PII: S0043-1354(01)00015-X

Wat. Res. Vol. 35, No. 13, pp. 31473152, 2001 # 2001 Elsevier Science Ltd. All rights reserved Printed in Great Britain 0043-1354/01/$ - see front matter

DYE REMOVAL FROM TEXTILE DYE WASTEWATER USING RECYCLED ALUM SLUDGE
W. CHU*
Department of Civil and Structural Engineering, Research Centre for Urban Environmental Technology and Management, The Hong Kong Polytechnic University, Hung-Hom, Kowloon, Hong Kong (First received 20 December 1999; accepted in revised form 30 October 2000) Abstract}The removal of dyes from textile dying wastewater by recycled alum sludge (RAS) generated by the coagulation process itself was studied and optimized. One hydrophobic and one hydrophilic dye were used as probes to examine the performance of this process. It was found that RAS is a good way of removing hydrophobic dye in wastewater, while simultaneously reducing the fresh alum dosage, of which one third of the fresh alum can be saved. The back-diusion of residued dye from the recycling sludge is detected but is easily controlled as long as a small amount of fresh alum is added to the system. The use of RAS is not recommended for the removal of hydrophilic dyes, since the high solubility characteristics of such dyes can cause deterioration in the water quality during recycling. # 2001 Elsevier Science Ltd. All rights reserved Key words}alum, dye, hydrophilic, hydrophobic, recycle, sludge

INTRODUCTION

Textile industries use large amounts of water and chemicals for nishing and dying processes. The chemical structures of dyes vary enormously, and some have complicated aromatic structures that resist degradation in conventional wastewater treatment processes because of their stability to sunlight, oxidizing agents, and microorganisms (Mishra and Tripathy, 1993). The removal of dyes from industrial euent is a major concern in the textile industry, with the increase in stringent legislation. Dye wastewater usually consists of a number of contaminants, including acids, bases, dissolved solids, toxic compounds, and color. Color is the most noticeable contaminant even at very low concentrations, and it needs to be removed or decolorized before the wastewater can be discharged. Various chemical processes have been used to remove color from textile dying wastewater. For example, Chu and Ma (1997) investigated the UV decoloration of sixteen (16) commercial dyes in the aqueous phase, where the removal rates of dyes ranged from 8 (anthraquinone dyes) to 98% (polyazo dyes) depending on the dye structures. A similar alternative is the use of UV/ H2O2 to oxidize dye wastewater (Ince and Gonenc, 1997). Fentons reagent was also used for dye decoloring, about 88% of dye being removed at pH 3.5 (Kuo, 1992).
*Tel.: +852-2766-6075; fax: +852-2334-6389; e-mail: cewchu@polyu.edu.hk

In addition to chemical oxidation, chemical coagulation by the use of inorganic coagulants such as alum, magnesium carbonate, ferrous sulfate, and vermiculite is another feasible way of removing color from dye wastewater. Judkins and Hornsby (1978) investigated the treatment of textile dye waste with magnesium carbonate. The results indicated that the removal of color was good with vat and sulfur dyes, but less eective on dispersed dyes. Mehrota et al. (1995) reported that 1000 mg/L magnesium carbonate removed 92% of color from vat dye and sulfur dye euent at pH 10, and 38% of color from basic dye euent at pH 11. A lower color removal of 75% was observed in vat dye euent where 14 000 mg/L of ferrous sulfate was used as the coagulant at an optimum pH of 10. Choi and Cho (1996) evaluated the performance of vermiculite extract solution as a coagulant for extracting color from dye wastewater. This process generated less sludge at lower coagulant doses than processes using conventional inorganic coagulants, and its performance increased with increasing temperature and agitation intensities. Although the use of coagulant for dye removal is applicable, huge amounts of chemical sludge are generated by treatment plants every day. The proper disposal, regeneration, or reuse of waste sludge has become a signicant environmental issue. An alum sludge recycling system consisting of sludge separation, alum solubilization, impurity screening, and alum reuse was reported feasible (Wang and Yang, 1975) and cost-eective (Ben et al., 1976; Krofta and Wang, 1988). A full-scale operation in the city of

3147

3148

W. Chu tion process. The standard coagulation procedure involved 1 min of rapid mixing at 80 rpm, followed by 20 min of slow mixing at 30 rpm, and 10 min of settling. A UV Spectronic Genesys-2 Spectrophotometer from Milton Roy1 was used to quantify the remaining color in the supernatant layer after coagulation. The preparing of waste alum sludge is exactly the same as the typical jar test mentioned above, except that the settled wet sludge was dewatered and collected by gravity, and reused in the next jar test with or without the addition of fresh alum. The dose of RAS was quantied by the dry weight of total suspended solid in the slurry at 1058C.
RESULT AND DISCUSSION

Durham, USA, showed that an overall recovery in a dilute liquid alum was about 75% of the fed alum with a decant-drying bed (Bishop et al., 1987). The operation of alum recovery, however, is extremely complicated. For example, conditions that will produce the most ecient recovery of aluminum from sludge may vary from day to day due to the organic substances contained in sludges and/or dissolved from sludges that might interfere with the function of the recovered aluminum solution as a coagulant (Hanzon, 1975). Also, Hawkins (1972) reported that the accumulation of magnesium hardness in the sludge would cause a signicant increase of specic resistance in the lterability of the sludge after multi-reuse. Consequently, reusing the alum sludge instead of recovering the alum itself could be a better strategy to fully utilize the coagulation capacity of alum (or its sludge) and to eliminate the operational cost required for alum recovery. Limited by the deciency of operational experience, to reuse waste alum sludge in potable water treatment may not be appreciated and may easily violate drinking water standards. Under these circumstances, the reuse of RAS to the less sensitive wastewater treatment process may be favorable. By recycling the RAS into the occulation tank, the fresh coagulant dose can be reduced, as can the time required for oc formation (i.e. a smaller tank size). It has recently been reported that the use of RAS to remove heavy metal from a wastewater stream is feasible (Chu, 1999). In this study, the removal of dyes with hydrophobic or hydrophilic characteristics by coagulation with the aid of RAS was investigated.

Removal of hydrophobic dye Various pH ranges for removing hydrophobic dye (Dianix Blue) from wastewater were studied with a fresh alum concentration of 100 mg/L and a polymer concentration of 31.25 mg/L (shown in Fig. 1), where the alum sludge (dry TSS weight of mixed liquid) generated in the process was also reported. The pH for maximum dye removal (85%) was found to be 9.13, and a relatively high yield of alum sludge (60 mg/L) was observed. Since 85% (out of 12.5 mg/ L) of the dye is transferred from the liquid phase to the solid phase, 31.25 mg/L of the polymer is used for bridging, and every 100 mg of alum usage will generate 26 mg of alum sludge (Al(OH)3, see equation (1)), theoretically, the total weight of sludge should be around 67 mg/L, which is quite close to the observation yield of 60 mg/L. The small dierence suggests that more than 90% of the coagulant (alum and polymer) will reside in the sludge, which ensures the feasibility of reusing waste alum sludge in the recycling process. Al2 SO4 3 14H2 O 6OH

METHODOLOGY

! 2AlOH3 3SO2 14H2 O 4

Two commercial dyes were selected to examine color removal performance using recycled alum sludge. To minimize interference due to uncontrollable and uctuating components in actual wastewater from the dying process, synthetic wastewater containing 12.5 mg/L hydrophobic dye or 125 mg/L hydrophilic dye was used to examine the recycling performance of alum sludge. The selected hydrophobic dye was Dianix Blue FBL-E, which is an anionic disperse dye of a deep blue color and maximum absorption wavelength of 568 nm. It contains the azo group (NN) and acetyl group (OCOCH3) in its molecules. The hydrophilic dye was Ciba-corn Yellow P-6GS, an anionic direct dye of a yellow color and maximum absorption wavelength of 475 nm. It contains the amine group (NH2). Aluminum sulfate (alum), Al2(SO4)318H2O, was employed as a coagulant which reacts with alkalinity in wastewater to form insoluble aluminum hydroxide sludge. A synthetic cationic polyelectrolyte was also used in all experiments, and proved useful in increasing the charge density in the diuse layer of the metal hydroxide particle, reducing its double-layer thickness and the corresponding repulsive forces of ne particles. In additions, the use of a polymer can help the formation of more rigid sludge and has no eect on the solution pH (Chu, 1999). Therefore, a constant polymer dosage of 31.25 mg/L was used in this study. A Stuart scientic occulator SW1, equipped with six 500 ml Pyrex1 breakers, was used to simulate the coagula-

The change in color removal due to changing alum concentrations was investigated, therefore, at an

Fig. 1. Removal of Dianix Blue FBL-E by alum coagulation and the generation of alum sludge (in terms of dry TSS) at various pH vaules. The fresh alum concentration, dye concentration, and polymer concentration are 100, 12.5, and 31.25 mg/L.

Dye removal by RAS

3149

initial pH of 9.13, as shown in Fig. 2, where the optimum alum concentration was 75 mg/L and the dye removal rate was 88%. A major drop in the dye removal rate to 48% was observed as the fresh alum increased to 125 mg/L. This is mainly due to the restabilization of dye particles, which can be justied by the observed sludge yield curve. Theoretically, hydrophobic (disperse) dyes in most cases have an extremely low solubility in water, and they can be treated as colloidal particles. Upon coagulation at suitable doses, agglomeration occurs and dye particles are destabilized (as a consequence of van der Waals force attraction, see Fig. 3(b)) and can be removed by gravity settling. However, if there is an overdose of alum (125 mg/L in this case), a repulsive force is established between the dye particles due to the accumulation of positive charges on the particle surface, and this cause restabilization (Fig. 3(c)). During the restabilization stage, the agglomerated

Fig. 2. Removal of Dianix Blue FBL-E by alum coagulation at various fresh alum concentrations. The initial pH, dye concentration, and polymer concentration are 9.13, 12.5, and 31.25 mg/L.

particles (i.e. dyealum particles) are suspended in solution and can not be removed by gravity settling. However, the agglomerated and restabilized particles can still be removed by ltration, as indicated in the TSS measurement. In Fig. 2, a smooth massyield curve is observed, indicating that dye particles associate with coagulants and that the particle sizes are larger than their origin. (Since the original dye particles are too small to be ltered, after the coagulation, the dye can be captured by ltration). This observation supports the theory that the lowered removal rate of the dye at 125 mg/L of alum is mainly due to restabilization since the coagulated particles are lterable but not settlable. When the alum dosage was increased to 150 mg/L, the dye removal rates increased again (to 75%) because of the accumulation of counter-ions (sulfate (SO)2) on 4 the particle surface, resulting in neutralization and destabilization, see Fig. 3(d). The use of 75 mg/L fresh alum (at the optimal condition) in the treatment process may not be attractive because of high chemical and operational costs. Since the coprecipitation between dye particles and recycled alum sludge (RAS) might lower the demand for fresh alum, a series of alum recycling studies was performed to justify this presumption. Various fresh alum concentrations (from 0 to 220 mg/ L) were added to the coagulation system as the level of RAS (the waste sludge generated from its previous coagulation) was kept at 75 mg/L. The results are shown in Fig. 4. By comparing Figs 2 and 4, the advantages of using RAS can be interpreted in two ways. First, while keeping the optimum dye removal rate at 88%, the amount of fresh alum required was reduced from 75 mg/L (without using RAS) to 50 mg/ L (with the use of RAS). Secondly, if the removal rate of the system using RAS is compared to that without using RAS (Fig. 2), the dye removal can be increased from 53 to 88% by using the same dose of fresh alum at 50 mg/L. Obviously, the additional 35%

Fig. 3. Schematic diagram of alum-treated dye particles. (a) Negatively charged dye particle; (b) particle destabilized by charge neutralization; (c) particle restabilized by excess alum hydrolyses species; and (d) destabilization by adsorption of sulte ions.

3150

W. Chu

Fig. 4. Removal of Dianix Blue FBL-E by 75 mg/L recycled alum sludge with the help of various fresh alum concentrations. The initial pH, dye concentration, and polymer concentration are 9.13, 12.5, and 31.25 mg/L.

Fig. 5. Removal of Dianix Blue FBL-E by various concentration of recycled alum sludge. The initial pH, fresh alum concentration, dye concentration, and polymer concentration are 9.13, 50, 12.5, and 31.25 mg/L.

(i.e. 8853%) of dye removal is exclusively contributed by RAS. This observation suggests that RAS is a good way of removing hydrophobic dye in wastewater while simultaneously reducing the fresh alum dosage. Back-diusion mechanism and control The results of dye removal rates in Fig. 4, however, were found to uctuate at certain fresh alum doses, where restabilization zones with negative dye removals were found. A further examination was carried out to clarify the reasons for water-quality deterioration in those areas. For this, the removal of dye solely by using recycled alum sludge without the addition of fresh alum was examined, and the result is incorporated in Fig. 4. The dye removal rate was 31% if 75 mg/L of RAS was used without the addition of fresh alum. Since the only source that may result in water contamination is the RAS itself, it is believed that some of the dye materials previously trapped in the RAS will be diused back into the aqueous phase and cause deterioration of the water quality. In addition, this back-diusion mechanism is associated with the overdose-restabilization mechanism (from the fresh alum), and results in several restabilization zones with negative removal rates at certain higher fresh alum doses. Judging by Fig. 4, the mass-yield of TSS also declined at those restabilization zones, indicating that the dye released from the RAS due to back-diusion belongs to free dye and is no longer associated with alum sludge. Fortunately, back-diusion can be eectively controlled if fresh alum is added to the recycling system. In Fig. 5, various doses of RAS (30200 mg/ L) were added to the coagulation process, with the addition of 50 mg/L of fresh alum. The increment of RAS, despite having a slight eect on the further promotion of dye removal rates (the removal rates

generally remain within the range of 8587%), will cause no deterioration in the water quality. Fresh alum now removes not only the dye in the aqueous phase but also the dye back diused from the RAS. From this nding, it is concluded that the addition of fresh alum is necessary in wastewater treatment to trap and remove the free dye particles resulting from back-diusion, and to avoid the re-contamination of water. In addition, as no restabilization was observed in Fig. 5, it can be concluded that the restabilization will only result from an overdose of fresh alum, not RAS. Stoichiometrical calculation for application The RAS apparently served as condensation nuclei, and the dye particles were enmeshed as the precipitate was settled by the sweep-oc mechanism. When a metal salt Al2(SO4)3 is used as a coagulant in concentrations suciently high to cause precipitation of a metal hydroxide (i.e. Al(OH)3 as shown in equation (1)), colloidal dye particles are entrapped in the amorphous aluminum hydroxide solids during the slow mixing. The nucleation of the precipitate usually occurs on the surface of alum ocs, leading to the growth of an amorphous precipitate and the entrapment of lead hydroxide in this amorphous structure. Theoretically, both fresh alum sludge (FAS) and RAS could contribute to the trapping of dye particles as shown in equation (2). aAlOH3
FAS

bAlOH3

RAS Dye

! Dye particles trapped in alum sludge

When dye removal rates were kept above 85% (to avoid the unpredictable ranges of restabilization), and the initial concentration of dye and initial pH were 12.5 mg/L and 9.13, a stoichiometrical formula of equation (2) resulted. The mole numbers of FAS

Dye removal by RAS

Table 1. The mole numbers of FAS and RAS required to remove one mole of dye % removal 85.2 85.5 86.0 86.5 87.0 Mol of FAS 5.51 5.49 5.46 5.43 5.40 Mol of RAS 31.51 41.87 62.43 74.49 82.29 RAS/FAS 5.72 7.62 11.43 13.72 15.24

3151

RAS+FAS 11.23 13.11 16.89 19.15 20.64

Fig. 6. Removal of Ciba-corn Yellow P-6GS by alum coagulation at various pH. The fresh alum concentration, dye concentration, and polymer concentration are 100, 125, and 31.25 mg/L.

Fig. 7. Removal of Ciba-corn Yellow P-6GS by alum coagulation at various fresh alum concentrations. The initial pH, dye concentration, and polymer concentration are 8.80, 125, and 31.25 mg/L.

and RAS required to remove 1 mol of hydrophobic dye are summarized in Table 1, where the values of a and b ranged from 5.51 to 5.40 and 31.51 to 82.29. Basically, the dye removal is proportional to the total alum sludge input (RAS+FAS), indicating that both fresh and recycled alum sludge play important roles in removing dye particles. In addition, the higher the RAS/FAS ratios, the higher the removal rates, suggesting that the operation of the coagulation process with the use of RAS and FAS in dye removal is quite exible. As long as the RAS is maintained at higher levels, precise dose control of RAS is unnecessary. Mechanism verication by using a hydrophilic dye Based on the above ndings, the hypothesis of using colloidal particles to characterize the hydrophobic dye in the back-diusion mechanism is practicable. However, this assumption can be further veried if the control of back diusion from RAS by FAS is in ruins for sources with non-colloidal particle properties, such as a water-soluble dye. A typical hydrophilic dye (Ciba-corn Yellow P-6GS) therefore was selected to perform similar coagulation tests. From Figs 6 and 7, the optimal pH and fresh alum dosage for coagulation were determined to be 8.87 and 75 mg/L. The highest performance for dye removal was 55%. In the presence of 100 mg/L of RAS, the required fresh alum dosage increased from

Fig. 8. Removal of Ciba-core Yellow P-6GS by 100 mg/L recycled alum sludge with the help of various fresh alum concentrations. The initial pH, dye concentration, and polymer concentration are 8.80, 125, and 31.25 mg/L.

75 to 175 mg/L in order to maintain an optimal treatment, while the optimal dye removal still dropped from 55 to 51% compared to the system without using RAS (see Figs 7 and 8). Apparently, the downgrading of removal eciency is likely due to the following reasons. First, as hydrophilic dye has higher water solubility, the adsorbed dye in the alum sludge from the previous coagulation cycle can easily be diused back into the fresh solution and

3152

W. Chu

contaminate the water quality. Second, since the capture ability of hydrophilic dye by fresh alum is relatively low, the recapture rate of the re-dissolved dye from the RAS is likely to be slower than the rate of back-diusion. This assumption is evident from the negative dye removal (42%) shown in Fig. 8, where 50 mg/L of fresh alum cannot compensate for the water deterioration due to the dye back-diusion from 100 mg/L of RAS. Therefore, the application of RAS to improve the coagulation process is limited to hydrophobic contaminants, and is not eective for hydrophilic ones.
CONCLUSIONS

philic dyes due to the uncontrollable back-diusion of pre-resided dye in the RAS.
Acknowledgements}The author is grateful to the Hong Kong Polytechnic University Research Fund for their nancial support.

REFERENCES

About 88% of hydrophobic dye, Dianix Blue, can be removed from wastewater with an alum concentration of 75 mg/L at pH 9.13. If 75 mg/L of RAS is used during the coagulation process, the fresh alum dose can be reduced to 50 mg/L to achieve a similar dye removal rate by the sweep-oc mechanism. Restabilization of dye materials is observed in the coagulation process at high fresh alum concentrations. If the RAS sludge is recycled during restabilization, negative dye removals will be observed due to the back-diusion of dye that previously resided in the alum sludge. However, the back-diusion mechanism can be eectively controlled if fresh alum is added to the recycling system. Restabilization is shown only to result from an overdose of fresh alum, not from the overdose of RAS, so the concentration of RAS used in the process needs no precise control, which makes the operation of RAS a simple add-on process to existing treatment works. However, the use of RAS is not feasible for the treatment of hydrophilic dyes. It shows no promotion of dye removal; instead, more fresh alum (about triple the amount) is needed to overcome the back-diusion of dye from the RAS in order to prevent water deterioration. The degrading of the removal eciency for hydrophilic dye is presumably due to the high water solubility of the dye and the lower rate of alum recapture than that of dye back-diusion. In conclusion, the use of RAS to remove hydrophobic dye from wastewater is quite ecient and feasible, but the process is not suitable for hydro-

Ben H. H., Chen R. M., King P. H. and Randall C. W. (1976) Alum recovery from representative watertreatment plant sludges. J. Am. Water Works Assoc. 68(4), 204208. Bishop M. M., Rolan A. T., Bailey T. L. and Cornwell D. A. (1987) Testing of alum recovery for solids reduction and reuse. J. Am. Water Works Assoc. 79(6), 7684. Choi Y. S. and Cho J. H. (1996) Color removal from dye wastewater using vermiculite. Environ. Technol. Lett. 17(11), 1169(12). Chu W. (1999) Lead metal removal by recycled alum sludge. Water Res. 33(13), 30193025. Chu W. and Ma C. W. (1997) Eects of UV-decoloring of aromatic dyes with dierent chemical structures. Toxicol. Environ. Chem. 63, 247255. Hanzon B. D. (1975) Some problems with aluminum recovery and reuse water treatment plant. AWWA 95th Annual Conference Minneapolis, June 813, pp. 517. Hawkins F. C. (1972) Water treatment sludge ltration studies. NTIS Report Pb-237 680, 72. Ince N. H. and Gonenc D. T. (1997) Treatability of a textile azo dye by UV/H2O2. Environ. Technol. Lett. 18(2), 179(7). Judkins J. F. and Hornsby J. S. (1978) Color removal from textile dye waste using magnesium carbonate. Water Pollut. Control Fed J. 50(11), 2446(11). Krofta M. and Wang L. K. (1988) Recycling of lter backwash water and alum sludge for reuse in water treatment plants. National Water Supply Improvement Association Biennial Conference, San Diego, CA, July 31 August 4, vo1. 1, no. (46). Kuo W. G. (1992) Decolorizing dye wastewater with Fentons reagent. Water Res. 26(7), 881(6). Mehrota R., Prasad S. and Srivastava B. K. (1995) Removal of color from dye-house euents by physicochemical processes. Appropriate Waste Management Technology for Developing Countries Third International Conference India, February 2526. vol. 2, p. 617(13). Mishra G. and Tripathy M. (1993) A critical review of the treatments for decolorization of textile euent. Colorage 10, 3538. Wang L. K. and Yang J. Y. (1975) Total waste recycle system for water purication plant using alum as primary coagulant. Res. Recovery Conserv. 1, 6785.