The 16th International Conference on TiO2Photocatalysis: Fundamentals and Applications

San Diego, California, USA, November 7-10, 2011
Juan Camilo Cardona ʈ, Juan Carlos Angrino ʈ Augusto Arce-Sarriaʈ, Miguel Angel Mueses§ʈ and Fiderman Machuca-Martínezʈ ʈSchool of Chemical Engineering, Universidad del Valle, Cali-Colombia §Department of Chemical Engineering, Universidad de Cartagena, Cartagena-Colombia

Universidad de Cartagena

Solar CPC Reactors Size Effect on Heterogeneous Photocatalytic Degradation of Phenol

Abstract The degradation of organic compounds by heterogeneous photocatalysis depends of several things like configuration, size and total reaction volume of the reactor under consideration. Consequently the reaction kinetic is influenced by this dependence too, limiting the application of experimental data to different geometries and scales. Thus, it creates the need to evaluate useful parameters to compare solar reactors among each other. In this study, the performance of pilot-scale solar reactors of different sizes was compared in function of a geometric parameter to evaluate the heterogeneous photocatalytic degradation of phenol aqueous solutions. Three solar CPC reactors, which irradiated surface areas and reaction volumes vary in proportion to their sizes were used. To adjust different levels of total reactor volume the geometric parameter is defined as 𝛽 = 𝑉𝑅 /𝑉𝑇 . The percentage of Total Organic Carbon (TOC) was chosen as key parameter to evaluate the performance of the reactors to measure the mineralization degree of solution. Geometry and scaling dependence In a previous work [1], two geometric parameters were proposed for pilot-scale photoreactors with recycle to study their effect in the photodegradation per surface area (ST) and treated volume unit. The parameters were:

Materials and Equipment It was used TiO2-P25 (Evonik-P25) as catalyst with phenol, CAS 108-95-2, besides phosphoric acid (H3PO4) and NaOH to adjust the solution pH. To measure the experiment conditions like pH and O2 it was used a Thermo Scientific Orion 5 Star Plus Meter, also a SHIMADZU® MODEL-VCPH device to measure the TOC. The tests were carried out using three pilot-scale CPC solar reactors of different sizes; each reactor is made of 10, 20 and 30 Schott-Duran borosilicate glass pipes of 32 mm of diameter respectively. Operation conditions The reactors operated in turbulent regimen and the photodegradation was done with 0.7 g/L TiO2, an initial concentration of 120 ppm Phenol, saturated oxygen about 80-100%, the adjusted pH at the initial Phenol concentration (about pH=5 at 120 ppm). All the tests were carried out till 25 W·m-2 of accumulated UV-A radiation. Experimental Procedure Perfect mixture, turbulent flow and O2 saturation was guaranteed using two air compressors and a recirculation system for each reactor. The tests were performed in the same way using a routine: water volume, catalyst concentration, substrate concentration and pH value was measured before to start. Then the samples were done throughout the reaction time. Results It can be observed in Fig. 1-a that β is directly proportional to mineralization percentage. According to this it could say that: CPC reactor size has a positive effect over phenol degradation if total reaction volume is fixed; on the other hand, the total reactor load presents an opposite effect, higher volume needs more energy or a greater area to reach the same result. According to Fig. 1-b the reactor efficiency is independent of β, however it´s shown a considerable increase in mineralization percentage and efficiency for a β value of 0.42, this disproportional increase is awarded to factors beyond the effect of the ratio between 𝑉𝑅 and 𝑉𝑇 . Conclusions The Phenol heterogeneous photocatalytic degradation is not affected by size reactor, however the geometric dependence of process makes that the parameter β directly influence the reaction mineralization rate. The geometric parameter β is effective to compare solar photocatalytic reactors among each other, because this one doesn´t compromise the fotonic efficiency of process and implicitly takes in count the configuration of radiant field, reactor size and total pollutant load.
Reacor1 40.0 Reactor2 Reactor3 50 40 η (mg∙W-1∙h-1) 30 20 10 0 0.28 0.34 β (VR/VT) 0.42 Reactor1 Reactor2 Reactor3 𝑆𝑇

𝛼 = 𝑉𝑅 𝑉𝑅 𝛽 = 𝑉𝑇

(1) (2)

First of them (α) relates reactor surface area (ST) with reaction volume (VR), and is a key parameter to evaluate performance of photoreactors with different configurations. On the other hand, β relates reaction volume with total reactor volume (VT) making possible to analyze the reactor size effect as the load increases in relation to decomposition of pollutants. Reaction Rate As the degradation due to hydroxyl radical formation is relatively non-selective there are numerous intermediaries produced to different operating conditions, this makes more difficult to monitor the studied substrate. For this reason it was used the total organic carbon as a general reaction way to follow instead the compound concentration C commonly used. So, It can be used an analogous equation to the Langmuir-Hinshelwood model [2-5] in order to describe the mineralization kinetics: 𝑟𝑇𝑂𝐶 𝐾𝑎𝑑𝑠

𝑇𝑂𝐶 = 𝑘 1 + 𝐾𝑎𝑑𝑠 𝑇𝑂𝐶

(3)
% Degradation

The equation that corresponds to the mass balance of a pilot-scale CPC solar reactor is combined with equation (3):

30.0

20.0 𝑑

𝑇𝑂𝐶 = 𝛼 ∙ 𝛽 𝑑𝑄𝑈𝑉 𝑟

1 𝐾𝑎𝑑𝑠 𝑇𝑂𝐶 −𝑘 𝑅 1 + 𝐾𝑎𝑑𝑠 𝑇𝑂𝐶

10.0 𝑑𝑟

(4)
0.0 0.2500 0.3000 0.3500 β (VR/VT) 0.4000 0.4500

Where 𝑄𝑈𝑉 is the accumulated radiation per volume unit and R is the radius. Thus solving the equation (4) yields a model that successfully represents the process kinetics and depends on size reactor. Reactor efficiency To quantify the reactor efficiency is necessary to evaluate the absorbed radiation in a specific volume V; thereby it’s defined a parameter that relates the total mineralized mass of phenol per irradiated volume unit:

Figure 1. a: (Above) Phenol degradation percentage vs β; b: (Below) Reactor efficiency vs β.

Acknowledgements The authors thank to the Universidad del Valle and the School of Chemical Engineering for the financial support “Grant 2520”. Also to the National Doctoral Program Support of COLCIENCIAS. 𝑆𝑇𝑂𝐶

= 𝑇𝑂𝐶

0

− 𝑇𝑂𝐶 𝑉𝑅

25

∙ 𝑉𝑇

(5)
References [1] Arce, A., Mueses, M., Colina, J., Machuca F. En The 15th International Conference on TiO2 Photocatalysis: Fundamentals and Applications (TiO2-15). San Diego, California, USA, November 15-18, (2010). [2] Medina, J., Moctezuma E., Sanchez, M., Frausto, C. Journal of Photochemistry and Photobiology A: Chemistry 174 (2005) 246-252.. [3] Colina, J., Machuca, F., Li Puma, G. Environ. Sci. Technol. 43 (2009) 8953-8960.

This mass volume ratio will be strongly dependent on the incident light energy. To account for the fluctuations of the spectral solar irradiance it is reasonable to divide 𝑆𝑇𝑂𝐶 by 𝑄𝑈𝑉 yielding the “efficiency”, 𝜂, of the reactor [6]: 𝑆𝑇𝑂𝐶

𝜂 = 𝑄𝑈𝑉

(6)

[4] Arce, A., Urrutia, L. Escuela de Ingeniería Química, Universidad del Valle, Cali-Colombia (2008). [5] García, O., Kichi, T. Escuela de Ingeniería Química, Universidad del Valle, Cali-Colombia (2010). [6] Alfano, M., Bahnemann, D., Cassano, A., Dillert, R., Goslich, R. Catalysis today. 58 (2000) 199-230.

Modeling and Application in Advanced Oxidation Process Research Group, Universidad de Cartagena Advanced Oxidation Process Research Group, GAOX, Universidad del Valle