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Anurag Garg1 Indra Mani Mishra2 Shri Chand2

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Research Article Oxidative Phenol Degradation Using Non-Noble Metal Based Catalysts
Phenol laden waste streams are not considered suitable for conventional biological treatment if phenol is present in amounts higher than 70 mg/L. Catalytic wet air oxidation (CWAO) is one of the potential methods for treating waste streams containing such compounds. The present work investigated the degradation of synthetic wastewater contaminated with phenol (1 g/L) using a CWAO process in the presence of homogenous (CuSO4) and heterogeneous (LaCoO3, CuX and CuO-ZnO/CeO2) catalysts. The reaction was conducted at low temperature (908C) and atmospheric pressure, and at moderate operating conditions (T F 1608C and total pressure f0.8 MPa). Among all the tested catalysts, CuSO4, LaCoO3 and CuX were used for WAO reactions performed at atmospheric pressure conditions, whereas the performance of CuO-ZnO/CeO2 catalyst was tested in above atmospheric pressure studies. At atmospheric conditions, homogeneous CuSO4 was found to be the best showing ca. 90% phenol degradation and ca. 83% chemical oxygen demand (COD) reduction after a 24 h reaction period. The above atmospheric studies with catalyst showed ca. 82% phenol reduction and 54% COD removal within 3 h reaction time. The effect of pH, catalyst concentration, pressure and temperature are also reported. Finally, the major results are summarized and the recommendations for future work are given.
Keywords: Homogenous catalyst; Heterogeneous catalyst; Phenol; Waste water Treatment; Wet air oxidation; Received: July 9, 2009; revised: September 28, 2009; accepted: November 4, 2009 DOI: 10.1002/clen.200900143

Centre for Environmental Science and Engineering, Indian Institute of Technology, Mumbai, India. Department of Chemical Engineering, Indian Institute of Technology, Roorkee, India.

1 Introduction
Wastewaters emanating from various chemical industries may contain several persistent organic and inorganic pollutants rendering these polluted streams unsuitable for direct biological treatment. Phenol and its derivatives are considered to be toxic and biorefractory compounds. These compounds are present in wastewaters originating from a wide variety of industries, such as, dyes, pharmaceuticals, plasticizers, coke ovens, blast furnaces and petrochemical processing [1]. These industries either use phenolic compounds as raw materials, or are produced as intermediate products during the processing. It has been reported that wastewaters containing phenol in the concentration range of 70300 mg/L are difficult to treat biologically due to excessive toxicity of phenol to microbial species. Several treatment techniques like adsorption using activated carbon [24] and adsorption with bioregeneration [5, 6], wet oxidation (WO) etc. have been used in the literature. Such techniques are used depending on the concentrations of phenols and other compounds, as well as the volume of wastewaters to be treated. Wet air oxidation
Correspondence: Dr. A. Garg, Centre for Environmental Science and Engineering, Indian Institute of Technology, Bombay, Powai, Mumbai 400076, India. E-mail: a.garg@iitb.ac.in Abbreviations: COD, chemical oxygen demand; CWAO, Catalytic wet air oxidation; SW, Synthetic wastewater; TOC, Total organic carbon

(WAO) is considered a promising treatment option for medium to high strength wastewater streams not amenable to biological treatment [7]. Excellent reviews on catalytic and non-catalytic WAO of pure compounds and industrial wastewaters are available in the literature [1, 710]. The process involves the aqueous phase oxidation of pollutant(s) at elevated temperatures (1253208C) and pressures (0.520 MPa) [1]. The severity of the oxidation reaction can be reduced by adding recoverable and less expensive catalysts in the reaction vessel. A number of heterogeneous and homogenous catalysts have been used. Generally noble metal based heterogeneous catalysts are very effective in removing chemical oxygen demand (COD) or total organic carbon (TOC) of wastewaters. However, the high cost of such catalysts makes the process uneconomical and practically unfeasible. Therefore, recent research studies are focused on the development of comparatively less expensive transition metal based heterogeneous catalysts. It is evident from the literature that homogeneous and heterogeneous copper based catalysts (either alone or mixed with other transition metal compounds) are quite efficient in removing organic compounds [7, 1118]. The addition of CuSO4 in synthetic waste water containing phenol (100500 mg/L) gave 100% phenol conversion within an hour at 1108C and 0.45 MPa oxygen partial pressure [11]. Higher removal efficiency was also due to the presence of sodium sulfite, an auxiliary oxidant. Vaidya and Mahajani [19] studied catalytic wet air oxidation (CWAO) of phenolic wastewater (COD = 2000 mg/L) at 1758C and 0.69 MPa oxygen partial pressure

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using CuSO4 and FeSO4 catalysts. CuSO4 showed better COD removal efficiency (95% in comparison to 78% with FeSO4 in 1 h reaction time). In another study, the performance of WO for phenol removal from aqueous solution was investigated in the temperature range of 1201408C and oxygen pressures ranging from 0.682 MPa using copper based heterogeneous catalysts [13]. Among all the tested catalysts, copper oxide-copper chromite and Al2O3-C-CuO-ZnO catalysts exhibited much higher efficiencies, destroying 100% phenol within 90 min. Kim et al. [20] conducted CWAO of phenol in the presence of CuO-Al2O3 catalyst at 1508C and air pressures greater than 2 MPa. They studied the effect of copper loading on phenol and TOC reduction. The results revealed that the addition of the catalyst caused rapid enhancement in substrate destruction (100% phenol and ca. 80% TOC reduction within an hour, in comparison to 64% phenol and ca. 20% TOC reduction in 3 h reaction time when no catalyst was used). Copper loading in the catalyst mixture was varied from 1 to 25 wt%. However, it was found that copper loading above 7 wt% did not cause any further increase in TOC reduction. Lopes et al. [21] used CuO-ZnO/Al2O3 catalyst containing (41% CuO and 47% ZnO) in a WO process for treating a solution containing phenolic acids at 2008C and 1.5 MPa air pressure. The presence of the catalyst reduced TOC by ca. 90% in 2 h, whereas only 30% reduction was obtained during non-catalytic oxidation under similar conditions. Few other research studies explored the combination of copper and zeolite (ZSM-5 and MCM-41) as catalysts for WO of phenolic wastewater [14, 16]. With Cu/ZSM-5 catalyst, about 100% phenol reduction was reported after 3 h reaction time. H2O2 was used as an oxidant and the temperature was maintained at 808C during the reaction [16]. A mixture of Cu and MCM-41 in varying proportions has also been used as catalyst in the oxidative degradation of phenolic wastewater [14]. The copper loading was varied from 81.3 to 262.2 mg/g of catalyst. The tests were conducted at temperatures of 150 and 2008C. The system pressures were 2.7 and 5.4 MPa, respectively, at these temperatures. Higher copper loading enhanced TOC removal at 1508C (ca. 55% at 178 mg of Cu/g of catalyst in comparison to ca. 40% at 81.3 mg Cu/g of catalyst). Catalytic WO of pulp and paper mill effluent has been found to be very effective in the presence of several copper based heterogeneous catalysts like CuO/CeO2, CuO/MnO2 and Cu/C [22, 23]. These catalysts exhibited good activity at moderate conditions (a1708C and 0.85 total pressure). The literature currently available suggests a need for further work on pH optimization, use of moderate reaction conditions with air as the oxidant, and the evaluation of catalytic activities of other non noble based compounds like perovskites and copper based catalysts. The present paper reports on the activities of homogenous CuSO4 and heterogeneous perovskites and copper oxide (either alone or in combination with zinc oxide) catalysts during CWAO of synthetic phenol solution at atmospheric and moderate operating conditions (up to 1408C and 0.8 MPa total pressure). 13X molecular sieve zeolites and ceria were used as supports. In addition, the effect of pH on phenol and COD reductions was also studied.

from Ranbaxy Laboratories, New Delhi, and 13X zeolite, cupric nitrate, zinc nitrate, cobalt nitrate, lanthanum oxide and cerium oxide were supplied by Loba chemie, Mumbai. CuSO4 N 5 H2O was purchased from s.d. Fine Chemicals, Mumbai. Air was supplied from an oil free air compressor.

2.2 Catalysts Used and Methods for Preparation

Copper sulfate (CuSO4 N 5 H2O) was used as a homogeneous catalyst, while CuO-ZnO/CeO2, Cu/13X and LaCoO3 were used as heterogeneous catalysts. 4% Cu/13X catalyst was prepared by an ion exchange method. The required amount of metal nitrate (4 wt% Cu) was mixed with the required amount of 13X zeolite powder in double distilled water (DDW). The mixture was heated at 908C under reflux for 15 h to allow the exchange of copper ions with the active centers of the zeolite. The ion exchanged catalyst was dried in an oven at 1108C for 24 h. Catalyst drying was followed by calcination at 6008C for 6 h. The prepared catalyst was characterized and used for WAO reaction. LaCoO3 perovskite was prepared by a ceramic method. The details of the preparation procedure have already been published elsewhere [24]. To prepare 5% CuO-5% ZnO/CeO2 catalyst, the stoichiometric amounts of copper and zinc nitrates were dissolved in DDW and coprecipitated under alkaline conditions (pH l 8.0). A balanced amount of CeO2 was added to the resulting solution and the mixture was heated to 608C on a hot plate for 2 h with continuous stirring using a magnetic stirrer. The mixture was left overnight at room temperature for further diffusion at the molecular level, and then dried in an oven at 1108C for 10 h. The dried material was then calcined at 4508C for 5 h. Later, the calcined material was characterized using X-ray diffraction.

2.3 Synthetic Phenolic Wastewater

Synthetic wastewater (SW) used for the WAO process was prepared by dissolving 1 g phenol in 1000 mL tap water. The SW had a pH of 4.0 and a COD equal to 2400 mg/L. The characteristics of the SW are given in Tab. 1. Fresh SW was prepared for each experimental run.

2.4 Experimental Procedure

WAO experiments at atmospheric pressure were conducted in a three necked atmospheric glass reactor (AGR) having a capacity of 0.5 L. A glass condenser was fitted in the central neck of the AGR to prevent any loss of water due to evaporation. The two other necks were used for temperature measurement and air supply through a flow meter. A temperature controller was used to control the temperature of the reactor. The temperature and air flow rate in the reactor were maintained at 908C and 0.25 L/min, respectively. WAO experiments at elevated pressure (>0.1 MPa) were carried out in a 0.5 L capacity stainless steel high pressure batch reactor. The reactor was equipped with all necessary arrangements like a temperature control system, heating jacket, pressure measurement device, reactor air sparger and a sampling port for drawing samples during the WAO experiments. The reaction mixture was agitated by means of a magnetic stirrer. CWAO was carried out in the temperature range of 1001408C. The pressure for both catalytic and noncawww.clean-journal.com

2 Experimental
2.1 Materials
All the chemicals used in the experiments were of analytical reagent grade and used as received. Phenol (>99%) was purchased

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talytic WAO experiments was varied in the range of 0.4 to 0.8 MPa total pressure. The operational procedure for both reactors was similar. The reactor was charged with 0.25 L SW having a phenol concentration of 1 g/L. The charging of the wastewater was followed by the addition of a predetermined amount of the catalyst. The reactor was heated to the desired reaction temperature. As soon as the reaction mixture attained the desired temperature, a sample was withdrawn (reaction time, t = 0) and air was sparged through the reaction mixture to increase its pressure to the desired level. In case of atmospheric pressure WAO studies, air was supplied to the AGR after achieving a desired temperature and the reaction was allowed to run for a fixed period of time. The samples were withdrawn at regular/predetermined intervals from the reactor and tested for various parameters. Table 1 provides the information on wastewater characteristics and WAO operating conditions.

Table 1. Summary of experimental runs.

Parameter/catalysts used Phenol concentration (g/L) COD (mg/L) pH Catalysts

For atmospheric runs

For pressure studies 1.00 2400 4.0 (5% CuO-5% ZnO/CeO2) 05 100160* 0.40.8 3

1.00 2400 4.0 CuSO4 N 5 H2O, LaCoO3, 4% Cu/13X Catalyst concentration (g/L) 15 Temperature (8C) 90 Total pressure (MPa) 0.1 Air flow rate (mL/ min) 0.25 Reaction duration (h) 24

* Only a non-catalytic WO reaction was performed at 1608C.

2.5 Analytical Methods

Heterogeneous catalysts were characterized using an X-ray diffractometer (Bruker AXS, Diffraktometer D8, Germany) using Cu-Ka radiation. The data was scanned between 20 and 908. Phenol concentration in wastewater was determined using a gasliquid chromatograph (Nucon 5700, Nucon Engineers Limited, New Delhi) with a flame ionization detector (FID). An OV-17 stainless steel column (15 cm long, 3.2 mm O.D. and 2.0 mm I.D.) was used to detect phenol in the waste stream. COD of the wastewater was determined by a standard open reflux method using dichromate solution [25].

3 Results and Discussion

3.1 Catalyst Characterization
The formation of all three heterogeneous catalysts, namely, 4% Cu/ 13X, LaCoO3 and 5% CuO-5% ZnO/ CeO2 was confirmed by comparing the XRD patterns with published data. The peak formation at a particular scanning angle (2 h) showed the presence of a specific component with its oxidation state. The prominent peaks and 2 h values observed in XRD patterns were matched, with patterns of individual components and previously reported data available in the literature [24, 26, 27]. Thus, the formation of desired catalyst was confirmed.
Figure 1. Activity of various catalysts at atmospheric pressure conditions (initial phenol conc. = 1 g/L, initial COD = 2400 mg/L, catalyst conc. = 5 g/L, T = 908C, P = 0.1 MPa, air flow rate = 0.25 L/min, reaction time = 24 h).

3.2 WAO Studies

3.2.1 Atmospheric Pressure Conditions
Phenol oxidation at 908C and atmospheric pressure was studied in the presence of CuSO4, 4% Cu/13X and LaCoO3 catalysts. A summary of the experimental runs is given in Tab. 1. The performance of these catalysts for the removal of phenol and COD in a 24 h duration run is shown in Fig. 1. It is apparent from the figure that CuSO4 exhibited the best performance in comparison to the other catalysts. Almost 90% phenol destruction (final phenol concentration = 100 mg/L) and 83% COD removal (final COD after treatment = 400 mg/L) was obtained with CuSO4 catalyst after 24 h. LaCoO3 and 4% Cu/13X showed phenol removals of ca. 48 and 38%, respectively in the same reaction period. The presence of LaCoO3 catalyst gave 46% COD removal in comparison to ca. 27% reduction with 4% Cu/13X catalyst (Final value = 1750 mg/L from an initial value of 2400 mg/L).

The catalytic activity of the three catalysts was found to be in decreasing order: CuSO4 > LaCoO3 > 4% Cu/13X. Since copper sulfate was found to be the best among all the catalysts, the effect of catalyst loading on phenol and COD reduction was observed only for copper sulfate. As evident from Fig. 2, a decrease in catalyst loading caused a drop in phenol and COD removals. For instance, an overall COD reduction was found to be ca. 83.3% at 5 g/L, in comparison to 74% obtained with 3 g/L catalyst loading. A further decrease in the catalyst loading to 1 g/L resulted in a COD reduction of 52%. The low increase in COD reduction may be attributed to the formation of lower molecular weight carboxylic acids which require severe oxidation conditions for their conversion [1, 20, 28]. The other intermediate products that are formed during phenol oxidation may include hydroquinone, catechol and benzoquinone [29]. The results also showed that an increase in catalyst loading from 1 to 5 g/L resulted in the phenol degradation from ca. 78 to 90% (i. e., only 12%). This suggests that the degradation of phenol into intermediates can be achieved with smaller catalyst concentrations, but complete removal of carbonaceous compound requires a higher catalyst loading. Kulkarni and Dixit [11] reported higher phenol reduction in less reaction time with CuSO4 catalyst than that obtained in the present study. This may be because of the lower phenol to catalyst ratio (by
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Figure 2. Effect of CuSO4 catalyst concentration on phenol and COD reduction (initial phenol conc. = 1 g/L, initial COD = 2400 mg/L, T = 908C, P = 0.1 MPa, air flow rate = 0.25 L/min, reaction time = 24 h).

weight), much higher oxygen partial pressure and the use of an auxiliary oxidant by the authors. The phenol to catalyst ratio (weight basis) in the present study was 0.20 as compared to 0.13 used by Kulkarni and Dixit [11]. The present work used air as an oxidant with a very small oxygen partial pressure (i. e., 0.021 MPa) in comparison to 0.25 MPa O2 partial pressure used in the previous study. They also added sodium sulfite to the reactor to promote the oxidation reac , SO3 , tion significantly by introducing several free radicals like O2 , SO5 , HSO4 and HSO5 . The major disadvantage with the CuSO4 SO4 catalyst is the solubility of the metal ion in water that necessitates an additional step to remove toxic copper from the treated wastewater, although copper can be removed from treated water by adjusting the pH in the range of 68 [30]. It has been mentioned in the literature that free radical mechanisms govern WO reactions [2, 31]. The reaction rate is highly dependent on the formation of free radicals. The WAO reactions occur in three steps, namely, initiation, propagation and termination. From Fig. 1, it can be observed that the induction period (slow reaction rate period in the beginning) was almost absent (phenol reduction curve) or very small (COD curve) in the CuSO4 catalyzed WAO reaction. The fast reaction step was followed by a slow reaction stage due to the termination of free radicals. On the other hand, the length of the induction period was found to be much larger (ca. 15 h) for two other catalysts in comparison to CuSO4. Slower phenol and COD removal rates may also be due to operating conditions during the reaction that delays the formation of free radicals and thus the initiation process. In addition, the pKa value of phenol is 9.8 [2]. This also inhibits the formation of active C6H5COO9 radicals retarding the overall reaction rate.

phenol and COD degradation. The results are discussed in the subsequent subsections.

3.2.2.1 Effect of pH
The pH of the wastewater was optimized for catalytic and non-catalytic reactions at 140 and 1608C, respectively. The performance of the process was observed at a pH of 4.0 (original), 7.0 and 9.0. As evident from Fig. 3a) and b), a pH of 4.0 was found to be best for the catalyst, with 5% CuO-5% ZnO/CeO2 showing more than 80% phenol reduction and ca. 55% COD removal in 3 h reaction time. The reduction at pH 4.0 was much higher in comparison to the other higher pH values (at pH 7.0, COD reduction was 4%; at pH 9.0, COD reduction was 8%). Since the original pH of the wastewater was also 4.0, the need for the addition of any chemical (acid/base solution) for pH adjustment was eliminated. For non-catalytic reaction, pH 9.0 showed the highest phenol and COD removals (26.5 and 12.5%, respectively) in the same reaction time (i. e., 3 h) but at a higher temperature (i. e., at 1608C). Further runs for catalytic and non-catalytic WAO were carried out at the optimized pH values. To compare the results, other experimental conditions were not changed.

3.2.2.2 Effect of Catalyst Concentration

Figure 4 shows the effect of catalyst concentration on phenol and COD reduction in a 3 h reaction time. The runs were carried out at 1408C, 0.8 MPa total pressure and at optimized pH for catalytic and non-catalytic reactions. The catalyst loading was varied from 1 to 5 g/L and the results were compared with non-catalytic oxidation. An addition of catalyst in a concentration more than 1 g/L increased the phenol removal marginally (at a catalyst concentration = 1 g/L, phenol removed = ca. 0.73 g/L, and at a catalyst concentration = 5 g/ L, phenol removed = ca. 0.82 g/L). It was found that a COD reduction of 29% was obtained with 1 g/L catalyst concentration. The COD reduction rate was lower in comparison to the phenol reduction rate. It may be due to the formation of not easily degradable intermediates (e. g., acetic acid). A marginal enhancement in COD reduction with an increase in catalyst concentration from 1 to 3 g/L dictated the formation of such compounds (COD removal = 33% with 3
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3.2.2 Pressure Studies

CWAO studies above atmospheric pressure were performed with a heterogeneous 5% CuO-5% ZnO/CeO2 catalyst, and the results were compared with that obtained from the non-catalytic reaction. CWAO was carried out between 1001408C, whereas the non-catalytic reaction was performed up to 1608C. In addition, the effects of pH, catalyst concentration and total pressure were also observed on

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from an initial value of 2400 mg/L in 3 h reaction time at 1408C using CuO-ZnO/CeO2 as catalyst. At lower temperatures, the COD reductions were of no significance (only ca. 4 and 2% at 120 and 1008C, respectively).

3.2.2.4 Effect of Pressure

The effect of pressure on the catalytic and non-catalytic WAO process at 1408C, 5 g/L catalyst loading and 3 h reaction time was investigated (see Fig. 6a) and b)). The pressure was varied from 0.4 to 0.8 MPa. It was seen that an increase in pressure enhanced overall phenol and COD removal. Non-catalytic WAO showed only ca. 11% phenol removal at 0.4 MPa total pressure in comparison to ca. 22% at 0.8 MPa total pressure. Similarly, COD removal depleted from ca. 8 to 2% with a drop in overall pressure from 0.8 to 0.4 MPa total pressure, respectively. For CWAO, a pressure drop from 0.8 to 0.6 MPa resulted in a substantial decrease in phenol and COD removals. Unconverted phenol in the wastewater was ca. 57 and 18% of the original value at 0.6 and 0.8 MPa total pressures, respectively, after 3 h reaction time, while COD was reduced by only ca. 54 (at 0.8 MPa total pressure) and 21% (at 0.6 MPa total pressure) of the initial COD.

3.2.2.5 Effect of Reaction Time

The phenol and COD removals at 1408C, 0.8 MPa total pressure and 5 g/L catalyst concentration during non-catalytic and catalytic WAO processes, are shown in Fig. 7. A longer induction period was observed for non-catalytic WAO with insignificant reductions in both COD and phenol. Most of the COD (around 150 out of 200 mg/L total reduction) removal occurred in the last 0.5 h. The CWAO appeared to occur in four segments: fast, slow, again fast and finally a slow zone. The third zone appeared to be the fastest. The trends for phenol and COD reductions were similar. No induction period was observed at the start of the reaction that indicated the presence of sufficient free radicals in the solution to initiate the reaction. After about 1 h reaction time, the termination of the free radicals started, along with the formation of new radicals. In addition, the formation of persistent compounds may be one of the reasons for the slow reaction rate. This caused no significant reduction in phenol and COD for another 1 h. After 2 h reaction time, the generation of free radicals overcame the termination step causing an increase in phenol and COD removal. As a result, a fast reaction step appeared for a short duration (ca. 30 min) during the reaction. The previous literature suggests that the presence of hydroquinone increases the organic removal rate due to the rapid formation of free radicals [19]. This step was followed by the slow reduction in phenol concentration and COD until the end of the WAO reaction. The results presented in this paper are comparable to those obtained in past studies made on WAO of phenol laden wastewater [32, 33]. Phenol degradation and COD reduction depend upon a number of factors such as catalyst, phenol/catalyst ratio, total pressure and temperature and reaction time. Another factor that can affect the catalytic activity may be the deactivation of catalyst by carbonaceous deposits on its surface [34].

Figure 3. Effect of pH on (a) phenol and (b) COD reduction in the presence and absence of 5% CuO-5% ZnO/CeO2 catalyst (initial phenol conc. = 1 g/L, initial COD = 2400 mg/L, catalyst conc. = 5 g/L, P = 0.8 MPa, reaction time = 3 h).

g/L). A further increase in catalyst loading helped in generating more free radicals resulting in the faster removal of COD (ca. 54% COD reduction).

3.2.2.3 Effect of Temperature

The effect of temperature on the catalytic and non-catalytic WAO process was studied in a temperature range of 1001408C at the total pressure of 0.8 MPa and the catalyst concentration (for catalytic runs) of 5 g/L. As expected, an increase in temperature enhanced the phenol degradation and COD removal (see Fig. 5a) and b)). It can be seen from Fig. 5a) that non-catalytic oxidation resulted in about 22% phenol degradation at 1408C in comparison to 5%, and almost no phenol degradation at 120 and 1008C, respectively, after 3 h reaction period. A similar trend was also observed for catalytic reaction although the phenol degradation was much higher (up to ca. 12.5, 13 and 82% at 100, 120 and 1408C, respectively). No COD removal was observed at temperatures lower than 1408C for non-catalytic WAO. This necessitates either longer reaction times (>3 h) or higher temperature and pressure conditions. During CWAO, the COD of the wastewater was reduced by >54%

4 Conclusions
Several conclusions can be elicited from the present study. It was found that the CWAO at atmospheric pressure did not show any significant results. CuSO4 was found to be the best among all the catawww.clean-journal.com

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Figure 4. Effect of catalyst concentration on phenol and COD reduction (initial phenol conc. = 1 g/L, initial COD = 2400 mg/L, catalyst conc. = 5 g/L, T = 1408C, P = 0.8 MPa, reaction time = 3 h).

Figure 5. Effect of temperature on (a) phenol and (b) COD reduction (initial phenol conc. = 1 g/L, initial COD = 2400 mg/L, catalyst conc. = 5 g/L, P = 0.8 MPa, Reaction time = 3 h).

Figure 6. Effect of total pressure on (a) phenol and (b) COD reduction (initial phenol conc. = 1 g/L, initial COD = 2400 mg/L, catalyst conc. = 5 g/L, T = 1408C, reaction time = 3 h).

lysts and showed ca. 83% COD reduction at 908C in 24 h under atmospheric pressure. CWAO under moderate operating conditions (T = 1408C and total pressure = 0.8 MPa) showed significant COD and phenol reductions (ca. 54 and 82%, respectively) in 3 h reaction time. The optimum pH for phenol oxidation with CuO-ZnO/CeO2 cat-

alyst was found to be 4.0 which was the original pH of the synthetic wastewater containing phenol (1 g/L). Non-catalytic WAO reaction gave only 26% phenol reduction and 12% COD reduction in 3 h reaction time at 1408C. The reaction pressure also had a significant effect on phenol and COD removal efficiencies. Reducing the total
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Figure 7. Change in phenol and COD with time (initial phenol conc. = 1 g/L, initial COD = 2400 mg/L, catalyst conc. = 5 g/L, T = 1408C, P = 0.8 MPa, reaction time = 3 h).

pressure from 0.8 to 0.6 MPa resulted in a decrease in phenol degradation from 82 to 43%. In order to improve the efficacy of CWAO reaction, the use of auxiliary (like sodium sulfite) and other oxidants (H2O2, O2) can be suggested. Future studies may be aimed at observing the leaching and deactivation characteristics of heterogeneous catalysts. A detailed kinetic study of the reaction should be performed. Operating conditions should be optimized by adjusting reaction temperature and pressure, since both these factors have opposite effects on oxygen solubility.

[8] S. Imamura, Catalytic and Noncatalytic Wet Oxidation, Ind. Eng. Chem. Res. 1999, 38, 1743. [9] G. Busca, S. Berardinelli, C. Resini, L. Arrighi, Technologies for the Removal of Phenol from Fluid Streams: A Short Review of Recent Development, J. Hazard. Mater. 2008, 160, 265. [10] F. Liotta et al., Heterogeneous Catalytic Degradation of Phenolic Substrates: Catalysts Activity, J. Hazard. Mater. 2009, 162, 588. [11] U. S. Kulkarni, S. G. Dixit, Destruction of Phenol from Wastewater by 2 -O2, Ind. Eng. Chem. Res. 1991, 30, 1916. Oxidation with SO3 [12] A. Pintar, J. Levec, Catalytic Oxidation of Organics in Aqueous Solutions 1. Kinetics of Phenol Oxidation, J. Catal. 1992, 135, 345. [13] J. F. Akyurtlu, A. Akyurtlu, S. Kovenklioglu, Catalytic Oxidation of Phenol in Aqueous Solutions, Catal. Today 1998, 40, 343. [14] Q. Wu et al., Copper/MCM-41 as Catalyst for the Wet Oxidation of Phenol, Appl. Catal., B 2001, 32, 151. [15] A. Santos et al., Route of the Catalytic Oxidation of Phenol in Aqueous Phase, Appl. Catal., B 2002, 39, 97. [16] K. M. Valkaj, A. Katovic, S. Zrncevic, Investigation of the Catalytic Wet Peroxide Oxidation of Phenol over Different Types of Cu/ZSM-5 Catalyst, J. Hazard. Mater. 2007, 144, 663. [17] S.-K. Kim, S.-K. Ihm, Characteristics of Titania Supported Copper Oxide Catalysts for Wet Air Oxidation of Phenol, J. Hazard. Mater. 2007, 146, 610. [18] A. Pintar, J. Batista, T. Tile, Catalytic Wet-air Oxidation of Aqueous Solutions of Formic Acid, Acetic Acid and Phenol in a Continuousflow Trickle-bed Reactor over Ru/TiO2 Catalysts, Appl. Catal., B 2008, 84, 30. [19] P. D. Vaidya, V. V. Mahajani, Insight into Sub-critical Wet Oxidation of Phenol, Adv. Environ. Res. 2002, 6, 429. [20] S.-K. Kim, K.-H. Kim, S.-K. Ihm, The Characteristics of Wet Air Oxidation of Phenol over CuOx/Al2O3 Catalysts: Effect of Copper Loading, Chemosphere 2007, 68, 287. [21] R. J. G. Lopes, A. M. T. Silva, R. M. Quinta-Ferreir, Screening of Catalysts and Effect of Temperature for Kinetic Degradation Studies of Aromatic Compounds During Wet Oxidation, Appl. Catal., B 2007, 73, 193. [22] A. Garg, I. M. Mishra, S. Chand, Catalytic Wet Oxidation of the Pretreated Synthetic Pulp and Paper Mill Effluent under Moderate Conditions, Chemosphere 2007, 66, 1799.

Acknowledgement
Financial assistance provided by Council of Scientific and Industrial Research (CSIR), New Delhi for conducting this experimental study is acknowledged.

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