Environmental Informatics Archives, Volume 5 (2007), 674- 683 EIA07-070 ISEIS Publication Series Number P002 2007 ISEIS

S - International Society for Environmental Information Sciences

Application of the Taguchi experimental design to the optimization of UV/TiO2 and UV/H2O2 process for copper complexes treatment
H.L. Shyu (1)** and L.L. Hsieh (2)
(1)

Department of Medical Laboratory Science and Biotechnology,

(2)

Department of Radiological Technology

Central Taiwan University of Science and Technology, 11 Pu-Tzu Lane, Pei-tun District, 40601 Taichung, Taiwan

Abstract.. The aim of this work is to study the optimization of UV/TiO2 and UV/H2O2 process for copper complexes by Taguchis experimental design. The complexes of copper metal with aminocarboxylic ligands in a ratio and different buffer solution was prepared. Each of experiments was repeated three times to calculate signal/noise (S/N).Then under the high-pressure mercury lamp photoinduced degradation, to achieve the optimization by means of the Taguchi experimental design. Five control factors at three levels were explored: The kind of catalysts, pH of the solution, the capacity of H2O2 and TiO2, the kind of aminocarboxylic acid, the ratio of the aminocarboxylic acid and Cu2+ and assigned to the columns of a L18 saturated orthogonal array. The copper removal efficiency of photodegradation with the presence in H2O2 Solution showed that H2C2O4/Cu(3:1moles)/pH=6.5 buffer solution reduced 97.8% .The effect of the kind of catalyst was found to be insignificant, the ratio of the aminocarboxylic acid and Cu2+ had the greatest influence to the optimization of . photodegradation. There had reciprocation in UV/TiO2 and UV/H2O2 process between each factor. Key wordOptimization, Statistical design, Pollution, photo-oxidation process

1.Introduction High-Technical Industry(Izumi, 2004) has been the main stress in ecnomic development of countries for high effectiveness and low energy consumed, But during the production of the semiconductor is accompanied with significant amount of waste. Copper is one of the most serious and ubiquitous waste. A lot of chemicals contain copper, including animal fodder additive, crease-resistant pigment, fertilizer, bactericide and the content of battery. Copper is highly toxic to plants, it inhibits root elongation and branching, reduces transroot potential, increases lignin synthesis, blocks the photosynthetic electron transport, usually in the micromolar range of exposure concentrations. Another organic acid in water are ethylenediaminetetraacetic acid(EDTA) Nitrilotriacetic acid(NTA) that are major components in various detergents and textile, acting as complexing agent hence appears in relative high concentrations in different types of wastewater. When Cu2+ across into aminocarboxylic acid to produce complexes that can alter the solubility of metal and toxicity. The complexed metals are generally less toxic to microorganisms than the free metal ions(Babich and Stotzky 1986), as the metal is less available when bound to a ligand. Oden(1993) Studied mutual reaction of copper and organic matter in nature that had influence on the
*

Corresponding author: hlshyu@ctust.edu.tw

674

transmission of copper and nature organic matter. Yang Zheng-liang(2005) presents the current progress of research on heavy metallic pollution in water bodies. Photo-oxidation is a promising technique among few newly developed but yet to be industrially employed techniques. Photocatalytic oxidation uses UV radiation and a catalyst for the destruction of the pollutants. Advanced Oxidation Processes(AOP) in wastewater treatment that has obtained popularity during the past two decades for the treatment of industrial effluent. These processes use ultraviolet light along with ozone and/or hydrogen peroxide to generate free radicals that react with the pollutants at a rapid rate. Legrini et al.(1993) provide a comprehensive review on AOP. Raj (2005) attempt to use Taguchis orthogonal design to optimize of UV/H2O2 process in integration with biological waste treatment. Four factors were considered for optimization: Dosage of H2O2, pH, circulation rate and number of doses of oxidant.Therefore, this research describes the application of UV/TiO2 and UV/H2O2 process for copper complexes treatment in water, because of Taguchi experimental design have been widely used for wastewater treatment(Daneshvar, 2007; Mohammadi, 2005), due to reduce experimental time and their experimental results reproductive. The Taguchi experimental design differentiates between control factors and noise or uncontrollable factors and treats them separately by means of special design matrices calledOrthogonal Arrays(OA). Columns and rows of an OA are arranged in a fixed way indicating the combination of factor levels in each experiment to be run, and allowing the simultaneous evaluation of several parameters with the minimum number of trials(Taguchi, 1991). The main advantage of the Taguchi parameter design, as opposed to the classic factorial design methods, lies in the introduction of noise factors in the experimentation which provoke an uncontrolled variation leading to a noise insensitive response, therefore to higher reproductibility. The UV/TiO2 and UV/H2O2 process for copper complexes treatment in water was optimized by means of the Taguchi experimental design.

2. Materials and methods 2.1 Materials All the chemicals used in this study were of analytical grade purity and purchased from Aldrich(copper(II) chloride dehydrate)Merck(hydrogen peroxide, Oxalic acid, Ethylenediaminetetracetatic acid disodium salt, sodium chloride, sodium dihydrogen phosphate)RDH(Tris(hydroxymethyl)ACROS(Nitrilotriacetic acid disodium salt). The water used was double deonized water to prepare all the solution. The buffer solutions were prepared with acetic acidsodium dihydrogen phosphateTris(hydroxymethyl) that were adjusted with diluted H2SO4 and NaOH solutions and then the pH values were measured with pH meter. The 1mmole carboxylic acid( EDTANTAH2C2O4 )in different buffer solution and 1mmole Cu2+ were prepared, then react in different proportions(acidCu2+) to produce complexes.All of solutions were filtered through 0.2 m membranes 2.2 Analytical Methods The reactor was equipped with the high-pressure mercury lamp(100W,ACE Glass Incorporated IL1700 Research Radiometer, International light, Newburyport, MA, 01950 )as a UV light source(Fig1), The concentration of Cu2+ from the reactor was analyzed by an atomic absorption spectrophotometer(Model Z-8200, Hitachi Co., Ltd., Japan) equipped with a copper hollow cathode lamp under recommended condition at

675

325.8 nm and 10 mA. The amount of Cu2+ by complexation and directly.

Photocatalytic oxidation was calculated

Fig. 1 Schematic of Photocatalytic oxidation

2.3 Orthogonal array and experimental factors Designing the matrix experiment. Taguchi provides many standard orthogonal arrays and corresponding linear graphs for the control parameters to fit a specific study. Control parameters are those design factors that can be set and maintained. The number of levels for each test parameter defines the experimental region. Table1 represents the control parameters and their levels for this study.

Table 1 Experimental variables : factors levels Level Factors A Kind of Catalyst 1 2 3 H2O2 TiO2 4 6.5 9 B pH C Kind of Carboxylic acid EDTA NTA H2C2O4 D acidCu
mole 2+

E Amount of Catalysts(mmole) H2O2 0.03235 0.06470 0.1618 TiO2 0.2504 0.6259 1.2518

1:1 2:1 3:1

After the experiments were conducted, the optimal test parameter configuration within the experiment design must be determined. To analyze the results, the Taguchi method uses a statistical measure of performance called signal-to-noise (SN) ratio.The S/N ratios are different according to the type of characteristic. In the case that bigger characteristics are better, the S/N ratio is defined as
n

SN(dB)-10 log y
i1

2 2 -10 log ( y +S )

n
Each of experiments was repeated three times to calculate signal/noise (S/N), eightteen experiments were required to study the effect of parameters on. The effect of photocatalytic oxidation was determined by the concentration of the copper, the lower the concentration of copper was, the more influences of photocatalytic oxidation.

676

3. Results and Discussion 3.1 The formation of complex As the Fig. 2 indicates, there is a marked decrease when the proportion of acid/Cu2+ increase in different buffer solution. There was the minimum concentration of copper when the proportions NTA/Cu2+=3:1 in pH

6.5 buffer solution. Clearing, the bigger the proportion of acid/Cu2+ caused the fewer dissociated copper ion.

40 30 20 10
1:1

H2O 4 6.5
2:1 NTA

9
1:1 2:1
9

3:1

3:1

H2C2O4

6.5

1:1

2:1

H2O

Fig. 2 The concentration of copper in different proportions(acidCu2+) complexes

3.2 The effects of factors

S/N -10.00 -12.00 -14.00 -16.00 -18.00

S/N(dB)

-20.00 -22.00 -24.00 -26.00 -28.00 -30.00 A1 A2 B1 B2 B3 C1 C2 C3 D1 D2 D3 E1 E2 E3

Factor/Levels Fig. 3 Effects of control factors on the signal-to-noise ratio

Figure 3 shows these effects on the measured responseH2O2 catalystpH 6.5H2C2O4 leading to the best response. Significant differences were found between the three levels of the D factors, leading levels 3(the proportion of mole acidCu2+ =3:1) to a smaller overlapping potential of copper complexes. Therefore, the

677

3:1

optimum condition is A1, B2, C3, D3 and E1 the optimal parameters (conditions) after the UV/TiO2 and UV/H2O2 process for copper complexes treatment in water are A (Kind of Catalyst) at level 1 (H2O2), B ( pH) at level 2 (6.5), C (Kind of Carboxylic acid) at level 3 (H2C2O4), D (the proportion of mole acidCu2+) at level 3 (3:1) and E (Amount of Catalysts) at level 1 (0.03235mmole).Finally, in this condition the copper removal efficiency of photodegradation was 97.8% .

35.00 30.00 25.00

S/N(dB)

20.00 15.00 10.00 5.00 0.00 B1 B2 B3

D1 D2 D3

Factor/Levels Fig. 4 The reciprocation of factor B (pH ) and factor D (the proportion of mole acidCu2+ )
30.00 25.00 20.00

S/N(dB)

15.00 10.00 5.00 0.00 A1 A2

D1 D2 D3

Factor/Levels

Fig. 5 The reciprocation of factor A (Kind of Catalyst ) and factor D (the proportion of mole acidCu2+ )
25.00 20.00 15.00 10.00 5.00 0.00 A1 A2

S/N(dB)

B1 B2 B3

Factor/Levels Fig. 6 The reciprocation of factor A (Kind of Catalyst ) and factor B (pH)

678

25.00 20.00

15.00

S/N(dB)
10.00

E1 E2 E3

5.00 0.00 A1 A2

Factor/Levels Fig. 7 The reciprocation of factor A (Kind of Catalyst ) and factor E (Amount of Catalysts )
25.00 20.00 15.00 10.00 5.00 0.00 A1 A2

S/N(dB)

C1 C2 C3

Factor/Levels Fig. 8 The reciprocation of factor A (Kind of Catalyst ) and factor C (Kind of Carboxylic acid)
30.00 25.00 20.00 15.00 C1 C2 C3

S/N(dB)
10.00 5.00 0.00 B1 B2 B3

Factor/Levels Fig. 9 The reciprocation of factor B (pH ) and factor C (Kind of Carboxylic acid)

679

35.00 30.00 25.00

S/N(dB)

20.00 15.00 10.00 5.00 0.00 B1 B2 B3

E1 E2 E3

Factor/Levels Fig.10 The reciprocation of factor B (pH ) and factor E (Amount of Catalysts)
25.00 20.00 15.00 10.00 5.00 0.00 C1 C2 C3

S/N(dB)

E1 E2 E3

Factor/Levels Fig. 11 The reciprocation of factor C (Kind of Carboxylic acid) and factor E (Amount of Catalysts)
30.00 25.00

S/N(dB)

20.00 15.00 10.00 5.00 0.00 C1 C2 C3 D1 D2 D3

Factor/Levels Fig. 12 The reciprocation of factor C (Kind of Carboxylic acid) and factor D (the proportion of mole acid Cu2+)

680

35.00 30.00 25.00

S/N(dB)

20.00 15.00 10.00 5.00 0.00 D1 D2 D3

E1 E2 E3

Factor/Levels Fig. 13 The reciprocation of factor D (the proportion of mole acidCu2+) and factor E (the proportion of mole acidCu2+)

From Fig.4 to Fig.13 are the reciprocation figures of five factors. Clearly, these figures indicate that there have strong reciprocation between five factors, because of chemical experiment itself have strong reciprocation situations. If to use traditional experimental design can not observe these reciprocation.

Table 2 Experimental layout using the L18 orthogonal array and experimental results for results for photocatalytic oxidation EXP A 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 1 1 1 1 1 1 1 1 1 2 2 2 2 2 2 2 2 2 B 1 1 1 2 2 2 3 3 3 1 1 1 2 2 2 3 3 3 Factor C 1 2 3 1 2 3 1 2 3 1 2 3 1 2 3 1 2 3 D 1 2 3 1 2 3 2 3 1 3 1 2 2 3 1 3 1 2 E 1 2 3 2 3 1 1 2 3 3 1 2 3 1 2 2 3 1 1(ppm) 28.8 24.2 12.6 16 4.9 0.3 17 7.9 34.5 15.3 27.9 13.7 22.8 21.1 19.8 9.4 27.4 17 Response 2(ppm) 27.9 23.5 12.3 15.8 4.4 0.2 16.4 7.5 33.9 15.7 27.2 13.1 21.9 20.9 18.9 8.8 26.4 16.4 3(ppm) 29.2 24.6 13.1 16.4 5.5 0.3 17.5 8.5 35.3 16.1 28.8 14.8 23.6 19.8 20.6 9.4 27.3 17.6 S/N(dB) -29.14 -27.64 -22.06 -24.12 -13.92 11.28 -24.60 -18.04 -30.77 -23.92 -28.94 -22.86 -27.15 -19.11 -25.93 -19.28 -28.64 -24.61

681

The structure of Taguchi's L18 design and the results of measurement are shown in Fig. 2

Table 3 Pooled ANOVA table for the regular analysis Factor A B C D E Error SUM S SS 43.38 702.01 33.85 2469.44 184.92 9.23 3442.84 0.46 DOF 1 2 2 2 2 44 53 Var 43.38 351.01 16.93 1234.72 92.46 0.21 F 137.86 1673.15 80.68 5885.59 440.74 Confidence(%) 100.00 100 100 100 100 Contribution(%) 1.260 20.390 0.983 71.727 5.371 100

In order to conduct an analysis of the relative importance of each factor more systematically, an analysis of variance (ANOVA) was applied to the data. The main objective of ANOVA is to extract from the results how much variations each factor causes relative to the total variation observed in the result. From the results of ANOVA in table 3 , the moles proportion of acidCu2+ had the largest variance and the pH of solution indicated the second, respectively. The pH is an importment parameter which control the adsorptivity (Kim 2003 ). Whereas the kind of carboxylic acid did not affect the response with the range of parameters tested.

4.Conclusion Experiments have been conducted based on the Taguchi method as an experimental design and the model parameter has been calculated using the experimental data of copper concentration. The effect of photocatalytic oxidation was dependent on the the proportion of mole acidCu2+ , pH, Amount of Catalysts. The copper removal efficiency of photodegradation with the presence in 0.03235mmole H2O2 solution showed that H2C2O4/Cu(3:1moles)/pH=6.5 buffer solution reduced 97.8%, there have strong reciprocation between five factors.

Acknowledgements The authors would like to express their gratitude to the University of Central Taiwan University of Science and Technology for the financial support and assistance..

References Izumi, S., (2004) Proceedings of Symposium on Semiconducting Silicides: Science and Future Technology of the 8th IUMRS International Conference on Advanced Materials. Thin Solid Films 461, 7 Oden, W. I., Amy, G. L., Conklin, M. (1993) Subsurface interactions of humic substances with Cu(II) in saturated media. Environ. Sci. Technol. 27, 1045-1051 Kim, M.S., Hong, K. M., Chung, J. G. (2003) Removal of Cu(II) from aqueous solutions by adsorption process wiyh anatase-type titanium dioxide. Water Research 37, 3524-3529

682

Babich, H. Stotzky, G. (1986) Environmental factors affecting the utility of microbial assays for the toxicity and mutagenicity of chemical pollutants. In:Dutka BJ, Bitton G(eds) Toxicity testing using microorganisms, vol 2. CRC Press, Boca Raton, FL, 9-42 Raj, C.B.Chidambara, Quen, Han Li (2005) Advanced oxidation processes for wastewater treatment Optimization of UV/H2O2 process through a statistical technique. Chemical Engineering Science 60, 5305-5311 Legrini, O., Oliveros, E., Braun, A.M.(1993) Photochemical processes for water treatment. Chemical Reviews 93, 671 Taguchi, G.(1991) System of experimental design. Quality Resources, Kraus and Americans Supplier Institute(eds), USA Yang, Zheng-liang, Feng, Gui-ying, Hu, Shi-bin, Zheng, Xue-bin(2005) Current research trends and controlling technique for heavy metal pollution in waters 23, 219-223 Daneshvar, N. Khataee , A.R. Rasoulifard, M.H. Pourhassan , M. (2007) Biodegradation of dye solution containing Malachite Green: Optimization of effective parameters using Taguchi method Journal of Hazardous Materials 143, 214-219 Toraj Mohammadi, Ahmad Moheb, Mohtada Sadrzadeh, Amir Razm (2005) Modeling of metal ion removal from wastewater by electrodialysis Separation and Purification Technology l41, 73-82

683