,499

10

138.9

694,444

93.1

931,013

56.6

849,541

429.9

2,149,306

275.2

2,752,416

168.9

2,533,726

14

178.5

892,361

113.3

1,133,379

69.3

1,040,192

10

134.0

670,139

83.6

836,026

51.7

775,602

67

4.4.2.3

4.8 4.184.26
NT$/m3
NT$ CRF 1 /12 1
/26 1000 m3/
CRF i 1i n 1i n1

n
10 % 15 0.1315

1200
ADMI 400 ADMI pH = 4.0 =
14 mg Cl2/L 12 % NaOClH2SO4
pH 6.0 NaOH NT$ 3.04 /m3
NT$ 0.07 /m3 NT$ 3.11 /m3 26
1000 CMD 8 9

68

 4.8
NT$/m3

pH

(mg Cl2/L)

2CSTR

3CSTR

3.0200 0.0893 3.11 3.0200 0.0968 3.12 3.0200 0.0927 3.11

10

3.6301 0.0629 3.69 3.6301 0.0775 3.71 3.6301 0.0743 3.70

14

4.1268 0.0380 4.16 4.1268 0.0489 4.18 4.1268 0.0472 4.17

2.1965 0.2151 2.41 2.1965 0.2412 2.44 2.1965 0.2277 2.42

10

2.7676 0.1273 2.89 2.7676 0.1745 2.94 2.7676 0.1650 2.93

14

3.0362 0.0702 3.11 3.0362 0.0910 3.13 3.0362 0.0868 3.12

10

3.0004 0.2181 3.22 3.0004 0.2939 3.29 3.0004 0.2804 3.28

2.1458 0.7493 2.90 2.1458 0.9941 3.14 2.1458 0.9424 3.09

7.5

2.9155 0.3834 3.30 2.9155 0.4641 3.38 2.9155 0.4456 3.36

10

2.6364 0.2927 2.93 2.6364 0.3924 3.03 2.6364 0.3724 3.01

2.6267 0.9059 3.53 2.6267 1.1601 3.79 2.6267 1.1106 3.74

14

2.2362 0.3761 2.61 2.2362 0.4777 2.71 2.2362 0.4560 2.69

10

2.0590 0.2824 2.34 2.0590 0.3524 2.41 2.0590 0.3400 2.40

7
8

69

6.0

6.0
-=5 mg Cl2/L

total

4.0
3.0
2.0
1.0

4.0
3.0
2.0
1.0

0.0
3

0.0

pH

4.18 pH
5 mg/L

6.0

pH

4.19 pH
10 mg/L

6.0

-=14 mg Cl2/L

2CSTR-=5 mg Cl2/L

total

5.0

5.0

4.0

total

4.0

3
NT$/m

3
NT$ /m

total

-=10 mg Cl2/L

5.0
NT$/m3

NT$/ m3

5.0

3.0

3.0

2.0

2.0

1.0

1.0

0.0

0.0
3

4.20

5
pH

pH

pH
14 mg/L

70

4.21

pH 2 CSTR
5 mg/L

6.0

6.0

total

5.0

4.0

NT$ /m3

NT$/m3

5.0

3CSTR-=5 mg Cl/L

total

3CSTR-=10 mg Cl2/L

3.0
2.0
1.0

4.0
3.0
2.0
1.0

0.0
3

0.0

pH

pH

4.22

pH 2 CSTR
10 mg/L

4.23

6.0

6.0
3CSTR-=10 mg Cl2/L

5.0

3CSTR-=5 mg Cl/L

total

total

5.0

4.0

3
NT$ /m

NT$/m3

pH 2 CSTR
14 mg/L

3.0
2.0
1.0

4.0
3.0
2.0
1.0

0.0

0.0

pH

4.24

pH

pH 3 CSTR
5 mg/L

4.25 pH 3 CSTR
10 mg/L

71

6.0
3CSTR-=14mg Cl2/L

NT$ /m3

5.0

total

4.0
3.0
2.0
1.0
0.0
3

4.26

5
pH

pH 3 CSTR
14 mg/L

72


5.1
1. pH NB-FBN
- dC / dt first order
reaction
2. Yellow-HE4R C(t)
Cu
Yellow-HE4R

3. pH

4. HOCl OCl HOCl HOCl

k OCl k2
k1 k2 HOCl OCl
HOCl pH

HOClOCl
pH pH

5. 1200
ADMI 400 ADMI pH = 4.0

73

 = 14 mg Cl2/L 12 % NaOClH2SO4
pH 6.0 NaOH NT$ 3.04 /m3
NT$ 0.07 /m3 NT$ 3.11 /m3
26 1000 CMD 8 9
5.2
1. 2-CSTR 3-CSTR 60
min

2. 2.4.4

74