DEGRADATION OF REMAZOL BRILLIANT BLUE USING OZONE IN A PIPE FLOW REACTOR

Noor Anis Kundari1, Kartini Megasari2, Dadit Eko Setyawan3, Kris Tri Basuki4, Maria Christina Prihatiningsih5 a Department of Nuclear Chemical Engineering, Polytechnic Institute of Nuclear Technology (POINT), National Nuclear Energy Agency, 55281, Yogyakarta, Indonesia E-mail: noor_anis_kundari@yahoo.co.id ABSTRACT Wastewater from textile industries contain different types of synthetic dyes included remazol brilliant blue (RBB), are mostly toxic, mutagenic, and carcinogenic. Moreover, they are very stable to light, temperature, and microbial attack, making them recalcitrant compound. Wastewater effluents from textile plants cause major water pollution problems. Strong colour of the textile wastewater is the most serious problem of the textile waste effluent. A degradation kinetic model for RBB using ozone in a pipe flow reactor was developed in this research. The necessary simplifications were made so that the proposed model could be easily used in designing the technology for RBB waste water treatment. Variation of residence time () is used to obtain the model and to determine its influence on RBB final concentration (CAf ), Chemical Oxygen Demand (COD), Biological Oxygen Demand (BOD), and Total Suspended Solid (TSS) which out from the reactor. Based on the research, ozone can degrade RBB continuously in a pipe flow reactor with the equation of: CAf = CA0.e0,392 and degradation rate equation is rA = 0,392CA with k value 2.58 times greater than batch process. The longer residence time, RBB concentration, COD, BOD, and TSS which out from the reactor will be smaller. Keywords: degradation, remazol brilliant blue, ozone, pipe flow reactor. 1. 1.1. INTRODUCTION Background Textile processing operations are considered an important part of textile industrial sector in developing and undeveloped countries. [Mahmoud et al., 2007][1], included batik industries in Indonesia. Wastewaters from textile industriies contain different types of synthetic dyes, wich are mostly toxic, mutagenic, and carcinogenic. Moreover, they are very stable to light, temperature, and microbial attack, making them recalcitrant compound. Wastewaters effluents from textile plants cause major water pollution problems. Strong colour of the textile wastewater is the most serious problem of the textile waste effluent. It has been estimated that more than 700,000 tones of dyes are used annually of which over 15-20 % are left in the effluent during the dyeing process [Robinson, 2001][2]. Dyes in the water bodies such as rivers and lakes undergo chemical and biological changes that consume dissolved oxygen resulting in fish and the distruction of other aquatic organism. Some dyes posses toxicity that is hazardous to aquatic life and posses serious health problem to human [Carreiro et al., 2005][3]. Textile dying effluents are also known to cause extreme variations of pH, dissolved oxygen (DO), temperature, chemical oxygen demand (COD) and dissolved salts of the receiving water bodies [Sevinmli and Sarikaya, 2002; Sevinmli M.F., and C. Kinaci, 2002][4,5]. Reactive dyes are the most common dyes used in the textile industry because of their brighy colours, exellent colourfastness, and ease to application [Yang and Al Duri, 2001][6]. Many reactive dyes are toxic to some organism and may cause direct destruction of aquatic life due to the presence of aromatc and metal chloride [Papic et al., 2004][7]. It has been reported that some azo dyes are particularly challenging to textile wastewater management because of their bright colours, high degree of colourfastness, resistance to aerobic biodegradation and the large amount of dye that exhausted from dye baths [Sarina et al., 2006][8]. Their high solubility, synthetic origin, and complex aromatic molecular structure make their removal a very difficult task [Pandit and Basu, 2002][9]. Removal of hazardous dyes from textile effluent is one of the important factors affecting the economic and environmental sustainability of the industry [Liu et al., 2003][10]. Traditional methods for textile dye wastewater treatment consist of various chemical, physical, and biological processes. More advanced treatment processes include electro coagulation, oxidation, electrochemical oxidation, photooxidation, nanofiltration, colloidal gas aphrons, pre-dispersed solvent extraction, ozonation, and supported liquid membrane. The colourimetric measurement technique has been used to evaluate the effectiveness of these various dye removal methods. In this technique, the absorbance of influent and effluent are measured at the appropriate wave length using spectrophotometer and the removal efficiency is determined. A standard calibration curve is ussually determined at ambient conditions. The impact of UVA and UV-C irradiation and pH and concentration of persulphate in dye removal under UV/K2S2O8 process for reactive blue 19 dye was investigated. The decolorization rate fitted to pseudo-first order kinetic with respect of dye concentration [Rezaee et al., 2008][11]. Otherwise, decolorization of Reactive blue dye by UV/H2O2 process, affected significantly by pH, UV dosage, hydrogen peroxide dosage, and initial dye concentrations, and the rate of dye photochemical follows first order. [Rezaee et al., 2008][12].

The complex process of RBB degradation describe by simple model using global approach. The degradation of RBB Blue is resulted by the action of hydroxyl radical (OH), which can be formed by the oxidation of the adsorbed water. The occurrence of degradation based mainly on the action of hydroxyl radical that produced by reaction of the ozone or electron with water was explained as follows. [Kundari, et.al., 2010][13] RBB + OH compound of RBB degradation or A + OH P (1) The research was carried out to degrade solution of remazol brilliant blue that usually used in batik industries as a model of effluent batiks dye pollutant by using ozone and radiation from electron beam machine. The objective of this research was to to find degradation rate of textile dye effluents involving ozone and electron beams have been investigated in a laboratory scale in order to serve usefull informations. The qualitative analysis showed that the product was oxalic acid. In order to evaluate the formulation of the degradation, the experiments were carried out in a batch process by varying the initial concentration of remazol brilliant blue against the injection time of ozone and electron beams. The formulation rate can be written as -rA =k1CA/(1+k2CA) ppm/min. The values of k1 and k2, by using ozone, were 0.991 and 0.016, respectively. While the values of k1 and k2, using the electron beam machine at 350 keV/10 mA and 23 kGy radiation dose, were 9.313 and 42.918, respectively. [13]. A degradation kinetic model for RBB using ozone in a pipe flow reactor was developed in this research. The necessary simplifications were made so that the proposed model could be easily used in designing the technology for RBB waste water treatment. 1.2. Basic Theory Kinetic pathway of the degradation RBB could be expressed by commonly reaction rate as follows [Levenspiel, 1999][14]. -dCA/dt = -rA = kCAn (2) Where CA is RBB concentration, dCA/dt or -rA is reaction degradation rate at concentration CA, is k is reaction rate constant and n is reaction order. The k and the n would be determined from a plot of the log -rA and the log of CA, the slope is n, while the log of intercept is k. Supposed that the reaction order is one, in a batch recator the design equation can be written as -rA= =kCA1 (3) In order to determine a model of the degradation in a pipe flow reactor it should assumed that the reactor is an ideal pipe flow reactor or as a plug flow reactor or PFR and to this pattern of flow as plug flow.[14] It is characterirized by the fact that the flow

of fluid overtaking or mixing with any other element ahead or behind. Actually, there may be lateral mixing of fluid in a plug flow reactor, however, there must be no mixing or diffusion along the flow path. The necessary and sufficient condition for plug flow is for the residence time in the ractor to be the same for all element of fluid. The residence time is time required to process one reactor volume of feed at spicified conditions. This term can be written as follow =V/v0=(reactor volume/volumetric feed rate (4) In a plug flow reactor the composition of the fluid varies from point to point along with a flow path, the material balance for a reaction component must be made for a differential element of volume, dV. The model would be developed based on mass balance by simplifying as an ideal plug flow reactor and`the distribution of A can be seen on Figure 1.

Figure 1. Distribution of reactance cncentration in a PFR So that for reactant A, the equation becomes CAf = CA0ek (4)

2 STRUCTURE OF WRITING 2.1 Ouline The paper will be written with the outline of Introduction, Structure of Writing, Methodology, Result and Discussion, Conclussions, and References. 2.2 Short description of the outline The introduction descriabe the background, The Structure of Writing contain the outline of the paper, The Methodology contain Materials, Equepments, Procedure, and Analytical Methods, The Result and Discussioan describe the result of the research, The conclussions contain the research conclussion, and the Reference contain the informations that refered. 3 METHODOLOGY 3.1 Materials Meterials used were the remazol brilliant blue purchased from material Batik Shop in Solo and used without purifications. Feeds were prepared by

dissolving the dye in water so the concentration becomes 100 ppm and pH 8. 3.2 Equipment Equipments used in this research is shown at Figure 2.

Figure 2. Equipment Arrangement 3.3 Procedure At first, experiments were done in a 250 mL glass beaker to determine the equation rate, carried out at different initial RBB concentration at the same initial pH of 8, injected with ozone that produced from 100 W ozonizer with ozone production rate of 3.05210-5 g/s for 1 minute. After that experiments were carried in a vertical pipe flow reactor with internal diameter of 1.6 cm and 100 cm at 5 (five) differrent resident time, using 100 ppm initial concentration of RBB and pH 8. While the samples were collected after steady state condition that indicated by constant concentration of RBB in the outlet. The concentration of RBB, COD, BOD, and TSS in the outlet then analyzed. 3.4 Analytical methods The amount of RBB that degradated may be known based on color removal of variations initial concentration of samples that has been processed in specified time. So that samples were collected and immediateley analyzed for the dye concentration using spectrophotometer UV-Vis Mini 1240. Dyes concentrations were calculated from calibration standard curve prepared from the dye concentration and the measured absorbance at wave length, = 592 nm. The COD analysys was done by pour 0.4 g HgSO4, 5 6 clean boiling stones, 20 mL sample solution (diluted with distilled water), 10 mL of 0.25 N K2Cr2O7 put in a 250 mL erlenmeyer COD (glass reflux). 5 mL H2SO4 reagent is inserted into the glass erlenmeyer COD and residual H2SO4 reagent 25 mL erlenmeyer glass is also incorporated into the condenser through bit by bit, and then refluxed for 2 hours over a Bunsen heater. Refluxed solution was cooled and then diluted twice the amount of solution in a glass reflux with distilled water. Then the solution was added 3 drops of

indicator ferroin 4. The rest of the dichromate solution was refluxed, the solution is titrated with standard 0.1 N ferrous ammonium sulfate until the color blue-green changed red-brownish. Shells composed of 20 mL of distilled water containing all reagents are added to the sample solution. Then refluxed in the same manner as above. The formula used [Alaerts, G. and Santika, 1994].[15] Analysis of Biological Oxygen Demand (BOD) is done by Winkler titration method. The sample is inserted into the two BOD bottles each 50 mL, half the number of samples that exist in the BOD bottles are stored in an incubator for 5 days at 20 1 C. Half was analyzed dissolved oxygen on day zero by adding 0.5 ml of MnSO4 + 0.5 ml of alkali reagent iodidaazida + 0.5 mL of concentrated H2SO4 + 3 drops of starch solution and titrated with sodium thiosulfate. Incubated samples were analyzed its oxygen dissolved in the first fifth days by adding 0.5 ml of MnSO4 + 0.5 mL of alkali reagent iodidaazida + 0.5 mL of concentrated H2SO4. Then BOD is calculated given by Alaert (1994). [15] Total TSS was done by heated the Cup of clean empty vaporizer at 105 C in oven for 1 hour, then cooled for 15 minutes in a desiccator and weighed. The sample is poured in the cup and the volume adjusted so that the weight of the residue between 25 to 250 mg. The cup containing the sample is introduced into the oven with a temperature of 98C and then forwarded by drying in an oven with a temperature of 103C 105C for 1 hour. Solid residue is cooled in a desiccator and weighed. Step 3 is repeated until a constant weight is obtained. TSS is calculated using the formula (Alaerts, G. and Santika, 1994). [15] 4 RESULTS AND DISCUSSIONS

The results of experiments with a batch process obtain the relation of reaction rate with the concentration, then created a relationship with log of reaction rate and log concentration shown in Figure 3.

Figure

3.

Graph of log concentrations

reaction

rate

vs

Based on Figure 3 it was known that the slope as reaction order and intercept as log of the rate constant. Based on the equation, the reaction order is 1 and the rate constant is 0.152 s-1, so that the rate equation is.

- rA =

dCA dt

= 0.152 CA1

(5)

Based on research using a pipe flow reactor with the feed concentration of 100 ppm and residence time vriations the concentration of RBB in the outlet (CAf) it can be plot as a graph that presented as Figure 4.

The result shows that the degradation of Remazol Brilliant Blue using a plug flow reactor is more effective than the batch. It also looks at its k value value for degradation in the plug flow reactor is greater in a batchwise. The comparison of k value in batch process and in a PFR is 1: 2.58 or 19:49. The greater value of k shows better contact of the reactant in the PFR. In the PFR ozone and the dye trapped inside the reactor so that good contact between the two. In the batch does not happen confinement so that the ozone would quickly escape into the air resulting in contact between ozone and the dye is less good. The ozone is Able to degrade RBB for treatmet of the textile wastewater. The success of this process for waste treatment can be marked with indigo reduction of COD, BOD and TSS. Table 1 shows the results of testing levels of COD, BOD and TSS of the dye Remazol Brilliant Blue before and after ozonation. Table 1. The influenc of residence time to the COD, BOD, and TSS (initial condition: COD=940; BOD=480, TSS=95) Run COD, BOD, mg/L TSS, mg/L , s mg/L 1 0.34 760 365 60 2 0.65 680 325 50 3 1.54 625 300 40 Based on Table 1, the general decline of COD, BOD, and TSS value after ozonation. In addition, it can be known that the longer residence time the lower of COD, BOD, and TSS value The Chemical Oxygen Demand is the amount of oxygen needed for the existing waste material in water can be oxidized through a chemical reaction that can be degraded both biologically and are difficult to degrade. Water with high COD values are not desirable for the interests of fisheries and agriculture. COD values in the unpolluted waters are usually less than 20 mg / L, whereas in polluted waters can be more than 200 mg / L and the waste industry can reach 60,000 mg / L (UNESCO, WHO / UNEP, 1992) [Wardhana, 2004] [16]. According to Government Regulation No. 28/2001 COD is the quality standard for waters used for second-class water recreation and fish farming (aquaculture), for example, is less than 25 mg / L. Based on the value of COD analysis results, the sample solution Remazol Brilliant Blue has ozonized in this research is still classified as contaminated. The BOD is the amount of oxygen needed by microorganisms in the aquatic environment to break down (degrade) the existing organic waste material in water to carbon dioxide and water. The number of microorganisms in water environment depending on the level of water cleanliness. Relatively clean water that contains microorganisms less than contaminated. Large levels of BOD is an indication that these waters have been polluted [Wardhana, 2004].[16] BOD values in

Figure 4. The influence of Residence time to RBB final concentration Based on Figure 4, the longer the residence time, the smaller the concentration of Remazol Brilliant Blue which comes out from the reactor (final concentration) and the mathematical model of degradation of Remazol Brilliant Blue in the plug flow reactor is CAf = CA0e0.392 (6) with reaction rate constants k = 0.392 and kinetics equation of degradation of Remazol Brilliant Blue in a plug flow reactor is -rA = 0.392CA Comparision between model with k that found from the batch process and the process using PFR can be seen at Figure 5.:

Figure 5. The comparison of model from batch process and the process in PFR

the solution of Remazol Brilliant Blue after ozonation is still too large and does not meet the quality standard of effluent in industrial activities. Based Kep.51/MENKLH/10/1995 BOD values for effluent quality standards for industrial activities of class I is 50 mg / L and group II was 150 mg / L [Wardhana, 2004][16]. According to Government Regulation No. 28/2001 is the quality standard BOD is less than 3 mg / L. The TSS value of quality standards for class B water (water that can be processed for drinking and domestic use) is 100 mg / L and for category C (waters for fisheries) is 200 mg / L). Based on TSS analysis the solution of Remazol Brilliant Blue that has been ozonised study has been reached the quality standard of waste water. Thus, to improve quality standards and to the polluters and safely discharged into the environment, then efforts will be made so that the dye concentration can be decreased until the value of quality standards. Efforts that can be done is to prolong the contact time between the ozone with the dye that is by minimizing the flow rate or extend the length pipe so that the contact time between the ozone with the dye to give it stuffing material into the pipe flow reactor to reach waste water quality standard. 5 CONCLUSIONS Based on the research, the conclusions are as follow: Ozone can degrade continuously Remazol Brilliant Blue in plug flow reactor. Mathematical model and kinetics equation of Remazol Brilliant Blue in a plug flow reactor in a row is the CAF = CA0e 0.392 and rA = 0.392CA with k value 0.392 a greater than batchs k value is 2.58 times. The longer residence time, the smaller RBB concentration, COD, BOD, and TSS which out from the reactor. REFERENCES

1. 2.

3.

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