Katyayani Prabhu et al.

/ International Journal of Engineering Science and Technology (IJEST)

COMPARISON OF EFFICIENCY OF SOLAR PHOTOCATALYTIC DEGRADATION OF PHENOL USING UV TRANSPARENT MATERIALS.

Katyayani Prabhu
Chemical Engineering Department, Manipal University, Manipal Institute of Technology, Manipal-576104, Karnataka, India. katyayani.ramdas@gmail.com

Shanmuga Priya
Associate Professor, Department of Chemical Engineering, Manipal University, Manipal Institute of Technology, Manipal-576104, Karnataka, India. shanpriyanitt@yahoo.co.in Abstract: Solar photocatalytic degradation of phenol has been studied under solar irradiation at Manipal test conditions. The experiments were carried out with 0.1 g/l of TiO2 for different concentrations of phenol ranging from 100, 200, 300, 400, 500 and 600 mg/l. In this study, two different UV transparent materials were tested namely Borosilicate Glass and Low Density Poly Ethylene. Titanium dioxide coated on polyester transparency sheets was used as catalyst. The results of experiments with and without catalyst for phenol degradation have been compared and discussed. The advantages of using fluoropolymers as material of construction are mentioned. The degradation rates obtained in LDPE is around twice that of Borosilicate glass. During the photodegradation, the disappearance of phenol was analyzed by UV- Visible spectrophotometer. Keywords: Borosilicate glass, Low density poly ethylene, Phenol, Solar degradation, Titanium dioxide coating, UV Spectrophotometer. 1. Introduction Phenol and phenolic compounds occur as waste from various industries like Oil refining, petrochemical, coal mining, lignite transformation etc. and result in bioaccumulation. Water from natural sources is mainly polluted due to chemicals present in the wastewater let out from industries of various domains. High COD, opacity, high alkalinity/acidity, high total solids and high BOD are the characteristic of industrial wastewater. This creates an imbalance in the ecosystem and hence treatment of such wastewaters is needed. Photocatalysis is a technique that uses solar radiation and a photocatalyst, the photon energy from sun is used for generating hydroxyl radicals formed as a result of oxidation of catalyst that remove organic matter in wastewater. Traditional methods employed involve phase transfer of contaminant like treatment using activated carbon, air stripping, and biological treatment, accompanied with disadvantages. Activated carbon adsorption involves phase transfer of pollutants without decomposition and thus induces another pollution problem. Chemical oxidation is unable to mineralize all organic substances and is only economically suitable for the removal of pollutants at high concentrations. For biological treatment, the main drawbacks are: slow reaction rates, disposal of sludge and the need for strict control of proper pH and temperature. Advantages of using photo-catalytic method are [1]: Complete oxidation of organic pollutants within few hours, no formation of poly-cyclised products, availability of highly active and cheap catalysts capable of adapting to specially designed reactor systems, oxidation of pollutants in the ppb range etc. TiO2 is one of the most popular and promising materials, because of its stability under harsh conditions, commercial availability, different allotropic forms with high photo-activity, possibility of coating as a thin film on solid support, ease of preparation in the laboratory etc. Its absorption spectrum overlaps with the solar spectrum and hence opens up the possibility of using solar energy as the source of irradiation. Many of the photocatalytic reactions, aimed at water purification, are carried out with the catalyst suspended as fine particles in the contaminated water, employing a low solid concentration and slurry reactor. Fixed bed [2], fluidized bed [3], an immobilized membrane fixed on the reactor walls [4], a reactive wall reactor [5] and an immobilized film coating a bundle of optical fibers [6] are the

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reactors that are tested for. Solar non-concentrating systems are better than concentrating ones because they employ both direct and diffuse components of UV spectrum of sunlight. 2. Materials and Methods Because of good UV transmittance, fluoropolymers pose a good choice for photoreactors. They also exhibit excellent ultraviolet stability and chemical inertness. Fluoropolymer materials transmit light as diffuse are poor IR-diffusers, but make an excellent visible/UV diffusers. Temperatures inside solar photochemical reactors can easily reach 40-50C, just in the case of nonconcentrating or one-sun reactor, due to the absorption of the visible portion of the solar spectrum. Therefore, photochemical reactors must be able to withstand summer temperatures of around 70-80C in order to insure that there will be no damage, which could reduce the flow [7]. A special LDPE photoreactor with six chambers of capacity 900 ml (150 ml each), and surface area around 225 cm2, depth 5 cm was fabricated. The reactions were carried out in open atmosphere under sunlight at temperature of 28-32oC. The samples were kept in sunlight for different time intervals. The reactions under solar irradiation were carried out in Manipal, latitude: 13.3484428N, longitude: 74.7852417E, in the month of January between 11 am and 4 pm. Solar light intensity was approximately 700 W/m2, determined using a Pyranometer. UV light intensity was approximately 30 W/m2 measured using Global UV Radiometer. For these reactions the temperature was maintained at 302 C. Phenol was obtained from Qualigens Fine Chemicals with molecular weight 94.11 and 99.5% purity. Wastewaters of different concentrations of phenol were synthetically prepared (100-600 ppm) using Millipore distilled water. The following are the properties of phenol: Sl No 1. 2. 3. 4. Molecular weight Freezing point Reaction with air Purity
Table 1: Properties of Phenol

Properties 94.11 40-41oC Becomes Pink 99.5%

TiO2 was obtained from HiMedia Laboratories Pvt. Ltd. with a molecular weight 79.88 with 99% purity. TiO2 was coated on polyester transparency sheets. Solvent Cement adhesive was purchased from Reliance Industrial Products and spread uniformly on the sheets. TiO2 was weighed and uniformly spread on the sheets and allowed to adhere overnight at room temperature. The sheets were cut into appropriate sizes and used in the photoreactor [7]. Experiments were carried out directly by immersing coated TiO2 sheets in Phenolic water and also by allowing it to stand in phenolic water for 24 hrs. (Adsorption equllibrium). The reaction was started by exposing the reactor to sunlight and during 5 hrs, aliquots of 5 mL were collected from the reactor and analyzed spectrophotometrically. Analysis was done using UV Visible Spectrophotometer. (UV-PharmaSpec 1700 Shimadzu). 3. Procedure All the experiments were performed using lab-scale photoreactor. The rectangular shaped photoreactor had minimum depth inorder to ensure maximum penetration of solar UV rays. The reactor was fabricated in such a way to accommodate six different concentrations of phenol. The sheets coated with TiO2 are dipped in all the chambers of the photoreactor and exposed to sunlight. The reaction time was started when the reactor was exposed to sunlight. The reactor was kept under solar irradiation for 5 hrs. The experiments were also carried out without immersing the catalyst. The procedure was repeated for Borosilicate glass. Aliquots of 5 ml were taken from the photoreactor and analyzed spectrophotometrically using UV-Visible spectrophotometer. 4. Results and Discussion From the experiments carried out, it can be seen that using LDPE as material of construction, it is possible to obtain better percentage degradation as compared to glass. All the experiments were carried out at constant catalyst concentration and time of irradiation. The maximum reduction in concentration obtained from Borosilicate glass and LDPE are 43 and 59 ppm, respectively, without catalyst. Similarly, 84 and 95 ppm concentration was reduced from initial phenol concentration, with catalyst, using Borosilicate glass and LDPE respectively. The variation in percentage degradation can be due to poor solar light intensity.

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4.1 Degradation using Borosilicate Glass 0.7

Absorbance of Phenol
0.6 0.5 Absorbance 0.4 0.3 0.2 0.1 0 0 100 200 300 400 500 Concentration (ppm) 600 700
With Catalyst Without catalyst Before treatment

Figure 1: Graph indicating the absorbance of phenol before treatment, after treatment (without catalyst) and after treatment (with catalyst).

18 16 14 12 % Conversion 10 8 6 4 2 0 0 100

Concentration v/s % conversion

With catalyst Without catalyst 200 300 400 Concentration (ppm) 500 600 700

Figure 2: Graph indicating concentration v/s percentage conversion with and without catalyst (for Borosilicate Glass).

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4.2 Degradation using LDPE 1

Absorbance of Phenol

Absorbance

0.5 Without catalyst With Catalyst Before treatment 0 0 100 200 300 400 500 600 700 Concentration (ppm)

Figure 3: Graph indicating the absorbance of phenol before treatment, after treatment (without catalyst) and after treatment (with catalyst).

Concentration v/s %conversion

30 25 20 % Conversion 15 10 5 0 0 100 200 300 400 500 Concentration (ppm)
Figure 4: Graph indicating concentration v/s percentage conversion, with and without catalyst. (for LDPE).

% Conversion without catalyst % Conversion with catalyst 600 700

5. Conclusion The efficiency of two different materials were tested for phenol degradation i.e. Borosilicate glass and LDPE using a lab scale photoreactor under uniform conditions of catalyst concentration and time of irradiation. The method of catalyst coating has its advantages i.e. there is no degradation of catalyst with respect to time and it can be reused. By increasing the concentration of catalyst and time of irradiation, it is possible to attain further more degradation of phenolic content. Further studies are being carried out for testing the efficiency of other fluoropolymers like PVC and High Density Poly Ethylene. Efforts are being made to modify lab scale photoreactor into industrial scale.

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