Leather tanning industry
3.2.5 Colour removal by chemical oxidation
There are a few studies for the removal of colour in tannery wastewaters as well as in synthetic samples prepared using dye stuffs that are commonly used in leather dyeing. Sauer et al. (2006) studied decolourisation of Direct Black 38 using advanced oxidation methods. Direct photolysis by UV (lamb emission 300–410 nm with maximum emission at 355 nm) provided 70 % colour removal together with only 8 % COD removal. Colour removals with H2O2/UV, TiO2/ UV and TiO2/H2O2/UV applications (residence time of 3 hours, initial dye concentration of 300 mg/L, pH = 2.5, initial H2O2 = 20 mg/L) were over 80 %.
In these experiments COD removal was less than 20 % for H2O2 but 68–82 % for the other methods. Ammonia removal in all experiments including direct photolysis was over 80 %. Preethi et al. (2009) investigated colour removal using direct brown azo dye effluent and tannery effluent by ozonation. Complete colour removals were obtained at pH 11 in 60 minutes with ozone dose of 500 ppm.
Colour removal in the tannery effluent was also over 90 % at pH 11, but with 5000 ppm ozone dose. Srinivasan et al. (2009) applied ozone to remove colour of Sandopel Brown BRR dye in synthetically prepared solution. Decolourization efficiencies over 80 % were obtained at pH 4, 7, 9 and 11 within 30 minutes using 3 g/h ozone feed in the 2 L reactor at 30 mg/L dye concentration. Increasing the dye concentration up to 360 mg/L increased the time required to 120 minutes for decolourization efficiencies over 90 %.
3.3 ConCLUDInG remArKS
Oxidation of sulphide by air oxygen is a well defined, economic and suitable method for segregated beamhouse wastewaters. Although, the complex mechanism of the process has still been searched, practical experience about the process ensures a sound basis for process design. Soluble manganese salts function well as a catalyst and due to advantages of cost and non-toxic nature, provide a good alternative.
The critical point in the design of the process is aeration and mixing. Particularly, mixing is of importance in dispersing the oxygen and catalyst homogeneously.
Hydrogen peroxide works well for sulphide oxidation but it is costly and requires pH adjustment to avoid excessive doses. Therefore, it can be considered as a means of polishing treatment following air oxidation. Electrochemical techniques are promising treatment methods, however, further studies are needed to solve operating problems such as pH control, and deposition of elemental sulphur on the electrodes. Among the other oxidants peroxymonosulphate may also be evaluated as a promising candidate.
Chemical oxidation, in addition to sulphide removal, has the potential for use in several stages to solve many of the complex problems that tannery wastewaters exhibit. Among them, increase of biodegradability of organics, control of toxic organics, colour removal, and residual COD removal as well as in-plant control and recovery applications are of importance. Electrochemical treatment is again a method of considerable potential. Its application to raw wastewaters, however may pose problems such as chromium oxidation, formation of sulphur deposits, and operation problems due to high suspended matter content of the wastewater.
Pretreated wastewater, namely the wastewater free from sulphide, chromium and excess suspended matter, however, may be handled by electrochemical oxidation and electrocoagulation. This application may be an alternative to biological treatment or can be combined with biological treatment. Use of ozone for oxidation may not be economical if this application preferentially removes biodegradable organics and having limited effect on inert or slowly degradable organics in biological treatment. However, its use as an intermediate step within biological treatment may be considered provided that this application solves residual COD problem. Use of advanced oxidation methods considering the quality and strength of the secondary effluent and power of oxidants is a viable alternative.
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