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