Proceedings of the International Conference on Chemical Engineering 2008 ICChE2008, 29-30 December, Dhaka, Bangladesh

CHEMICAL TREATMENT OPTIONS FOR TANNERY WASTEWATER

Shaikh Obaidullah Al Mahmood*
Department of Environment, Ministry of Environment and Forest Dhaka, Bangladesh,

Dr. Rowshan Mamtaz

Department of Civil Engineering, Bangladesh University of Engineering and Technology, Dhaka, Bangladesh,
Environmental pollution by chromium from tannery industry is posing a serious threat for developing countries like Bangladesh. Tannery effluents contain excessive amount of toxic chromium, COD, colour and sulphides which represent an immense pollution load, causing difficulties in effluent treatment. The present research demonstrates the applicability of economical and effective chemical precipitation processes to remove chromium and other heavy metals from tannery wastewater. Removal of total chromium, iron, copper, manganese and lead have been investigated using two different coagulants, such as liquid bittern (a by product in the salt making industry) and alum, and precipitating agents such as NaOH and Ca(OH) 2. Of the two coagulants, liquid bittern along with pH adjustment (above 10) by NaOH was found to be very effective (about 99.9% removal) in removing chromium and other heavy metals whereas the performance of conventional coagulant alum was not good (removal only 34%). The precipitation by NaOH and Ca(OH) 2 (without any coagulants) at pH 10 were also very effective (about 99% removal) in treating tannery effluents. Therefore, only use of alkaline agents like NaOH or Ca(OH) 2 at pH about 10 in the precipitation process could be a low cost and effective chemical treatment options for tannery effluents. Although in terms of percent removal efficiency, both the processes (coagulation with liquid bittern and precipitation with only NaOH) were found to be equally effective (removal efficiency about 99%) since the initial concentration of chromium was very high (385 5736 mg/L), but to make a very critical comparison between liquid bittern and precipitating agent NaOH, LB was found to be more effective as it could lower the final concentration of chromium in the effluents well below the Bangladesh standard limit (0.5 mg/L) for effluent disposal in the surface water. An effect of settling time on the removal of chromium has also been investigated. In the shorter settling time (0.5 6 hr), NaOH was found to be more effective than Ca(OH)2 whereas after 24 hr, the performance of the two alkalis became almost same.

1. INTRODUCTION
Industrial pollution is a growing concern of the present days. Wastes from industrial activities includes wastewater or effluent, gaseous emissions and solid waste. Liquid waste or effluents are having the most devastating effects on people and the environment. Effluents, mostly untreated are primarily discharged into rivers and streams. Since the water bodies are used for drinking, washing, domestic purposes, as well as irrigation and fisheries, pollution of the natural water bodies from industrial discharges is having the most damaging effect on the environment. Among the industries, tannery industry is one of the major concerns. Toxic chromium is present in the effluents from tannery industry. There are 270 registered tanneries in Bangladesh and about 90% of these are located at Hazaribagh, Dhaka

(Bangladesh Environment, 2004). A survey conducted by the Society for Environment and Human Development (SEHD) revealed that about 90% of Hazaribagh tannery workers die before they reach the age of 50 due to unhygienic environment, about 58% workers suffer from ulcer, 31% skin disease etc. Tannery wastewater is characterized by strong color, high COD, low pH, high dissolved solids and high concentration of toxic chromium. Therefore the treatment of this wastewater prior to disposal into water courses has become essential to protect the environment and public health. The method of treatment of tannery effluent can be classified as physical, chemical, and biological. Several coagulants like alum, ferric chloride, ferrous sulfate, magnesium salts are

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Proceedings of the International Conference on Chemical Engineering 2008 ICChE2008, 29-30 December, Dhaka, Bangladesh
usually used in chemical treatment techniques (Rao and Datta, 1987). Ayoub et al (2001) showed that seawater liquid bittern which is rich in magnesium salt (a by product in salt manufacturing process), could be used as an inexpensive coagulant in chemical precipitation process to remove heavy metals from wastewater. In recent years, the need for economical and effective methods for the removal of chromium and other heavy metals has necessitated research towards the low-cost alternatives. Keeping this in mind, the present study is undertaken to investigate the extent of chromium and other heavy metals such as lead, iron, copper and manganese removal from tannery effluents in chemical precipitation processes using alum and liquid bittern. Comparing all the processes, finally a suggestion has been made for a suitable option to treat tannery wastewater which can be applicable to and affordable by developing countries like Bangladesh. Average Conc. SD 0.61

Parameter

Unit

Max Min Range

Table 2: Liquid bittern characteristics. Parameter pH Magnesium Unit mg/L Concentration 4.0 197.0

2. MATERIALS AND METHODS

Tannery wastewaters collected from a tannery factory named Lexco Ltd. In Hazaribagh, Dhaka have been characterized as shown in Table 1. Four samples were collected from the discharge point of chrome tanning unit where the factory authority discharged the effluent to the municipal drain and samples were analysed following Standard Methods (APHA, 1998). Table 1: Tannery Wastewater characteristics Parameter pH COD (K2CrO7 Method) Colour (Filtered) Turbidity Total Chromium Lead Iron Copper Manganese
*

Liquid bittern (LB) in clay form, was collected from a salt factory named Comilla Salt Industries situated at Old Bank Road, Narayangonj. The sediments produced in the processing of common salt is the source of liquid bittern which is rich in magnesium content. The pH and magnesium content of this LB were tested and presented in Table 2. LB solution was prepared to be used as a coagulant in the present study. For this purpose it was first dried at 1180C for seven days so that there was no moisture content in the sample. It was then grounded to finer particle size with mortar. Then 5 gm of the LB was weighed in a precision electronic balance and a 500 ml solution was made by adding distilled water in it and subjected to continuous stirring so that no particle could settle down till the jar test. A series of jar tests were conducted using alum and LB following standard procedure. Jar tests using LB were carried out at pH 10 since Ayoub et al. (2001) found that optimum pH occurred above 10 in case of LB coagulation process. pH was adjusted by using NaOH and Ca(OH)2 and measured using a pH meter. After flocculation, the flocs were allowed to settle down for a specified time such as 30 min, 6 hr and 24 hr. The supernatants were collected and analyzed for the final concentration of Fe, Mn Cu, Pb and Cr following standard methods (APHA, 1998) using Flame Atomic Absorption Spectrometer (AAS). Precipitation tests were also conducted to study the effectiveness of alkalis like NaOH and Ca(OH)2 to remove Cr and other heavy metals in the process of raising the pH. The procedure of precipitation test was same as that for jar tests. The only difference was that, in this case, no coagulants were added, only NaOH or Ca(OH)2 were added to maintain pH about 10.0. Then the supernatants were analysed for final concentration of pollutants after the specified settling time. The test conditions of the jar tests and doses of coagulants were presented in Table 3.

Unit mg/L Pt-Co NTU mg/L mg/L mg/L mg/L mg/L

Max Min Range 4.5 2.67 12450-1600 7125-2725 146-21 5736-385 6.5-0.37 20.3-5.2 1.8-0.127 3.8-2.4

Average Conc. SD 3.67 0.78 6866 4498 4803 1812 93 56 3317 2219 2.6 3.40 17.42 6.38 0.72 1 3.20

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Proceedings of the International Conference on Chemical Engineering 2008 ICChE2008, 29-30 December, Dhaka, Bangladesh

3. RESULTS AND DISCUSSION

3.1 Removal of chromium using liquid bittern Liquid bittern (LB) as an inexpensive source of magnesium, demonstrated its effectiveness in reducing heavy metal concentration from municipal wastewater (Ayob et al., 2001). In the present study jar tests were conducted using various doses of LB to see its effectiveness of removing Cr and other heavy metlas from tannery wastewater. Since the wastewater samples collected from disposal points at different dates had a large variation of chromium concentration (Table 1), therefore LB doses were selected within a range of 1 1000 mg/L depending upon the initial concentration of Cr in the samples (Table 3). Table 4 shows the final concentration of Cr and the % removal using LB after jar tests. Table 3: Test Conditions of Jar Tests Sample Coagulant Test Conditions ID Dose (mg/L) Sample 100 Coagulant: Liquid 1 Bittern 200 pH 10 using 300 NaOH 500 Setting Time: 24 h 1000 30 Coagulant: Liquid Bittern 50 Sample pH 10 using 2 NaOH 75 Setting Time: 6 h 1 Coagulant: Liquid Bittern 2 Sample pH 10 using 5 3 NaOH 10 Setting Time: 24 h pH 10 using NaOH Setting Time: 0.5 h, 6 h and 24 h Nil pH 10 using Sample NaOH 4 Setting Time: 0.5 h, 6 h and 24 h Coagulant: Alum pH = 6.5 using 60 NaOH Setting Time: 24 h From Table 4, it is clear that the concentration of chromium in the effluent after jar tests has been reduced substantially. Since the initial concentration of Cr was very high in the samples, about 99% removal was achieved in each case
*

although the final concentration in each sample after jar tests varied over a considerable range (0.053 2.03 mg/L). For sample 3, the average final concentration is around 0.06 mg/L which is much less than the industrial effluent discharge standard (ECR, 1997) whereas for Sample 1, although the removal efficiency is 99% but the final concentration exceeds the industrial effluent discharge standard which is 0.5 mg/L (ECR, 1997). Table 4: Removal of Chromium with varying doses of LB Initial Final LB % Sample Conc. Conc. dose Removal ID of Cr of Cr (mg/L) of Cr (mg/L) (mg/L) 1 0.053 99.99 2 0.063 99.98 Sample 385 3 5 0.066 99.98 10 0.063 99.98 30 0.463 99.99 Sample 3259 50 0.289 99.99 2 75 0.384 99.99 100 1.68 99.97 200 2.03 99.96 Sample 300 5736 1.78 99.97 1 500 1.35 99.98 1000 1.51 99.97 3.2 Removal of Pb, Fe, Cu, and Mn using liquid bittern Table 5 shows the removal of iron, lead, copper, and manganese in treating Sample 2 using liquid bittern as a coagulant. From Table 5, it has been observed that for Fe and Mn, about 99 % removal was achieved but removal decreased slightly for Pb (max 78%) and for Cu, removal was very poor compared to other metals (max 3%). From Table 5, it is found that the iron concentration in effluent is lower than the effluent discharge standard in surface water (2 ppm) as per ECR (1997). 3.3 Effectiveness of alum in treating tannery effluent An attempt was made to investigate the effectiveness of alum in the treatment of tannery effluent. For this, jar test was carried out using Sample 4 with an alum dose of 60 mg/L and pH 6.5. The dose and pH was such selected as it was found optimum from the previous study (Rahman, 1984). From the jar test result (Table 6)

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Proceedings of the International Conference on Chemical Engineering 2008 ICChE2008, 29-30 December, Dhaka, Bangladesh
it was found that alum was not effective in reducing the concentration of the pollutants. Removal efficiency of chromium in alum coagulation was found in this study about 34% and iron removal efficiency was found 19.5% which were much less compared to that of LB Table 5: Removal of Heavy Metals using LB LB Dose (mg/L) 50 Final Conc Percent Final Percent (mg/L) Removal Conc Removal (mg/L) Fe 20.31 <MDL >99 <MDL >99 Pb 6.54 0.92 86 1.47 78 Cu 0.12 0.11 0.85 0.10 3 Mn 3.60 <MDL >99 <MDL >99 Note: Method Detection Limits (MDL) of Fe = 0.02ppm, Mn = 0.016 ppm. 30 Table 6: Removal of Pollutant in Alum Coagulation Test description Sample Id #4 Alum dose: 60 ppm pH: 6.5 (using NaOH) Settling time: 24 hr coagulation. 3.4 Precipitation by NaOH and Ca(OH)2 and effects of settling time The effectiveness of NaOH and Ca(OH)2 was studied in the treatment of tannery effluent. Esmaeili et al. (2005) reported that the optimum pH range in the precipitation process using NaOH and Ca(OH)2 was 8.5 to 11.0. Therefore, jar tests were conducted for the Sample 4 using only NaOH and Ca(OH)2 to raise pH about 10. pH 10.0 was selected because, the optimum pH for LB is 10.0 and it would be logical to compare the performance of the different chemicals if tests were carried out at the same pH. Parameter Iron Manganes e Chromium Unit mg/L mg/L mg/L Initial Conc. 13.88 3.14 3888 Final Conc. 11.18 2.7 2566 % Removal 19.5 14.3 34.0 Parameter Initial Conc (mg/L) 75 Final Conc Percent (mg/L) Removal <MDL 1.43 0.10 <MDL >99 78 3 >99

Fig. 1: Final concentration of Cr in precipitation process at varying settling time. In the present study, initial chromium concentration of sample 4 was 3888 mg/L. Supernatants were collected after 30 min, 6 hr and 24 hr settling time and final concentration of Cr in the supernatants were measured (Fig. 1). It is observed from Fig. 1 that up to 6 hour settling time, NaOH worked better than Ca(OH)2. However after 24 hour settling time, final concentration reduced from 3888 mg/L to about 1.47 mg/L and 1.66 mg/L using NaOH and

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Proceedings of the International Conference on Chemical Engineering 2008 ICChE2008, 29-30 December, Dhaka, Bangladesh
Ca(OH)2 respectively which is not a significant variation between two alkalis. Therefore, it can be said that for a longer settling time, both the alkalis are almost equally effective in removing Cr from the effluents. 3.5 Comparison between the performance of Coagulation with LB and Precipitation with NaOH It has been found from the study that both the coagulation test with LB and precipitation test with NaOH can remove Cr (above 99%) effectively (Mahmood, 2008). In coagulation test NaOH was also used to raise pH about 10. Therefore a question may arise whether LB or alkaline reagent NaOH is the causal factor in removing Cr. Fig. 2 shows that for the same sample (sample 2), final concentration of Cr becomes 0.3 ppm after 6 hr settling time in coagulation with LB whereas in precipitation with NaOH (and without LB) it becomes 5.82 for the same settling time. Again for sample 3, the average final Cr concentration in the treated water is 0.06 ppm in coagulation with LB and 0.31 ppm in precipitation test without LB (Fig. 2). Therefore it can be said that coagulation with LB is more effective in removing Cr than precipitation with NaOH in the treatment process. from the study, the following conclusions can be drawn: Liquid bittern is found effective in removing chromium from tannery effluent. About 99% removal efficiency can be achieved using LB. The removal of iron, copper, lead, and manganese is also found effective in the LB coagulation process. Precipitation by NaOH/Ca(OH)2 is found to be effective in removing chromium. Therefore using only alkaline agents like NaOH to raise pH in the range of 8.5 to 10 can offer a low cost and effective chemical treatment option for treating tannery wastewater. Alum is not found as effective as LB or alkaline reagent in the treatment of tannery effluent. Coagulation with LB is found to be more effective than precipitation with NaOH. Therefore enhanced Cr removal can be achieved by using LB.

REFERENCES
1. APHA, AWWA, and WEF (1998), "Standard Methods for the Examination of Water and Wastewater", Washington DC, 19th Edition. 2. Ayoub, G. M., Semerjian, L., Acra, A., Fadel, M.El. and Koopman, B. (2001), Heavy Metal Removal by Coagulation with Seawater Liquid Bittern, Journal of Environmental Engineering, ASCE, Vol 127, Page 196 207. 3. Bangladesh Environment (2004), Peoples Report 2002-2003, Published by Unnayan Shamannay. 4. Environment Conservation Rules, (1997) (ECR, 97), Gazette Notification, 27 August, Ministry of Environment and Forest, Government of the Peoples Republic of Bangladesh. 5. Esmaeili, A., Alireza, M. and Reza, V. (2005), Chromium (III) Removal from Tannery Wastewater by Precipitation Process, American Journal of Applied Sciences 2(10), Science Publication. 6. Mahmood S.O.A. (2008), Chemical Treatment Options for Tannery Wastewater, M Eng. Thesis (Environmental), BUET, Dhaka.

Fig. 2: Comparison between coagulation with LB and precipitation with NaOH.

4. CONCLUSION
The main objective of the study was to find out a cost effective chemical treatment option for the tannery wastewater. Based on the results obtained

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Proceedings of the International Conference on Chemical Engineering 2008 ICChE2008, 29-30 December, Dhaka, Bangladesh
7. Rahman, M. H. (1984), "A Study on Tannery Waste Treatment", MSc. Thesis, Department of Civil Engineering, BUET, Dhaka. 8. Rao, M.N. and Datta, A.K. (1987), "Waste Water Treatment", 2nd Edition, Oxford & IBH Publishing Co. Pvt. Ltd., Delhi.

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