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PRE-OXIDATION AND COAGULATION OF PAPER AND PULP WASTEWATER BY FENTON-LIKE PROCESS

Jos Luiz Tambosi*, Michele Di Domenico, Regina F. P. M. Moreira Departamento de Engenharia Qumica e Engenharia de Alimentos Universidade Federal de Santa Catarina Abstract. : This paper evaluates a Fenton-like process, involving oxidation and coagulation, for the treatment of a pulp and paper wastewater. The main parameters that govern the complex reactive system (pH, Fe(III) and hydrogen peroxide concentration) were studied. Concentrations of Fe(III) between 100 and 1000 mg/L, and H2O2 between 0 and 2000 mg/L were chosen. The main mechanism for color removal was the coagulation at optimum pH (5.0). The maximum removal efficiencies for COD, color and aromatic compounds were 75%, 98% and 95%, respectively, under optimal operating conditions ([Fe(III)]=400 mg/L; [H2O2]=1000 mg/L; pH=2.5; followed by coagulation at pH 5.0). The biodegradability of the wastewater during treatment increased from 0.4 to 0.7 under optimal conditions and no residual hydrogen peroxide was found. However, partially or non-oxidized compounds present in the treated wastewater presented higher acute toxicity to Artemia salina than the untreated wastewater. Keywords: Pulp and paper mill wastewater; Fenton process, Advanced oxidation process, Toxicity, Hydrogen peroxide.

1. Introduction
The pulp and paper industry is one of the most important in the world, but it discharges a variety of gaseous, liquid, and solid wastes into the environment. Pollution of water bodies is of major concern because large volumes of wastewater are generated, about 80 m3 of wastewater for each ton of pulp produced (Almeida et al., 2004). More than 250 chemicals have been identified in effluents that are produced at different stages of papermaking (Ali and Sreekrishnan, 2001). While some of these pollutants are naturally occurring wood extractives (tannins, resin acids, stilbenes, lignin) others are xenobiotic compounds that are formed during the process of pulping and paper making (chlorinated lignins, resin acids, phenols, dioxins and furans). Biological processes are commonly used in several pulp and paper industries, but some drawbacks are associated with these methods, such as, the large area required for the aerobic process, the difficulty in controlling the population of microorganisms, and the rigorous control of pH, temperature and nutrients. Also the presence of toxic or recalcitrant compounds is harmful to biological degradation (Freire, 2002). Nowadays, advanced oxidation processes (AOPs) are used for pollutant abatement due to the high oxidative power of the OH radical (Hirvonen et al., 1996). One of the most important AOP processes used to generate OH radicals employs the Fe2+/H2O2 system, where the catalyst (the ferrous ions) is dissolved in water, this being known as the Fenton process. Fe3+ can also be used to decompose H2O2 and to produce oxidative radicals in the Fenton-like process. For most applications, it does not matter whether Fe2+ or Fe3+ ions are used to catalyze the reaction, although Pera-Titus et al. (2004) have suggested that if low doses of Fentons reagent are used, ferrous ions may be preferable.
*

To whom all correspondence should be addressed. Address: Departamento de Engenharia Qumica e Engenharia de Alimentos, UFSC - Centro Tecnolgico, Campus Universitrio, Caixa Postal 476, Trindade, 88040-900, Florianpolis Santa Catarina Brazil E-mail: jltambosi@bol.com.br

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For the Fentons reagent, it is generally considered that the reaction between H2O2 and Fe2+ in acidic aqueous solution (pH 3) produces hydroxyl radicals (OH) and Fe3+. Other intermediates such as the ferryl ion (FeIVO2+) can also be formed and these may contribute to the oxidation of organic compounds. Once formed, Fe3+ can also catalyze the decomposition of H2O2. Organic matter in wastewaters from the papermaking process is usually biodegradable (Thompson et al., 2001). Nevertheless, the initial values of COD and BOD5 are high and conventional biological reactors can not be employed (Amat et al., 2005). It has been reported that the combination of two biological stages, consisting in the sequential application of an anaerobic and an aerobic, results in an accumulation of the non-biodegradable fraction of the organic compounds in the processed water (Habets and Knelissen, 1997). Thus, Fentons reagent could be used in combination with biological process in order to reduce the toxicity, and to improve the biodegradability, odor and color removal. In spite of numerous studies of the Fe2+/H2O2 system, the chemistry and kinetics of the oxidation of organic compounds by Fenton-like processes (Fe3+/H2O2 system) have not been well elucidated (Gallard and De Laat., 2000). In this paper, we report on a study of the oxidation and coagulation of the organic compounds present in a typical pulp and paper effluent, by a Fenton-like reaction. The main experimental parameters, such as pH, reagent concentration and time, were optimized in order to achieve high COD, color and toxicity reduction.

2. Experimental
The effluents used in this research were supplied by a Brazilian paper manufacturer, and obtained from the equalization tank in the wastewater treatment plant and used without any pre-treatment. The wastewater was maintained at 5oC to conserve its characteristics (Table 1). Hydrogen peroxide (50%) was supplied by Degussa (Brazil) and the rest of the chemicals used were, at least, of reagent grade. Table 1. Characteristics of the pulp and paper wastewater pH Total solids (mg/L) Dissolved solids (mg/L) Suspended solids (mg/L) Total COD (mg/L) Soluble COD (mg/L) BOD5 (mg/L) Color (PtCo) (mg/L) 10.0 1396 1132 264 964 950 400 4236

Experiments were conducted in cylindrical Pyrex cells of 400 cm3 capacity. The reaction mixture inside the cell, consisting of 300 cm3 wastewater and the required amount of Fe3+ and H2O2, was continuously stirred in Jar Test equipment. During the oxidation step, the mixture inside the cell was vigorously stirred for one hour at 90 rpm. The pH was then adjusted to the desired value and the coagulation step was performed for 20 minutes under agitation at 30 rpm. All the characteristics of the wastewater (Table 1) were measured according to procedures described in Standard Methods (AWWA, 1995). Residual hydrogen peroxide concentration was determined by the 2

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iodometric method (Kolthoff, 1920) and the iron concentration in the treated wastewater was measured by the ophenantroline colorimetric method (AWWA, 1995). The aromatic compounds content was measured according to the method proposed by Ravikumar and Gurol (1994) and Akmehmet et al. (2003). The toxicity of untreated and treated wastewaters was evaluated using a bioassay with Artemia salina. A. salina cysts were incubated in artificial seawater illuminated by a tungsten filament light and gently sparged with air at 20oC. After 24 hours, hatched A. salina cysts were transferred to fresh artificial seawater and incubated for a further 24 h under artificial light with air sparging (Dantas et al., 2003). Subsequently, different dilutions of the wastewater in artificial seawater were poured into wells in polystyrene microtiter plates, and 7 to 10 A. salina nauplii were placed in each cell. Deaths were recorded after incubating at 20oC for 24 hours. The evaluation of toxicity was performed according to the Reed Muench method (1993).

3. Results and Discussion

3.1. Factors affecting the performance of the Fenton-like process 3.1.1 Effect of Fe3+ concentration It has been shown that in the absence of Fe2+/Fe3+ no radical or other active intermediate species are formed when hydrogen peroxide is added to a wastewater. As the concentration of Fe2+ is increased, the removal of color and COD accelerates until a point is reached where further addition of iron becomes inefficient. The feature of an optimal dose range for the iron catalyst is characteristic of Fentons reagent, although the definition of the range varies for different contaminated wastes. Typical ranges are [Fe2+]:[H2O2]= 5 - 25 (Pera-Titus et al., 2004). Figure 1 displays the effect of the iron dosage on the COD, color and aromatic compounds removal, using different initial H2O2 concentrations. The results reveal that the efficiency of the Fenton-like process depends on the Fe3+ concentration as also occurs in the classical Fenton process using Fe2+. In fact, Kang et al. (2002) have demonstrated that the COD removal is nearly the same using Fe2+ or Fe3+ in the degradation of a textile wastewater by the Fenton process. The maximum COD removal achieved in this study was in the range 30-50%, depending on the hydrogen peroxide concentration dosage, while nearly 100% of color and aromatic compounds were removed. This indicates that the removal of color by Fenton-like process requires relatively low dosages of hydrogen peroxide and iron, whereas, much higher dosages of both are required to obtain the same level of COD removal.
Color Removal (%)
COD Removal (%) 60 40 20 0 0 200 400 600 800 1000 [Fe ] (mg/L)
3+

200

400 [Fe
3+

600 ] (mg/L)

800 1000

UV

100 80 60 40 20 0

Removal (%)
280

100 80 60 40 20 0 0 200 400

3+

600

800 1000

[Fe ] (mg/L)

(a) (b) (c) Figure 1 Effect of the Fe3+ dosage on the Fenton-like process efficiency using different initial H2O2 concentrations: (a) COD removal; (b) color removal; (c) aromatic compounds removal ([H2O2]= ()100, ()500, ()1000 mg/L; Reaction time = 1 h; Reaction pH = 3.0; Coagulation pH = 6.0)

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Figure 2 shows the BOD5/COD ratio after treatment using different Fe3+ and hydrogen peroxide dosages in the Fenton-like process. Before treatment, the BOD5/COD ratio was 0.4 (Table 1) and even when a high color removal was measured using a Fe3+ dosage above 400 mg/L, the ratio remained at nearly 0.4, indicating that biodegradable and non-biodegradable compounds are partially oxidized. It has been demonstrated (Dantas, 2003) that Fenton-like process increases the biodegradability and mainly non-biodegradable compounds are oxidized. However, the results presented in Figure 2 shows that even the relationship BOD5/COD decreased from the initial value (0.4) to values on the range 0.1-0.4 depending on the Fe3+ and H2O2 concentration used in Fenton-like treatment. .In all experiments, the residual H2O2 was measured and it was below the limit detectable by the iodometric method (10 mg/L) (EPA, 2004).
0.5
Biodegradability

0.4 0.3 0.2 0.1 0 0 200 400

3+

600

800

1000

[Fe ] (mg/L)

Figure 2 BOD5/COD ratio measured after treatment using different iron and hydrogen peroxide dosages ([H2O2]= ()100, ()500, ()1000 mg/L; Oxidation pH = 3.0; Coagulation pH = 6.0; Reaction time = 1h) Figure 3 shows toxicity to A. salina after treatment using different Fe3+ and hydrogen peroxide dosages in the Fenton-like process. The untreated wastewater did not present acute toxicity to A. salina (mortality 0%) but using different dosages of iron and hydrogen peroxide, the treated wastewater presented acute toxicity. As the iron dosage increased, a higher COD (Figure 1) and a lower toxicity were measured. Twiner et al. (2001) have reported that the LC50 for A. Salina in the presence of hydrogen peroxide is 884 mg/L, but the toxicity increases in the presence of iron ions. The concentration of iron after coagulation in all treatments was less than 1.5 mg/L. Although the residual hydrogen peroxide measured after the oxidationcoagulation was less than 10 mg/L (limit of detection through the iodometric method), this increase in the toxicity may be partially due to the unmeasured hydrogen peroxide or to the formation of more toxic partially oxidized compounds during the treatments.
100 Mortality (% 80 60 40 20 0 0 200 400
3+

600

800

1000

[Fe ] (mg/L)

Figure 3 Acute toxicity of treated wastewater under different conditions ([H2O2]= ()100, ()500, ()1000 mg/L; Reaction pH = 3.0; Coagulation pH = 6.0; Reaction time= 1h) 4

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3.1.2. Effect of pH during the oxidation and coagulation step It has been observed that the pH affects significantly the degradation of organics by the Fenton reaction and acidic conditions are required to produce the maximum amount of hydroxyl radicals by the decomposition of hydrogen peroxide catalyzed by ferrous ions (Lin and Lo, 1997; Tang and Huang, 1996). Generally, the optimum solution pH is about 2.5-3.0 (Kang and Hwang, 2000; Hsueh et al., 2005). At a reaction pH higher than 5, it has been observed that the COD removal efficiency by oxidation decreases, not only due to decomposition of hydrogen peroxide (Kang and Hwang, 2000; Hsueh et al., 2005), but also because of deactivation of the ferrous catalyst with the formation of ferric hydroxo complexes (Kang and Hwang, 2000). However, the effect of pH on the COD removal through a Fenton-like process has not been discussed appropriately. Figure 4 shows the COD and color removal as a function of initial pH. Clearly, the COD removal is significantly influenced by the pH and the optimum pH was 2.5, as also reported by Hsueh et al. (2005). As the pH decreased, the scavenging effect of the OH by H+ becomes stronger (Tang and Huang, 1996) and at a pH higher than 3.0, the hydrolysis of Fe3+ in the solution reduces the rate of OH production (Hsueh, 2005).
100

Removal (%)

80 60 40 20 0 0 1 2 3 4

COD color

Reaction pH

Figure 4 COD and color removal as a function of reaction pH ([Fe3+] = 400 mg/L; [H2O2]= 500 mg/L; Reaction time = 1 h; pH coagulation = 6.0) On the other hand, the color removal was nearly the same under different pH conditions, possibly effected by ferric coagulation, since coagulation tests showed that color is almost completely removed by ferric coagulation alone. Figure 5 shows the UV/vis spectra for the wastewater before and after treatment by coagulation and by the Fenton-like process. A decrease in absorbance can be observed in the visible range wavelength after coagulation treatment, but aromatic compounds are only partially removed.

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5 Absorbance 4 3 2 1 0 190 290 390 490 590 690 790 Wavelength (nm)
Untreated Wastewater Coagulation Fenton-like Process

Figure 5 UV/vis spectra for untreated wastewater and after treatment by coagulation and by the Fenton-like process. (Coagulation: [Fe3+] = 400 mg/L and pH =5.0; Fenton-like treatment: [Fe3+] = 400 mg/L; [H2O2]= 1000 mg/L; Reaction time= 1h; Reaction pH= 2.5; Coagulation pH = 5.0) The coagulation after oxidation step favors COD removal (Kang et al., 2002), but it is important to prevent the subsequent conversion of ferric ions back to Fe2+ in the reaction system. The optimal conditions, such as pH, during the coagulation step in terms of COD removal need to be investigated. The effect of the pH during the coagulation step on the COD and color removal efficiencies was evaluated in the range 4.5 to 8.5, as shown in Figure 6. As the oxidation step was performed at pH 2.5, the degradation occurred to the same extent and the effect of removal of pollutants by coagulation/settling could be measured. Figure 6 shows that the removal efficiency for color remains better than that for COD using different coagulation pH values, but as the pH increases the difference between the efficiency of color and COD removal decreases, indicating that color is removed mainly by coagulation/settling and the optimum pH to remove COD and color is in the range 5.0-6.0.
100 Removal (%) 80 60 40 20 0 4 5 6 7 8 9 Coagulation pH
COD color

Figure 6 Effect of the coagulation pH on the COD and color removal. ([Fe3+] = 400 mg/L; [H2O2]= 500 mg/L; Reaction pH = 2.5; Reaction time = 1h) 3.1.3. Effect of hydrogen peroxide dosage Generally, the degradation rate for organic compounds increases as the hydrogen peroxide concentration increases until a critical H2O2 concentration is achieved (Hsueh et al., 2005; Lin and Peng, 1995). Above this critical concentration, the degradation rate for organic compounds decreases as a result of the so-called scavenging effect, according to Equation 1 (Ito et al, 1998; Hsueh et al., 2005).

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H2O2 + OH HO2 + H2O

(1)

It is clear in Figure 7 that increasing amounts of hydrogen peroxide lead to greater COD and aromatic compounds removal, with no detrimental effects detected for the highest H2O2 concentration. Nevertheless, the small difference between the COD removal attained with 1000 and 2000 mg/L of H2O2 indicates that improvements in terms of degradation may not be worth the large loads of oxidant expended. As previously discussed (Figure 4) a high color removal was found, because ferric coagulation is the main process to remove color. However, only 50% of COD removal could be achieved to the ferric coagulation.
100 80 60 40 20 0 0 500 1000 1500 2000 2500

Removal (%)

COD UV 280 color

[H2 O2 ] (mg/L)

Figure 7 Effect of H2O2 dosage on COD, color an aromatic compounds removal. ([Fe3+] = 400 mg/L; Reaction pH = 2.5; Reaction time = 1h; Coagulation pH = 5.0) The BOD5/COD ratio increased from 0.4 to 0.7 as the H2O2 dosage increased (Figure 8) and no residual hydrogen peroxide was measured using the iodometric method, indicating the improvement in the biodegradability of partially or non-oxidized reminiscent compounds (Harmsen and Voortman, 1996; Preis et. al. 1995). However, using a hydrogen peroxide concentration higher than 1000 mg/L, some residual H2O2 was found, and a detrimental effect on the biodegradability was measured.

BOD5/COD 1 0.8 0.6 0.4 0.2 0 0 400

Biodegrability

Residual H2O2 1 0.8 0.6 0.4 0.2 0

Residual H 2O2 Fraction

600 1000 2000

[H2O2] (mg/L)
Figure 8 Effect of H2O2 dosage on the relationship BOD5/COD ([Fe3+] = 400 mg/L; Reaction pH = 2.5; Reaction time= 1 h; Coagulation pH = 5.0) The effect of hydrogen peroxide dosage on the toxicity of treated wastewater is shown in Figure 9. The mortality of A. salina was practically independent of the hydrogen peroxide dosage used, but was higher for treated wastewater than for untreated wastewater, indicating the formation of partially oxidized compounds that present acute toxicity in this bioassay. The increased of toxicity after AOPs was also observed by Balcioglu and Arslan (1998) due the formation of toxic partially oxidized compounds. 7

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100 Mortality (% 80 60 40 20 0 0 500 1000 1500 2000 [H2 O2 ] (mg/L) 2500

Figure 9 Toxicity of treated wastewater using different H2O2 dosage using a bioassay with Artemia salina. ([Fe3+] = 400 mg/L; Reaction pH = 2.5; Reaction time= 1h; Coagulation pH = 5.0) 3.2. Kinetics of color and COD removal by the Fenton-like process The kinetics of color and COD removal was investigated under optimal conditions determined previously (Figure 10), and showed that color is completely removed in a reaction time of less than 5 minutes at pH 2.5 followed by coagulation at pH 5.0, since the main mechanism for color removal is coagulation/settling. The kinetics of COD removal showed a behavior typical of a two-step process. The fast first step occurs in the first 5 minutes followed by a slow second step reaching 75% of COD removal after 1 h. The analysis for residual hydrogen peroxide after different reaction times revealed (not shown) that it is rapidly consumed in the first 5 minutes, and could explain the fast first step through reaction 2. Fe3+ + H2O2 Fe2+ + H+ + HO2
100 Removal (% 80 60 40 20 0 0 20 40 Time (min) 60 80
COD color

(2)

Figure 10 Kinetics of color and COD removal by Fenton-like process ([Fe3+] = 400 mg/L; [H2O2] = 1000 mg/L; Reaction pH = 2.5; Coagulation pH = 5.0) 3.3. Costs considerations The evaluation of the treatment costs is today one of the most important aspects. The overall costs are represented by the sum of the capital, operating and maintenance costs. For a full-scale system these costs strongly depend on the nature and the concentration of the pollutants, the flow rate of the effluent and the configuration of the reactor (Esplugas et al., 2002). In this study the costs related to the chemicals needed for the Fenton-like process under the previously described optimal conditions were evaluated (Figure 11). The costs were calculated for industrial scale and the chemical products involved were ferric sulfate (Kemwater, 2004), hydrogen peroxide (Degussa, 2004), sodium hydroxide and sulfuric acid (Projesam, 2004). Hydrogen peroxide is the most expensive reagent required to achieve 72% COD removal and the total cost doubles when 82% COD removal is required. (Brazil Bank, 2005). 8

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5 4 $/m 3 2 1 0 40 50 60 70 80 90 COD Removal (% )

3

Figure 11 Cost estimate for chemical reagents required to achieve different COD removal in the treatment of pulp and paper wastewater by the Fenton-like process.

4. Conclusions
The Fenton-like process is efficient for treating pulp and paper wastewater. The COD removal efficiency using oxidation was greatly affected by the pH reaction. The most effective reaction was observed at pH 2.5 and the optimal coagulation pH range to maximize the COD and color removal efficiency was between 4.5 and 6.0. Color is mainly removed by coagulation/settling and the residual hydrogen peroxide is negligible after the treatment. The results showed that ferric coagulation achieved 95% color removal and nearly 50% COD removal. Considering only economic aspects, the coagulation could be a more suitable process than Fenton-like. However, the mineralization of organic compounds would be a advantage of the Fenton-like process. The hydrogen peroxide required to achieve a high COD removal is the most important consideration in the estimate of operating costs. Considerable dosages of hydrogen peroxide are required in order to achieve a satisfactory COD removal.

References
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Acknowledgments
CAPES, FINEP/CTHidro and CNPq. 10