Treatment of Textile Wastewater Containing Black Sulfur Dye Using Ceramic Membrane Based Separation Process

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Abstract
Ceramic Membrane based separation processes are unique considering the extent of purification, efficiency of the process because of faster permeation rate and extent of eco-friendliness. Textile industry involves processing of fabric and consumes about 100 litres of water for every ton of cloths processed and produces extremely polluting effluents. In the present study, textile wastewater was collected from an industry located at of Mahestala, Budge Budge in Kolkata Metropolitan Area, which is under extreme industrial pollution. The low cost ceramic membranes module developed by CG & CRI were used for the treatment to combat this situation. The effluent containing black sulphur dye and composite sulphur dye was pretreated using aluminum sulfate as coagulant and a polymer based flocculant at varying doses and at various pH of the solution. The supernatant was collected after overnight settling and treated further by MF process. Microporus alumina support and different coated membranes in a tubular single channel module configuration (filtration area 0.0178 m2) was used. Experiments were carried out at transmembrane pressure of 1.0 kg/cm2. The efficiency of the separation process was evaluated in terms of the COD, color, turbidity, TDS, pH, conductivity etc. Key-words: textile effluent, reactive dyes, sulfur dyes, ceramic membrane, microfiltration, coagulation.

Introduction
Ceramic Membrane based separation processes are unique considering the extent of purification, efficiency of the process because of faster permeation rate and extent of eco-friendliness. Textile industry involves processing or converting raw material/fabric into finished cloth/materials employing various processes and consumes large quantities of water and produces extremely polluting effluents. In a typical dyeing and finishing mill, about 100 litre of water is consumed on the average for every ton of cloths processed. Textile dyeing and finishing processes generate a large quantity of colored wastewater containing residual dyes, textile auxiliaries and chemicals. Effluents from the textile industry usually contain high concentrations of organic compounds and are characterized by strong colour as well as high COD values. Dyes from the dyeing operations are the major source of color in textile effluents. Among all the technological classes of dyes applied to the dyeing of various textile fibres, the lowest exhaustion level is exhibited by the reactive dyes for cellulosic fibres since they have a low substantivity to the substrate and are very sensitive to hydrolysis at the required alkaline dyeing conditions [1]. Dye wastewater usually consists of a number of contaminants including acids, bases, dissolved solids, toxic compounds and fixing compounds characterized by its high chemical oxygen demand (COD), and color. In the present study, textile wastewater was collected from an industry located at of Mahestala, Budge Budge in Kolkata Metropolitan Area. The entire area of Mahestala is under extreme industrial pollution. To combat this situation, the Govt. of West Bengal is about to set up a Textile Park there which will be having ETP with all advanced treatments. This prompted the present research group to quest for an appropriate green Separation technology to treat dye wastewater for its safe reuse. Considering the ecofriendliness and user friendliness low cost ceramic

membranes module developed by CG & CRI were used for the purpose. Two types of highly polluted wastewater were chosen: i) effluents from sulfur dyeing process of garment processing industries and ii) effluents from the reactive dyeing process of hosiery dye houses. The effluents were treated using a single stage process as well as a two-stage process and performance of both the processes were compared in terms of the permeate quality and the permeate flux. In the single stage process, the effluents were directly treated by cross-flow microfiltration (MF) process. In the two-stage process, the effluents were first pretreated using aluminum sulfate as coagulant and a polymer based flocculant at varying doses and at various pH of the solution. The supernatant was collected after overnight settling and treated further by MF process. Microporus alumina support and different coated membranes in a tubular single channel module configuration (filtration area 0.0178 m2) was used. Experiments were carried out at transmembrane pressure of 1.0 kg/cm2. The efficiency of the separation process was evaluated in terms of the COD, color, turbidity, TDS, pH, conductivity etc.

Experimental
The textile effluents were characterized in terms of color, turbidity, pH, TDS, conductivity, COD etc. shown in Table1. The effluents were treated taking two approaches. In the first approach (process 1), the effluents were initially pretreated and thereafter treated in the microfiltration unit. In the second approach (process 2), the effluents were treated directly by microfiltration (without pre treatment). The scheme of the treatment process is shown in Fig. 1. The pretreatment of the effluents prior to the MF process was carried out supplied by Clariant Chemicals (India) Ltd. in the varying dose of 0.6-2.0 ml/l with or without combination of Aluminum sulfate, Magnesium sulfate, Ferric chloride, Ferric sulfate, Calcium carbonate [All supplied 0.1 g/l by Merck.] The pre treatment was carried out at various pH (6-12). The solution after adding desired amount of the coagulant was stirred at about 200 rpm for 5 minutes. The solution was placed in a graduated cylinder and kept for overnight settling. Supernatant was collected next morning and analyzed in terms of the turbidity, TDS, conductivity, pH, UV-Vis. spectra etc. Based on the results of the jar test, pretreatment of the bulk volume of the effluent was carried out taking the optimum dose of the chemicals and at solution pH of 7.0. The supernatant of the pre treatment process was collected and treated further in the ceramic membrane based microfiltration unit. Microporus alumina support (KM/B11/30) in a tubular single channel configuration was used. The filtration area of the membrane was 0.0178 m2. Physical properties of the porous ceramic tube are given in Table 2. Experiment was conducted taking 4-4.5 lit feed solution, at transmembrane pressure of 1.0 kg/cm2. Permeate samples were collected at specific time intervals and analyzed. Permeate flux was measured continuously. The duration of each experiment was about 60 min.

Results and Discussions

Turbidity Reduction Turbidity of the permeate sample of black sulfur effluent collected after 1 hour of microfiltration decreases from 5912 NTU to 1.10 NTU in process 1 (MF after PT), and in process 2 (direct MF), the turbidity of permeate decreases to 11.9 NTU. Colour Removal: Colourless permeate samples were obtained for the composite sulfur dye effluent. In black sulfur dye effluent, trace amount of colour remains in the permeate samples of both processes:

When the effluent was treated directly through microfiltration. When the effluent was first pretreated and then microfiltration was carried out using porous ceramic membrane 1 and 2.

Chemical Oxygen Demand: The chemical oxygen demand in mg/l in black sulfur dye effluent is 3910 mg/l. After the membrane study of pretreated permeate with aluminum sulfate the COD removal was found to be 700 mg/l. The %COD removal was found to be 78.12%. Total Suspended Solids: The total suspended solids of black sulfur effluent with pH variation when treated with aluminum sulfate, was found to be ranging from 76% to 80%. When treated with ferric chloride, the range was found to be in between 75% to 80%. When treated with ferric sulfate and lime, the range was found to be in between 76% to 79%. During membrane study, when the permeate was treated with aluminum sulfate the removal was 99%.

Conclusion
Considerable turbidity removal was achieved for all the effluents (>99%). In the combined process of pre treatment followed by MF, colour removal was reasonable for most of the effluents, except the black sulphur effluent . The Pre treatment process results in better permeate flux compared with the direct CMF process.

References
[1] S. Bandyopadhyay, S. Ghosh, G.C.Sahoo and H.S. Maiti, Treatment of a Textile Dye-Bath Effluent Using Coagulation Followed by Microfiltration. In Proceedings of Water 2006, NEERI, International Workshop on R&D Frontiers in Water and WastewaterManagement [2] S. M. Burkinshaw, S. N. Chevli, D. J. Marfell, The dyeing of nylon 6,6 with sulphur dyes, Dyes & Pig. 45 (2000) 65-74. [3] G. Vera, V. Aleksandra, S. Marjana, Efficiency of the coagulation/flocculation method for the treatment of dyebath effluents, Dyes and Pig. 67 (2005) 93-97. [4] C. Fersi, L. Gzara, M. Dhahbi, Treatment of textile effluents by membrane technologies. Desal. 185 (2005) 399-409.

Figure Legends:
Table1: Characterization of the raw effluents

Sl No EFFLUENT NAME

TDS (g/dm3) 20.2

pH

Turbidity (NTU) 5912

Conductivity (mS/cm) 36.9

1. Black sulphur effluent (United Laundry India Pvt Ltd.)

12.07

2. Composite sulphur effluent (United Laundry India Pvt Ltd.)

1.336

7.75

398

2.87

Table 2 :Properties of the ceramic element Dimension Bulk density Water absorption Apparent porosity

200 mm X 36 mm X 28 mm (L, OD, ID)

2.12 g/cc

17.01%

36.01%

Fig 1.

450 400 350 300

Black sulfur effluent (UL) after PT Black sulfur effluent (UL) raw Composite sulfur effluent (UL) after PT

Flux (LMH)

250 200 150 100 50 10 20 30 40 50 60

Time (min)

Fig 2.

120 110 100 90 80

Composite Effluent 2 (SB) after PT Composite Effluent 2 (SB) raw

Flux (LMH)

70 60 50 40 30 20 10 0 0 10 20 30 40 50 60 70 80 90

Time (min)

Feed (Raw Textile Effluent) Characterization (Turbidity, Multiparameter, UV-Vis. Spectra, COD, Particle size) Cross flow Microfiltration Permeability Test, Characterization of Permeate (Multiparameter, Turbidity, COD, UV-Spectra)
Fig.3

As Such

Pre Treatment