h2o2/uv...

Prepared by Prof. Chih-Hsiang Liao of CNU

1

H2O2/UV程序處理染整業放流水之研究

講員 : 廖志祥教授

嘉南藥理科技大學環境工程科學系台南縣仁德鄉二仁路一段 60 號

Tel: 06-266-0414; 06-266-4911轉 300; Fax: 06-266-7323 E-mail: [email protected]; [email protected]

講授大綱

þ 染整業放流水標準

þ H2O2/UV程序基本概念

Ü UV光譜

Ü H2O2物化特性

Ü HO•生成機制

þ H2O2/UV程序反應系統

þ H2O2/UV程序效率

þ 總結

þ 附件


2

染整業放流水標準

生化需氧量三０化學需氧量一六０懸浮固體三０印花、梭織布染整者

真色色度五五０

生化需氧量三０化學需氧量一四０懸浮固體三０

筒紗、絞紗染色、針織布

及不織布染整者真色色度五五０生化需氧量三０

化學需氧量一００

懸浮固體三０

印

染

整

理

業

整理、紙印花、刷毛、剪

毛、磨毛及非屬前二類者

真色色度五五０

中華民國九十年十一月二十一日（九０）環署水字第００六九０九七號令修正


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H2O2/UV程序基本概念

UV光譜

(Source: http://www3.sympatico.ca/csatari/index5.htm)

Name Wavelength Range / nm Wavenumber Range / cm-1 Energy Range

(kJ einstein-1)

UVA 315 ö 400 31,746 ö 25,000 299 ö 380

UVB 280 ö 315 35,714 ö 31,746 380 ö 427

UVC 200 ö 280 50,000 ö 35,714 427 ö 598

Vacuum Ultraviolet

(VUV)

100 ö 200 100,000 ö 50,000 598 ö 1196


4

UV燈及石英套管

(one end)

(two ends)

(4 pins)

(2 pins)


5

H2O2物化特性*

2 H2O2 ----> 2 H2O + O2

Hydrogen Peroxide (H2O2) solutions are clear, colorless,

water-like in appearance, and can be mixed with water in

any proportion. At high concentrations, it has a slightly

pungent or acidic odor.

過氧化氫用途

End Use Industries

• Landfills

• Oil refining

• Mining / metallurgy

• Machining

• Textiles

• Power production

• Composting

• Potable water

• Chemicals and resins

• Food processing

• Electronics

• Pulp and paper

• Timber products

• Hazardous wastes

• Site remediation

• Municipal wastewater

氧化電位

Oxidant Oxidation Potential, V Fluorine Hydroxyl radical Ozone Hydrogen peroxide Potassium permanganate Chlorine dioxide Chlorine

3.0 2.8 2.1 1.8 1.7 1.5 1.4

* Source: http://www.h2o2.com


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相對氧化電位

Species Relative Oxidation Power (Cl2=1.0) Flourine Hydroxyl radical Atomic oxygen (singlet) Hydrogen peroxide Perhydroxyl radical Permanganate Hypobromous acid Chlorine dioxide Hypochlorous acid Hypiodous acid Chlorine Bromine Iodine

2.23 2.06 1.78 1.31 1.25 1.24 1.17 1.15 1.10 1.07 1.00 0.80 0.54

H2O2重量濃度換算表


7


8


9

Molecular extinction coefficient ε, liters/mole.cm

NOTES: 1. The absorption coefficient for both liquid and vapor H2O2 is essentially the same.

2. The shape of the curve relating the extinction coefficient to the wavelength is slightly parabolic. 3. The absorption of ultraviolet radiation by H2O2 results in dissociation of the molecule into two hydroxyl radicals (HO.), although other reactions are possible and may occur to some extent. 4. Beer’s law is not strictly obeyed by H2O2 solutions, as higher concentrations of H2O2 absorb to a greater extent than Beer’s law would predict (i.e., the molecular extinction coefficient decreases as H2O2 concentration increases > 50% wt.%). 5. The presence of alkali shifts the absorption curve toward the visible (i.e., increases the absorption coefficient). This is due to the dissociation of H2O2 into the perhydroxyl ion (HO2

-) that absorbs more intensely than H2O2.


10

HO•生成機制

+

Þ

2 HO•

反應機構

UV + H2O2 à 2 HO•

HO• + H2O2 à HO2• + H2O

HO• +ΣSi à ΣSi oxi (Si: HCO3-/CO3

=, organics, etc.)

HO2• ↔ H+ + O2

-• (pKa = 4.8)

HO2• + O2

-• + H2O à H2O2 + O2 + OH-

HO2• + HO2

• à H2O2 + O2


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H2O2/UV程序反應系統

(Source: http://www.llnl.gov/IPandC/op96/03/3n-uv.html)


12

H2O2/UV程序效率

H2O2劑量影響效應(Ref. 1)

0 50 100 1500

100

200

300

400

500

600

700

800

900

1000

1100

the original influent the secondary effluent the final effluent

CO

D r

esid

ue, m

g/l

Time, day

Figure 1 The Day-to-day Monitoring of COD Residues for the Original, Secondary, and the Final effluent

of the Studied Textile Factory

Figure 2 Experimental Setup of Recirculated Photoreactor System


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染整二級出流水質: pH = 7.2, COD = 168 mg/l, color = 420 in ADMI unit.

0 50 100 150 200 250 300

0.0

0.2

0.4

0.6

0.8

1.0 H

2O

2(748 mg/l) alone

UV(14 watts) alone H

2O

2(187 mg/l)/UV(14 watts)

H2O2(374 mg/l)/UV(14 watts)

H2O

2(561 mg/l)/UV(14 watts)

Rem

oval

Fra

ctio

n of

CO

D

UV Dose, watt-min/l

Figure 3 Effect of H2O2 Dosage on COD Removal

0 50 100 150 200 250 300

0.0

0.2

0.4

0.6

0.8

1.0

H2O

2 (748 mg/l) alone

UV (14 watts) alone H2O2 (187 mg/l)/UV (14 watts)

H2O

2 (374 mg/l)/UV (14 watts)

H2O

2 (561 mg/l)/UV (14 watts)

Rem

oval

Fra

ctio

n of

Col

or

UV Dose, watt-min/l

Figure 4 Effect of H2O2 Dosage on Color Removal


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HCO3-/CO3

=影響效應(Ref. 2)

0 20 40 60 80 100

0.0

0.2

0.4

0.6

0.8

1.0 (a)

[HCO3-/CO

3=]

o = 0 mM

[HCO3-/CO

3=]

o = 1.29 mM

[HCO3-/CO

3=]

o = 2.50 mM

Res

idua

l Fra

ctio

n of

NP

DO

C

Time, min

0 20 40 60 80 100

0.0

0.2

0.4

0.6

0.8

1.0 (b)

[HCO3-/CO3

=]o = 0 mM

[HCO3-/CO3

=]o = 1.29 mM

[HCO3-/CO

3=]

o = 2.50 mMRes

idua

l Fra

ctio

n of

H2O

2

Time, min

Figure 5. Residual Fraction of NPDOC (a) and H2O2 (b) versus time at different initial HCO3

-/CO3=

concentrations: [H2O2]o = 29.7 mM; [HA]o = 6 mg/L; pH = 10; without aeration.


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pH 影響效應(Ref. 3)

2 4 6 8 100.1

1

10

100 BuCl H

2O

2

c HO

, j/i

, c

H2O

2, j

/i

pH

Figure 6. Effect of pH on the cHO, j/i and cH2O2, j/i profiles (CT = 0 mM): [H2O2]o = 192±6 µM, UV

power = 64 watts, [Cl-]o = 2500 mM, [BuCl]o= 16 µM.

2 4 6 8 10 12 140.01

0.1

1

10

100

c HO

, j/i

, c

H2O

2, j

/i

BuCl ([Cl-]o/C

T=1)

H2O

2 ([Cl-]

o/C

T=1)

BuCl ([Cl-]o/C

T=10)

H2O2 ([Cl-]o/CT=10)

BuCl ([Cl-]o/CT=100)

H2O2 ([Cl-]o/CT=100)

pH

Figure 7. Effect of pH on the cHO, j/i and cH2O2, j/i profiles ( [Cl-]o/CT = 1, 10, 100): [H2O2]o = 188±28

µM, UV power = 64 watts, CT = 25 mM, [BuCl]o= 16 µM.


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Cl-影響效應(Ref. 3)

10 100 1000 100000.0

0.5

1.0

1.5

2.0

2.5

3.0

c HO

, j/i

, c

H2O

2, j

/i

BuCl H

2O

2

[Cl-]o, mM

Figure 8. Effect of chloride concentration on the cHO, j/i and cH2O2, j/i profiles (CT = 0 mM): [H2O2]o =

195±4 µM, UV power = 64 watts, pH = 5, [BuCl]o= 16 µM.

0.1 1 10 100 1000 100000.0

0.5

1.0

1.5

2.0

2.5

3.0

c HO

, j/i

, c

H2O

2, j

/i

BuCl H2O2

[Cl-]o, mM

Figure 9. Effect of chloride concentration on the cHO, j/i and cH2O2, j/i profiles (CT = 25 mM): [H2O2]o =

198±4 µM, UV power = 64 watts, pH = 7.00±0.00, [BuCl]o= 16 µM.


17

Cu2+影響效應(Ref. 4)

0.0

0.2

0.4

0.6

0.8

1.0

a

CuSO4 . 5H2O = 0 mg/L



TO

C F

ract

ion R

emain

ing

0 20 40 60 80 100 120

0.0

0.2

0.4

0.6

0.8

1.0

c




H2O

2 Fra

ctio

n R

emain

ing

Time, min

Figure 10. Effect of initial Cu2+ concentration on (a) TOC removal, and (c) H2O2 degradation: TOC

= 8.1 mg/L; pH = 6.0; H2O2 = 91.1 mg/L; UV Power = 14 watts.


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H2O2/UV、Fenton、Photo-Fenton 比較(Ref. 5)

稀釋後實廠染料製程廢水水質: ADMI color value = 1100, COD = 350 mg/l, Cl- = 1638 mg/l, SS = 35 mg/l, and pH = 3.5.

Fig. 11. Schematic Reaction Pathways of HO• Radical Formation

0 20 40 60 80 100 120

0.2

0.4

0.6

0.8

1.0

0.2

0.4

0.6

0.8

1.0 H2O

2/UV

H2O

2/Fe2+

H2O

2/UV/Fe2+

Res

idua

l CO

D F

ract

ion

Time, min

Fig. 12. Process Performance Comparison on the Removal of COD :

the initial H2O2 = 680 mg/l, the initial Fe2+ = 105 mg/l, the UV power = 128 watts


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0 20 40 60 80 100 1200.0

0.2

0.4

0.6

0.8

1.0

0.0

0.2

0.4

0.6

0.8

1.0

H2O

2/UV

H2O

2/Fe2+

H2O

2/UV/Fe2+

Res

idua

l AD

MI C

olor

Val

ue F

ract

ion

Time, min

Fig. 13. Process Performance Comparison on the Removal of ADMI Color Value:

the initial H2O2 = 680 mg/l, the initial Fe2+ = 105 mg/l, the UV power = 128 watts


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REFERENCES

1. Chih-Hsiang Liao, Ming-Chun Lu, Ying-Hsien Yang, and I-Chun Lu (2000). UV-catalyzed

Decomposition of Hydrogen Peroxide As an Innovative Technology for Advanced Treatment of

Textile Wastewater. Environ. Eng. Sci. 17(1), 9-18.

2. Shyh-Fang Kang, Chih-Hsiang Liao, and Hung-Pin Hung (1999). Peroxidation Treatment of Dye

Manufacturing Wastewater in the Presence of Ultraviolet Light and Ferrous Ions. Journal of

Hazardous Materials B65, 317-333.

3. Wang G.S., Liao C.H. and Wu F.R. (2001). Photodegradation of Humic Acids in the Presence of

Hydrogen Peroxide. Chemosphere 42(4), 379-387.

4. Chih-Hsiang Liao, Shyh-Fang Kang, and Fu-An Wu (2001). Hydroxyl Radical Scavenging Role of

Chloride and Bicarbonate Ions in the H2O2/UV Process. Chemosphere 44(5), 1193-1200.

5. Chih-Hsiang Liao, Ming-Chun Lu, Shyh-Hsiung Su (2001). Role of Cupric Ions in the H2O2/UV

Oxidation of Humic Acids. Chemosphere 44(5), 913-919.

6. Shyh-Fang Kang, Chih-Hsiang Liao and Shei-Tue Po (2000). Decolorization of Textile Wastewater

by Photo-Fenton Oxidation Technology. Chemosphere 41(8), 1287-1294.


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附件

North America's First UV/Peroxide System to Treat Public Drinking Water Set to Go On-line in Salt Lake City, Utah - Calgon Carbon's Corporation's Rayox® Tower System Chosen for Historic Application PITTSBURGH -- April 8, 1998 -- Calgon Carbon Corporation announced that the first-ever, full-scale UV/Peroxide system for drinking water treatment in North America is scheduled for start-up in Salt Lake City, Utah, this summer. The Salt Lake City Department of Public Utilities selected Calgon Carbon Corporation's UV/Peroxide system to treat perchloroethylene (PCE), which was found at low levels in a well in its public drinking water system. PCE is a suspected carcinogen commonly found in groundwater supplies and regulated under the 1986 Safe Drinking Water Act. City officials chose the Calgon Carbon Corporation UV/Peroxide system technology after conducting an analysis of other technologies including air stripping and ozone. The system that Salt Lake City will use is a Calgon Carbon Corporation 360 kW Rayox® Tower using 12x30 kW lamps. The capital cost for the Salt Lake City system is $450,000, and operating costs are expected to be less than $0.20 per 1,000 gallons of treated water. According to Florence Reynolds, water quality and treatment administrator for Salt Lake City, "We considered air stripping but felt that the technology was problematic because of the need to treat air emissions. We ultimately selected the Rayox system technology because it has several unique advantages that the other systems couldn't offer. One key advantage is that there is no transfer of contaminants from one medium to another. Residents here are very pleased about that." Adds Reynolds, "the Rayox system is compact enough that it fits inside an existing building at the well site. The system also retains the well's full 3,000 gpm flow capacity because the UV/Peroxide system is able to effectively treat 100 percent of the water." John Mickler, managing director of Calgon Carbon Corporation's Advanced Oxidation Technologies Business Unit, said "This design flexibility not only will minimize Salt Lake City's capital expenditures, but it will allow city officials to maintain the aesthetics of the historic building that houses the system, as well as the integrity of the surrounding residential neighborhood." Adds Mickler, "Both factors were very important to the city. They contributed significantly to the overall attractiveness of using the Rayox system." The Rayox system destroys PCE to below detection levels by injecting small quantities of hydrogen peroxide into the contaminated water, and then exposing it to ultraviolet light. In addition, and in contrast to ozone-based processes, the UV/Peroxide process neither produces bromate ion in bromide-ion-bearing waters, nor does it produce any off-gases. Calgon Carbon Corporation is a world leader in UV technologies for water treatment. Worldwide, the company has more than 250 UV/Oxidation systems treating a broad range of contaminated groundwaters, industrial wastewaters and process waters. The Pittsburgh-based company is the world leader in activated carbon technologies, serving approximately 4,000 customers worldwide. Contact: Gail Gerono, Director of Investor Relations and Corporate Communications, (412) 787-6795; [email protected]


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h2o2/uv...

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