Environmental Pollution, Vol. 97• No. 1 2, pp. 147 152, 1997 ,~ 1997 Elsevier Science Ltd All rights reserved. Printed in Great Britain 0269-7491/97 $17.00+0.00

Apostolos G. Vlyssidesa* and Cleanthes J. Israilides b
aNational Technical University of Athens, Laboratory of Organic and Chemical Technology, 9, Heroon Polytechniou Street, Zographou 157 00, Greece blnstitute of Technology of Agricultural Products, National Agricultural Research Foundation, 1, So./: Venizelou Street, Lycovrissi 141 23, Greece
(Received 14 February 1997; accepted 23 April 1997)

Abstract This paper describes an electrochemical treatment and detoxification of tannery waste liquors ( T W L ) . In this technique, T W L was passed through an electrolytic cell using a Ti/Pt anode and a stainless steel304 cathode. Owing to the strong oxidizing potential of the chemicals produced (chlorine, oxygen, hydroxyl radicals and other oxidants) the organic and inorganic pollutants (ammonia, sulfides and chromium) were wet oxidized to carbon dioxide, nitrogen oxides and sulfur dioxide. In addition, chromium was precipitated a s C r 2 ( S 0 4 ) 3. Experiments were run in a batch, laboratory-scale, pilot-plant, and the results are reported herein. After 30 min and 3 h of electrolysis at 0.26 A cm -2, 45°C and p H 9, total chemical oxygen demand (COD) was reduced by 52 and 83% and biochemical oxygen demand (BODs) was reduced by 35 and 66%, respectively. Additionally, total suspended solids ( TSS) were reduced by 8.6 and 26%, total phenolic compounds were reduced by 95.6 and 99.4%. Ammonia, sulfides and soluble chromium were reduced by 100% in both cases, while the mean anode efficiency was 81gh -1 A - l m -2 and 1.9gh -1A - l m - e . Also, the mean energy consumption was 4.8kwh kg -1 of COD reduced and 200kwh kg -1 of COD reduced for 0.5 and 3 h, respectively. These results strongly indicate that this electrolytic method of total oxidation of T W L cannot be cost effective for wide use. However, it can be used as an effectivepretreatment stage for detoxification of the wastewater, owing to great efficiency especially with respect to COD and toxicity (phenolics ) reduction. © 1997 Elsevier Science Ltd Keywords: Tannery waste liquors, electrochemical treatment, oxidation of phenols, chromium(Ill) removal.

Environmental pollution owing to tannery waste liquors (TWL) is an important problem and causes great concern to the leather industries owing to the strain it creates on their resources. The T W L are among the most *To whom correspondence should be addressed. Fax: 30 17723163. 147

difficult wastes to treat due to their high organic load. Tanneries are producing about 7-15m 3 of T W L per tonne of rough leather. An average composition of T W L is given on Table 1 (ESCAP, 1982). Among the organic compounds which are present in these wastes are tannins (polyphenolic compounds) which are difficult to break and are considered to be highly toxic pollutants. Among the inorganic compounds, which are present in T W L in high concentrations, .are ammonia (Szpryokowicz et al., 1995; Naumczyk et al., 1996), sulfides and chromium (Sykes and Corning, 1987) that are strong inhibition factors for any kind of biological treatment. There is not any universally accepted method for an effective treatment of T W L at worldwide level. A thorough review of tannery wastewater treatment was given by Tsotsos (1986). Existing technologies for the treatment of T W L include the use of ozone gas, ozone and UV, and UV and hydrogen peroxide. In spite however, of improvements resulting in less expensive ozone production, the cost of ozone generation is still one of the main drawbacks when it is compared with other technologies• The most widely used technology, the aerobic treatment of the sludge after a primary removal of proteins by sedimentation is not considered cost effective in small and medium size industries like most of those which occur in Greece. In general, biological treatment methods whether aerobic or anaerobic, even though they lead to a significant removal of chemical oxygen demand (COD) and biochemical oxygen demand (BOD), still leave unacceptable levels for direct discharge. Moreover, full nitrification cannot be established (Grenschow and Hegemann, 1993). Oxidation technologies for the treatment of industrial wastewaters have been an attractive alternative to biological methods, especially where biorecalcitrant and toxic wastes are to be treated (Mantzavinos et al., 1996). In the case of TWL, electrochemical treatment has been reported as a feasible process (Szpryokowicz and Zillio Grande, 1994). However, some researchers are in favour of a combined oxidative and biological treatment for tannery wastewaters (Szpryokowicz and Zillio Grande, 1994, 1995; Jochimsen et al., 1996; Kaul and Szpryokowicz, 1996; Naumczyk et al., 1996).

free chlorine and maybe some amounts of ozone and chlorine oxides are the main secondary oxidants as byproducts of the direct oxidation process. C102. based on the products that can be determined (C12. O and C1OH have a very short life owing to their high oxidation potential and they are either decomposed to other oxidants (C12. O H . The direct electro-oxidation rate of organic pollutants is dependent on the catalytic activity of the anode. oxygen. 1991).. 02) and secondary (C102. 1997) that can take place in a mixture of brine solution and wastewater in an electrolysis cell using Ti/Pt anode. C1OH. 1996).148 A. 1996) during the continuous production of free hydroxyl radicals. oxygen and some amounts of hydrogen peroxide and maybe ozone. J.2 e R + C12--* RCI + C I .+ 3 H 2 0 .e R + OH----~ RO + H ÷ + 2 e RC1 + O H . which contained the wastewater to be treated. C. which was a stainless steel 304 cylinder of 20 cm diameter. Israilides of chloride--chlorine-chloride is reduced owing to the production of C103. Vlyssides et al. concentration of NaCI used. Prentice. CO2). which produces OCI-. 1) of the electrolytic cell.25 mm thick. Therefore.. Vlyssides. which was located in the centre of the cylinder and which was made of titanium alloy. the recirculation system. 1977.C.. Only in moderate alkaline to neutral conditions. and on the applied current density (Antropov. and current and voltage applied (Vlyssides et al. on the diffusion rates of organic compounds in the active points of the anode. and 100 amperes. The electrodes were operated at 15 volts D. Mean composition of tannery waste liquors (TWL) Characteristics BOD5 COD Total suspended solids Total chromium Sulfides Chlorides Total phenolic compounds Ammonium nitrogen Kjehdahl nitrogen Fats and oils pH Range (mg litre. H2.~ C l ~ + 2 O H Oxidation reactions In a closed anode area R + M[OH-]---~ M [] + RO + H + + eR + M [ C I O H ] ~ M [ ] + RO + H + + CI. In moderate alkaline solutions a cycle of chloride-chlorine-hypochlorite--chloride takes place. 03. in acid solutions.that is a stable chlorate anion.6 e . The electrochemical reactions. Table 2 shows the electrochemical and chemical reactions (Israilides et al. 02. O . based on the principle of oxidative degradation of all its organic compounds in an electrolysis system. H202. and of the anode.1) 210-4300 180-27 000 925-36 000 3-350 1-500 1500-28 000 0. G. The recirculation system The recirculation system included a vessel of 15 litres. CIO2. time of recirculation. An effective pollutant degradation is based on the direct electrochemical process because the secondary oxidants are not able to completely convert all organics into water and carbon dioxide.+ H + + eEquilibrium reactions C12 + 2 0 H . The radicals O H . the pH-correction system and the cooling system for the wastewater. 02. The primary (C12.~ 3 / 2 0 2 + 6 H ÷ + 4 C 1 . For the time being only assumptions can be made.54 cm in diameter.+ eH20 + M[OH-]---*M[] + 02 + 3H + + 3 e H20 + M[C1OH-] + C1. and a Table 2.~ R O + C1. 03.~ M [CIOH-] + H + + 2eH20 + M [ ] ~ M [OH-] + H + + eSecondary electrochemical reaction 6OC1. 1987. measuring 48 cm in length and 2.. F r o m previous investigations (Wilk et al. The electrolytic cell The electrolytic cell consisted of the cathode.. 1996). pH of the solution. which take place during the electrolysis of a brine solution.~ H20 + OCI.~ C12 + M[] + 02 + 3H ÷ + 4 e Away from electrodes R + 02 + 2H ÷ ~ R O + H 2 0 . and H202) or they oxidise organic compounds (direct oxidation). 03. the initial concentrations of chlorides remain stable (Vlyssides et al. at low pHs the chlorides are reduced during the electrolysis process producing free chlorine. Table 1.+2C103Cathode Primary electrochemical reactions 2 H30 + + 2e. The indirect electrooxidation rate is dependent on the diffusion rate of secondary oxidants into the solution.4-100 17-380 90-630 49-620 1-13 This study deals with a physicochemical approach to the treatment of TWL.+ H20 + 2 e .. M A T E R I A L S AND M E T H O D S Theoretical approach The time of oxidation depends upon the stability and concentration of compounds.+ CI- .~ H2 + 2 H20 2 H20 + 2e----~ H2 + 2 OHSecondary electrochemical reaction OC1. size of the anode. temperature. temperature and the pH. In strong alkaline solutions the cycle The laboratory pilot plant The experimental plant consisted (Fig. Electrochemical reactions Anode Primary electrochemical reactions n 2 0 + M [ ] + Cl. while in high p H the chlorides are oxidised producing chlorates. and H202) oxidants that are produced from the destruction of radicals have quite a long life and are diffused into the area away from the electrodes continuing the oxidation process (indirect oxidation). covered by platinum alloy foil approximately 0. are complicated and not entirely known.

ammonia. which continuously recirculated the reactor contents into the electrolytic cell. pHIR = pH indicator recorder.) during the electrolysis treatment. RIR = redox indicator recorder. Whenever the temperature of the water exceeded 45°C. respectively.0 and 45°C. The change of redox potential in the reactor was continuously recorded by a redox indicator-recorder (RIR). 1989). chlorine and total oxidants were measured. total Kjeidahl nitrogen (TKN). Each experiment was of batch operation and its duration was 3 h. chlorides. The cylinder wall and the cooling jacket constituted the cathode. samples were taken for total phenolic compound determination.~ . Additionally. E = electromagnetic valve. Four experiments under the same conditions were run.. the pH is kept constant at 9. The samples for analysis were drawn from the recirculation reactor. sulfides and free chlorine analysis were carried out according to the Standard Methods for the Examination of Water and Wastewater ( A P H A . total suspended solids (TSS). 1.W P C F . Every 5 rain samples were taken from the reactor. redox.A W W A . sulfides. and the results presented in this work are the average of the four separate measurements. ammonia. Cooling system The cooling system included a temperature indicator controller recorder (TICR). 2. Methodology The efficiency of the electrolytic cell was studied when pH and temperature remained stable at 9. P = recirculating pump. BODs. The COD. an electric valve for the water and a cooling water jacket which was located in the reactor.. Material The composition of the T W L that was used in all experiments is shown in Table 3. minutes Fig.) and BODs ( . Experimental laboratory pilot plant. TSS. T K N . TICR = temperature indicator controller recorder. COD ( . Soluble COD. Table 3.. . The The pH correction system The pH correction system consisted of a pH indicatorrecorder (pHIR) which continuously measures the pH content of the surge vessel and with the help of the dosing pumps PP-1 and PP-2 which supply H C L and NaOH. Reduction of total suspended solids (--F-I--). until the temperature returned to the desired value. The determination of ozone and the total oxidants except for chlorine was carried out according to Wilk (1989).0.0 . BODs. during the experiment. centrifugal pump (P) of 40 litre min -I flow rate. total soluble chromium. cooling water was circulated in the jacket.. PP = peristaltic pump. respectively. C = electrolytic cell.Detoxification of tannery waste liquors 149 + anode Pt/Ti cathode SS-304 cooling jacket pp I -NaOH C vE F S~-------~-'\ -1 cooling water surge vessel sampling Fig. Composition of tannery waste liquor (TWL) used in experiments Characteristics pH BOD5 COD Total suspended solids Total dissolved solids Total chromium Sulfides Chlorides Total phenolic compounds Ammonium nitrogen Kjehdahl nitrogen Alkalinity as CaCO3 Fats and oils Value (mg litre-I) 4 1720 8540 6200 22 400 67 385 18 500 91 288 520 1770 280 9000 8000 7000 6000 E 5000 4000 8 3000 2000 1000 0 time. pH.

Chromium was determined by atomic absorption using a Perkin Elmer (model 2380) analyser. = 70 ~. 1977). chromium is found in the form of a trivalent and a much more toxic six-valent atom.) production during electrolysis treatment. m i n u t e s ~ 10 --It-~.Q .~. at least during the first hours of electrolysis. .A .. 600 . JL__. . Total Kjeldahl nitrogen (--D--). Vlyssides.5% during the first 30min of the electrolysis. ammonia ( .7.5OO 400 j 3OO 8 20O 100 0 . C. Cr2(SO4)3... . Israilides 400 350 30O o 250 r 200 ~o 150 o 10o 50 0 time. R E S U L T S AND D I S C U S S I O N As shown in Fig. As a result. The reduction of chromium could probably be connected with the parallel reduction of sulfides according to the following reactions (Jorgensen and Johnsen. .-7. during the first 25 min of the electrolysis.7.7.7.~2 . ~ .7. when the ammonium nitrogen was depleted and reached its highest concentration (21 mglitre -~) at 120 min.. There was also a very rapid reduction of the sulfides (Fig. In the environment.7. 2 the TSS were reduced by only 26% (from 6200 to 4560mglitre -~) during the 3h of electrolysis.._L ~O oo -- 8 20000 18000 16000 14000 12000 10000 8000 4000 20OO 0 +-H-H÷ H--~ ~ ~ ~ +~--'~c-t I I t I I I ~-H-++-~-++q-++- time. 5. They were reduced by 95.3.. total chlorine (--@--) and other oxidants (--/k--) changes during electrolysis treatment. G. J. The C O D / B O D ratio which is an index of toxicity during biological treatments was improved considerably and dropped from 5 to 2..l (65% during the 3 h of electrolysis)... 2. Fig. Its salts and oxides (CrC13. as shown in Fig. it was reduced by 99% during the first 60 min of the electrolysis.~t.'-117.. m i n u t e s Fig... minutes Fig. Chlorides (--I7--).. In the T W L chromium is found in the trivalent form. . as shown in Fig. 6. . 4. As shown in Fig. 3. . Concentration of total phenolic compounds during electrolysis treatment as a function of time. _ .. minutes Fig.~. The same figure shows that an increase of nitrates was observed which started to be produced after 30min of electrolysis. there was a great decrease of BOD5 (Fig. from 1720 to 590mglitre . time. The T K N was almost completely degraded (98% reduction) during the 3 h of electrolysis (Fig..~. Then it was gradually reduced to 11 mg litreat the end of the 3 h of electrolysis.. During the strong oxidative conditions of electrolysis the trivalent chromium was converted to six-valent. jL. 5) which were reduced from 385mglitre -1 to nil.~.~... Cr203 ) are easily removed due to their low solubility in water. On the other hand. 3..150 100 90 ~¢ 80 e. . . 2).. 1989): total phenolic compounds were measured by the FolinCiocalteu method (Slinkard and Singleton. The COD was reduced even further from 8540 to 1370 mg litre -I. 4). . 60 o o 40 30 A. time.) reduction and nitrates ( . in contrast with the six-valent chromium salts and oxides which are water soluble. 4. The reduction of ammonium nitrogen was also very fast. Sulfides (--I-1--) and total soluble chromium (--@--) reduction during electrolysis treatment. it remains in solution while the toxicity of the solution increases. There was an impressive decrease in the concentration of soluble chromium which was nullified during the first 10-15 rain of electrolysis.. Phenolic compounds were destroyed very quickly._ ::. This is an indication of the very slow rate of hydrolysis. a reduction of about 84% during the 3 h of electrolysis..

Only very little chromium was removed (15%) and the chromium was present in the solution in its main form Cr(VI). Energy consumption (a) repetition of the experiment under the same conditions without the presence of sulfides which were removed by nitrogen stripping. These results cannot be considered satisfactory. Later. The chlorine was increased during the first 10rain from zero to 6300mglitre -I and remained stable thereafter.6 67. During the first 10min of electrolysis the energy consumption was fairly low (from 4.8 mg litre-I rain -~.00 3.84 3. minutes Fig.2 93. 1992). Anode efficiency during electrolysis treatment. 5) reaching 5 mg iitre -t after 3 h of electrolysis.7 100 100 Soluble chromium reduction (%) 85. 250 . Table 4.4 95.0 48. although at a slower rate. Energy consumption during electrolysis treatment. Efficiency of electrolysis for the first 30 min of electrolysis Duration of electrolysis (min) 5 l0 15 20 25 30 Soluble COD reduction (%) 20.8 to 11.. (b) analysis of the precipitant showed that chromium was present as Cr2(504)3. chlorides-chlorine-chlorides. The gradual decrease of electrode efficiency indicates the increasing difficulty for oxidation of residual organics in the waste.73 50.5 Sulfides reduction (%) 28.4 52.1 84.4 98.2 A -1.96 4.0 80.0 49. increased rapidly in the first 10rain from zero to 5840mglitre -1 and then continued to increase with a rate of 6.Detoxification of tannery waste liquors 90 80 < 70 60 151 . Production of oxidants time.+ 02 --~ S02 + eS02 + 1120 --~ H2S03 3H2S03 + 2H2Cr04 --~ Cr2(S04)3 + 51120 The above considerations may be confirmed by: Figure 7 shows the anode efficiency of the electrode measured in Kg COD removed per hour per m 2 of anode surface and per ampere applied (kg COD~ h -I m . Then it continued to be reduced reaching 1.6 Ammonium nitrogen reduction (%) 19.8kg COOt h -1 m . S .I ) .4 27. 7. the energy consumption continued to increase reaching 200 Kwh per kg CODr rendering unfavorable the application of the electrolytic oxidation for the complete treatment of TWL.00 4.6 64.70 .2 A -1 at the end of the 3h. The presence of 03 and H 2 0 : was also detected. 8.~ 50 m © 40 o 30 ~ 20 10 to appear (Fig. minutes Fig.7 47. This is clearly seen in Fig.00 4. where the demands in energy consumption are shown.0 34.0 98. after the 15min of electrolysis. With the start of the electrolysis the efficiency was 81 kg CODr h -1 m -2 A -I which is considered very satisfactory (Comninellis. except for chlorine.0 38. Anode efficiency o 100 50 o time.0 Total phenolic compounds reduction (%) 27.5 63. This proves the existence of the theoretical cycle.Z A .5 100 ---- COD/BOD ratio 4. The resolubilisation of chromium was probably due to the oxidation of precipitants and to an inability to reduce Cr(VI) to Cr(III) due to the absence of sulfides. The other oxidants.8kg COD~ h J m . but in the next 15min it was reduced to 6. (c) after 1 h of electrolysis soluble Cr(VI) has started Figure 8 shows the energy demands versus time in the electrolysis system.1 and was stabilised at this concentration during the whole process of electrolysis. as well as of other oxidants as a whole.0 Kwh per kg CODr) but then increased abruptly to 58 Kwh per kg CODr.7 42.~ 200 O Figure 6 shows the concentrations of chloride ions and total chlorine. The concentration of chlorides was reduced in the first 10 min from 18 540 mg litre-I to 12 300 mg litre.4 40. 8.

17th edn. IAWQ. Israilides. A short survey of the methods applied for wastewater treatment. A. mainly for the detoxification of TWL. L. Kaul. G. L. complete sedimentation of chromium. E. the application of electrolysis as a pretreatment and for residence time up to 30min seems to be very efficient. pp. The pretreatment of T W L is favoured by the fact that it contains high amounts of NaCI: 0. J. and Zillio Grandi. G. Szpryokowicz. IAWQ. NJ. Szpyrkowicz. K. gwf Wasser Abwasser 134. Athens. Prentice Hall. Sykes. ESCAP (1982) Report on Industrial Pollution Control Guidelines Part VII. W. R. S. (1987) Antimicrobial activity of electrolyzed saline solutions. Atlanta. industry and environment. Wilk. pp 135-137. . J. Mourafeti. Water Research 29(2). gwa 11. J. 385386. Proceedings of the International Symposium on Wood and Pulping Chemistry. 1st edn. 9-22. Comninellis... E. 386-395. I. Altmann. D. 4. 3. The Science of the Total Environment 63. Prentice. (1989) Economic advantages of an electrolysis system for pulp bleaching. (1996) The wet oxidation as a pretreatment method for wastewaters contaminated by bioresistant organics. 2nd edn. IAWQ. (1992) The electrochemical treatment of wastewater. I. 1st edn. U and Corning. American Journal of Enol. I.. reduction of COD by 52%.5%. Mir. 262-268. D.. Szpryokowicz. (1977) Theoretical Electrochemistry.7. complete oxidation of sulfides. C. V. Slinkard. (1993) Anaerobic treatment of tannery wastewater. and Metcaife. In Principles of Environmental Science and Technology. and Hegemann. N.. W. J. Vlyssides. F. and Mourafeti. reduction of ammonium nitrogen by 64.96 to 3. 69-76. United Nations. Antropov. D. Athens. G. Athens. (1986) Tanneries. Washington. improvement of biodegradability index (COD/ BOD) from 4. Jochimsen. and Zillio Grandi. (1994) Application of electrochemical processes for tannery wastewater treatment. Hellenbrand.. 209-216.25-4. Elsevier. S. L. GA. V. Lauer. R. J. However. UNEP/IEO 10(2). Trans IChemE 74(Part B). I. (1995) Electrochemical treatment of tannery wastewater using Ti/Pt and Ti/Pt/Ir electrodes. L. eds E. G.. (1996) Electrochemical treatment of tannery wastewater containing high strength pollutants. Israilides The electrolytic oxidation as an integrated solution for the treatment o f T W L does not seem to be feasible due to high energy demands. Jorgensen. R. and Johnsen. pp. Bioresource Technology (in press). pp. and Hegemann.8. (1996) Biological process as a pretreatment for electrochemical oxidation.. G. and Singleton.152 CONCLUSIONS A. Loizidou. Proceedings of the 2nd Specialised Conference on Pretreatment of Industrial Wastewaters. 59-68. reduction of phenolic compounds by 95%. Jekel. Toxicology and Envirnonmental Chemistry 44. L. E. Vlyssides. 404-412. C. A. Livingston. 2. Johnsen. J.. J. 5. F. V. M. D. Bangkok. (1996) Electrochemical treatment of vinasse from beet molasses. R. Karvouni. 6. M. G. Water Science and Technology 18. A. Athens.. American Public Health Association.. pp. N. R. C. G. REFERENCES APHA-AWWA-WPCF (1989) Standard Methods for the Examination of Water and Wastewater. (1997) Olive oil wastewater treatment with the use of an electrolysis system. Tsotsos. S. 522-529. Grenschow. F. (1989) Removal of heavy metals. TAPPI. J. and Berg. (1977) Total phenol analysis: automation and comparison with manual methods. Moscow. Wiik. (1987) Pollution abatement and control in leather industry. De Faveri. 2. and Zillio Grandi. 183-220.." Tanning Industry. Mantzavinos. Vitic. In the first 30 min of electrolysis the following could be achieved (Table 4): 1. Proceedings of the 2nd Specialized Conference on Pretreatment of Industrial Wastewaters. pp. D. (1991) Electrochemical Engineering Principles. Israilides. 49-55. 517-524. IAWQ. A case study for cluster of tanneries from a common effluent treatment plant. Proceedings of the 2nd Specialized Conference on Pretreatment of Industrial Wastewaters. DC.6%. Proceedings of the 2nd Specialized Conference on Pretreatment of Industrial Wastewaters. Vlyssides. C. S. Naumczyk. S. C. 191-197. Jorgensen and I.792-797. and Szpryokowicz. (1996) Combined oxidative and biological treatment for separated streams of tannery wastewater. M. and Karvouni.

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