UV Assisted Fenton Oxidation of Organics Present in the Reverse Osmosis Concentrate of a Textile Waste Water Treatment Plant

UV Assisted Fenton Oxidation of Organics Present in the Reverse Osmosis Concentrate of a Textile Waste Water Treatment Plant

UV Assisted Fenton Oxidation of Organics Present in the Reverse Osmosis Concentrate of a Textile Waste Water Treatment Plant

Amali Gitanjali R1

1Former Undergraduate, Department of Civil Engineering, Anna University Tiruchirappalli, Tiruchirappalli, TamilNadu, India.

SR Lavanya2 2Assistant Professor,

Department of Civil Engineering,

Karpaga Vinayaka College of Engineering and Technology, TamilNadu, India

Aditya Sharma3

3Assistant Professor, Department of Civil Engineering,

ITM University, Gwalior, Madhya Pradesh, India

Abstract – The concept of zero discharge is accelerated in the mean time on the rising trend of discharging the waste water by the industries which have been identified under red category by the Ministry of Environment and Forest, Government of India. Textile dyeing is one such industry where the implementation of zero discharge from the textile water treatment plant. In practical cases there are plethoras of difficulties because the concentrate of reverse osmosis is coloured, highly alkaline and high COD content. This paper deals about the attempts of removal of color and COD from the reverse osmosis concentrate. In this paper the reverse osmosis concentrate is been subjected to UV radiations with homogenous catalyst like Ferrous, Copper ions and Manganese ions. The results of the concentrate in COD content varied in the duration of 2hours with the usage of catalyst. However, it is found that COD reduction is highest in the combined catalyst of ferrous and copper ions. Further color removal was also observed. This treated effluent is further treated with nano filtrations, reverse osmosis or evaporator to achieve zero discharge.

Keywords – Fenton Oxidation, Zero discharge, Reverse Osmosis Concentrate

1. INTRODUCTIONs

   Textile is one of the oldest industries in the world with a major contribution to the economy of the nation. In India the contribution from the textile industries amounts to approximately 5% and 27% to the foreign exchange earnings. Specifically in TamilNadu the regions around Coimbatore, Tirupur, Karur, Erode is referred as Textile Valley of India. Tirupur generates an export around Rs 50,000 million per year and Karur Rs 35,000 million per year in foreign exchange from textile industries.

   Large amount of water is been consumed by the industries for the dyeing process and for the production of different types of fabrics. The water discharged from the industries has large amount of hazardous chemicals and

   dyes in it which affects the environment. The textile effluent is characterized by colour, pH, BOD/COD ratio, Total Dissolved Solids (TDS), Suspended solids. The textile reject treatment is a complicated problem due to the following reasons

   • High Total Dissolved Solids (TDS) content

   • Presence of Heavy chemical such as Cr, As, Cu, Zn

   • Non Biodegradable organic dye stuffs

   • Presence of free chlorine and dissolved silica

   In the textile reject there are large amounts of undigested organics. Inorder to oxidize the organic particles present in wastewater it is essential to use oxidation process. The organic particles present in the textile reject is digested in the presence of more heat energy so as to induce high amount of heat energy for the digestion of organic particles makes a necessity towards Advanced oxidation process(AOP) as the conventional treatment process was unable to degrade the coloured dyes and toxicity. There are four ways for Advanced Oxidation Process

   • Combination of Ozone (O3)/ Hydrogen Peroxide (H2O2)

   • Combination of Ozone (O3)/ Ultra Violet Radiations

   • Combination of Ultra Violet (UV) Radiation Hydrogen Peroxide (H2O2)

   • Combination of Ozone (O3)/Ultra Violet Radiation/ Hydrogen Peroxide (H2O2)

     This paper deals with Advanced Oxidation Process by the combination of Ultraviolet radiations (UV) and hydrogen peroxide (H2O2) for the degradation of COD in the textile reject. On the exposure of Ultra violet radiations, hydrogen peroxide will be photolyzed to form hydroxyl radicals as the primary oxidant. This hydroxyl radical digests the organic molecules and thereby reducing the chemical contamination and toxicity in the textile reject.

     In order to make a complete ecofriendly atmosphere led to the concept of zero discharge. This is considered to be beneficial to the textile industries and to the environment. This is a most advanced waste water treatment plant which reuses the waste water in such a way that water is free from impurities and chemicals. The main aim of the zero discharge is to recover the usable materials like water, salt from the effluent and minimize the generation of waste so that it can be safely stored on site without the need for discharge into the environment.

2. OBJECTIVES

   The main objective of the project is to reduce the COD content in the textile reject using Advanced Oxidation Process. The reduction of COD content in textile reject is being carried out by the exposure of Ultraviolet rays with different types of Catalyst like Ferrous (Fe2+), Copper ions (Cu2+) and Manganese ions (Mn2+).

3. MATERIALS AND METHODS SAMPLE COLLECTION

   The textile reject is collected from the textile waste water treatment plant in SIPCOT, Perundhurai, TamilNadu, India. The collected textile reject consists of large amount of Suspended Solids, BOD and COD. The reject is the effluent collected after primary (aeration) and secondary (reverse osmosis) treatment. The textile effluent characteristics like pH, Total Dissolved Solids (TDS), COD and Chloride were determined in the collected raw textile waste water given in the table 1

   Table 1: Characteristics of Textile Effluent collected from reverse osmosis concentrate stream
   pH	7.75
   TDS (mg/l)	23,000
   COD (mg/l)	790
   Conductivity (µ Siemens)	35,300
   Chloride (mg/l)	78,500

   CATALYST USED

   • Ferrous ions (Fe2+)

   • Copper ions (Cu2+)

     • Manganese ions (Mn2+)

   • Combination of Ferrous ions (Fe2+) and Copper(Cu2+)

   • Combination of Ferrous ions (Fe2+) and Manganese ions (Mn2+)

   KINETICS UNDER UV LIGHT

   The setup of the sample is shown in figure 1 and it consists of beaker with a nozzle, Quartz Test Tube, UV light (primary radiation at 254nm)

   Figure 1: UV Photoreactor

   Before performing the kinetics in the apparatus, the procedure is followed initially the beaker is filled with 100ml of the collected sample and the catalyst with hydrogen peroxide (1:1 of 5ml) is added in the sample and stirred thoroughly without any air bubbles in the beaker. Before starting the process collect a 3ml sample by the use of syringe which is considered as a sample for zero minutes. After the start of the process for every 15minutes a sample of 3ml is taken continuously up to 2 hours. This procedure is repeated using different types of catalyst. The collected samples are placed in the COD photometer for the determination of COD content.

   COD PHOTOMETER

   2ml of the sample is taken in the COD vial with the reagent present in it. The vial is made to mix thoroughly with the reagent and paced in the digestor for a period of 2hours. After 2 hours the vial is allowed to cool and it is placed in the COD photometer for the determination of COD content.

4. RESULTS AND DISCUSSIONS REACTION KINETICS OF TEXTILE REJECT WITH FERROUS (Fe2+) AS CATALYST

   The readings shown below are obtained with Ferrous (Fe2+) as catalyst, hydrogen peroxide as oxidant. The COD: Hydrogen peroxide (H2O2): Catalyst mixed in the molar ratio of 1:1:1. This mixture is exposed to Ultra violet (UV) radiations for 2hours. Samples were taken out in the interval of 15minutes for 2 hours and COD is measured. The results are tabulated in the table 2. Inorder to find the rate constant, the ratio between initial concentration of COD (A0) and the

   Table 3: Kinetics of UV- Fenton Oxidation of Organics present in the textile effluent with Copper ions ( Cu2+ )as catalyst
   The COD: Hydrogen peroxide (H2O2): Catalyst (Cu2+) mixed in the molar ratio of 1:1:1
   Time (min)	COD (mg/l)	A0 / A	ln(A0 / A)
   0	381	0	0
   15	293	0.769	-0.283
   30	284	0.745	-0.314
   45	280	0.734	-0.328
   60	271	0.711	-0.361
   75	224	0.589	-0.551
   90	244	0.640	-0.466
   105	263	0.690	-0.391
   120	222	0.582	-0.561

   concentration of 15mins interval (A) is plotted against time in the Graph 1. The COD reduction from the table 2 is 64% in 2hours. The calculated rate constant for this type of catalyst is -0.0092.

   Table 2: Kinetics of UV- Fenton Oxidation of Organics present in the textile effluent with Ferrous ( Fe2+ )as catalyst
   The COD: Hydrogen peroxide (H2O2): Catalyst ( Fe2+)mixed in the molar ratio of 1:1:1
   Time (min)	COD (mg/l)	A0 / A	ln(A0 / A)
   0	389	0	0
   15	341	0.877	-0.131
   30	301	0.774	-0.256
   45	273	0.702	-0.340
   60	221	0.568	-0.556
   75	192	0.494	-0.705
   90	167	0.429	-0.846
   105	142	0.365	-1.008
   120	139	0.357	-1.030

   Graph 2: Kinetics of UV Fenton Oxidation of organics present in the textile effluent using Copper ions ( Cu2+ )as catalyst

   REACTION KINETICS OF TEXTILE REJECT WITH FERROUS (Fe2+) AND COPPER IONS (Cu2+) AS A CATALYST

   Graph 1: Kinetics of UV Fenton Oxidation of organics present in the textile effluent using Ferrous ( Fe2+ )as catalyst

   REACTION KINETICS OF TEXTILE REJECT WITH COPPER IONS (Cu2+) AS CATALYST

   The sample is mixed with Copper ions (Cu2+) as catalyst and hydrogen peroxide as oxidant is subjected to Ultra violet radiations (UV). The readings are tabulated in Table 3 and the respective graph in Graph 2 is plotted for the determination of rate constant. The COD reduction using copper ions is calculated as 42% with rate constant of – 0.00344.

   Table 4: Kinetics of UV- Fenton Oxidation of Organics present in the textile effluent with Ferrous ( Fe2+) and Copper ions ( Cu2+ )as catalyst
   The COD: Hydrogen peroxide (H2O2):: Catalyst ( Fe2+) and ( Cu2+ ) mixed in the molar ratio of 1:1:1
   Time (min)	COD (mg/l)	A0 / A	ln(A0 / A)
   0	389	0	0
   15	341	0.876	-0.132
   30	304	0.781	-0.247
   45	283	0.727	-0.318
   60	222	0.570	-0.562
   75	167	0.429	-0.846
   90	124	0.318	-1.145
   105	93	0.239	-1.431
   120	72	0.185	-1.687

   The COD reduction is a combination of Ferrous (Fe2+) and Copper ions (Cu2+) as a catalyst with equimolar concentration with (1:1) ratio. The COD reduction is calculated from the table 4 as 81.15% and the corresponding rate constant is determined from the Graph 3 as -0.01441. This combination of catalyst shows the higher amount of COD reduction compared to other conditions that is organic particles in the reject is broken in higher rate.

   COMPARISON OF THE OBTAINED RESULTS

   Table 6: Summary of Experimental Results
   Experi ment No	Catalyst	Rate Consta nt	R2	COD Reductio n after 2hours (%)
   1	Ferrous( Fe2+)	0.009	0.990	64.10
   2	Copper ions ( Cu2+ )	0.003	0.702	41.70
   3	Combined Ferrous( Fe2+) and Copper ions ( Cu2+ )	0.014	0.963	81.49
   4	Combined Ferrous( Fe2+) and Manganese ions (Mn2+)	0.011	0.924	71.15

   Graph 3: Kinetics of UV Fenton Oxidation of organics present in the textile effluent using Ferrous ( Fe2+) and Copper ions ( Cu2+ )as catalyst REACTION KINETICS OF TEXTILE REJECT WITH FERROUS (Fe2+) AND MANGANESE IONS (Mn2+) AS A CATALYST

5. CONCLUSIONS

   The importance of the usage of advanced oxidation process for the treatment of textile waste water is emphasized because higher level of TDS content in the textile reject makes unsuitable for biological treatment process. This paper focus on the attempts to remove the color and COD in the textile reject using various homogenous catalyst like Ferrous (Fe2+), Copper ions (Cu2+ ), Combined Ferrous (Fe2+) and Copper ions (Cu2+ ) and Combined Ferrous(Fe2+) and Manganese ions (Mn2+) employed here. A maximum of COD reduction 81.49 % is achieved in Combined Ferrous (Fe2+) and Copper ions ( Cu2+ ) and the least amount of

   2+

   The results of COD are shown in table 5 and the rate

   COD reduction 41.70% in Copper ions ( Cu

   ) catalyst.

   constant is calculated from the Graph 4. Thus the COD reaction in method is found to be 71.15% and the rate constant is 0.01054

   Graph 4: Kinetics of UV Fenton Oxidation of organics present in the textile effluent using Ferrous ( Fe2+) and Manganese ions (Mn2+) as catalyst

   Further color removal was also observed. Hence this process

   can be adopted by the textile industries for achieving zero discharge.

   Table 5: Kinetics of UV- Fenton Oxidation of Organics present in the textile effluent with Ferrous ( Fe2+) and Manganese ions (Mn2+) as catalyst
   The COD: Hydrogen peroxide(H2O2):: Catalyst ( Fe2+) and (Mn2+) mixed in the molar ratio of 1:1:1
   Time (min)	COD (mg/l)	A0 / A	ln(A0 / A)
   0	371	0	0
   15	351	0.946	-0.055
   30	332	0.894	-0.112
   45	305	0.822	-0.196
   60	284	0.765	-0.267
   75	221	0.595	-0.519
   90	172	0.463	-0.770
   105	135	0.363	-1.013
   120	107	0.288	-1.244

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