Desalination 126 (1999) 219–226

Treatment of an industrial effluent by reverse osmosis
Antonio Pérez Padillaa*, Eduardo L. Tavanib
Instituto de Investigaciones en Tecnología Química (INTEQUI), Universidad Nacional de San Luis, CONICET, CC 290, 5700 San Luis, Argentina Fax +54 (2652) 26711; email: apadilla@unsl.edu.ar b Centro de Tecnología de Recursos Minerales y Cerámica (CETMIC), Comisión de Investigaciones Científicas de la Provincia de Buenos Aires, CONICET, CC49, 1897 M.B. Gonnet, Argentina
a

Abstract The treatment of tanning wastewater was studied by means of reverse osmosis and ultrafiltration. Tests were carried out on laboratory scale using membranes of polyamide (reverse osmosis) and of polysulfone (ultrafiltration). The evaluation of the system was performed by chemical analysis, pH measurements and visible spectrophotometry. Effects of the protein contained in the industrial effluent, the applied pressure and the feed temperature on the permeate flux were analyzed. The polyamide membrane used allowed us to obtain permeates with a low chromium (III) content = (7–10 mg/L) but with appreciable amounts of SO4 (1–3 g/l), Cl (9–14 g/L) and Na+ (5–10 g/L). The presence of chromium (III) polymers was determined in the original effluent and in the concentrates obtained by reverse osmosis. Finally, it was established that during the operation of reverse osmosis, the transport of H+(H3O+) from the concentrate to the permeate was produced. Keywords: Tanning wastewater; Reverse osmosis; Ultrafiltration; Chromium (III); Recovery; Leather

1. Introduction Leather is a material that has a reasonable mechanical resistance, good chemical stability and acceptable thermal behaviour. This material is obtained by means of specific reactions among
*Corresponding author.

carboxylic groups of the protein fiber network of animal skin (collagen) and tanning reagents. The basic chromium (III) sulfate [Cr(OH)(H2O)5SO4] is a primary tanning agent widely used at the present time [1]. During the tanning process, large amounts of wastewater; sludge; and solids containing chromium, sodium, chloride and sulfate are

Presented at the Conference on Desalination and the Environment, Las Palmas, Gran Canaria, November 9–12, 1999. European Desalination Society and the International Water Association. 0011-9164/99/$– See front matter © 1999 Elsevier Science B.V. All rights reserved

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produced. In all these wastes the chromium is present only in the trivalent form since the tanning process not generate chromium (VI) [1,2]. Both oxidation states of the chromium are abundant in environment. Chromium (III) is the form most stable and its presence is necessary, in small amounts, for human health. Chromium (VI) is found in several commercial products and its presence may have immediate adverse effects for human health [2,3]. Chromium (VI) is transformed rapidly to chromium (III) under environmental normal conditions, with only contamination risks near direct emissions. However, under very specific conditions, the oxidation of trivalent to hexavalent form may also occur [4,5]. Technical regulations for disposal of wastes containing chromium (III) are stringent and are based on the probable presence of chromium (VI). Wastewater is the effluent of the tannery that has a fast interaction with the environment. The amount of wastewater varies between 30 and 50L per kilogram of processed skin [6,7]. From the total amount of liquids, nearly 10% corresponds to the tanning stage (tanning wastewater) and the remainder to the other stages of processing (dehairing, pickling, neutralization, fat-liquoring, dyeing and washings). The greatest content of chromium (III) is found in the tanning wastewater. The composition of this effluent varies according to the tanning process used and to the type of leather to be obtained. Most of the components of the tanning wastewater and their most frequent contents are: 16–25 g/L sulfate, 17–26 g/L chloride, 14–21 g/L sodium, 0.6–2.0 g/L of chromium (III) and a residual acidity between pH 3.5 and 5.0. Precipitation and adsorption are two alternative methods for the recovery of chromium (III) contained in tanning wastewater. Chromium (III) is easily precipitated by the addition of an alkali (generally, calcium hydroxide) to the liquid effluent. In this way a supernatant free of the

metallic element and a precipitate containing chromium (III) hydroxide are obtained. From the precipitate it is possible to recover the chromium by calcination at 600 C (as hexavalent chromium) or by acid leaching [8]. The adsorption occurs on the surface of a substance called adsorbent and the addition of any reagent is not required. To carry out under favorable economic conditions, the separation of chromium (III) by adsorption, it is necessary to select an adequate adsorbent with high adsorption capacity and able to remain stable at low pH. Smectite is a natural adsorbent with good adsorption capacity, but it does not have selectivity [9]. Thus, adsorption of chromium (III) (0.040 g/g of adsorbent) and of sodium (0.006 g/g of adsorbent) were determined on the smectite from tanning wastewater without dilution [10]. The alteration of this adsorbent in contact with sulfuric acid is produced at pH ~ 1.7 [11]. Activated clay (a kaolin amorphous derivative) with an adsorption capacity nearly three times higher than the smectite is altered at lower acid concentration (the chemical attack starts at pH ~3.0) [12]. The separation (desorption) of chromium (III) retained on the adsorbent surface requires the addition of reagents. The facility of a cation replacement depends on its valence, on the water layer thickness surrounding it, and on its atomic configuration [9]. Protons (hydronium) H+(H3O+) have high capacity to replace to other cations, but their use is not always convenient since some adsorbents may be altered by acid attack. In brief, the adsorption and the desorption must be made under very specific operative conditions to impede generation of new wastes. According to the two methods mentioned above, several operations and processes must be used to separate chromium (III), but they are not commonly utilized in the tannery. Based on these facts, it was considered as appropriate to study the separation of chromium (III) contained in a tanning wastewater by means of reverse osmosis

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(RO). In this method that is easier to be fulfilled than the precipitation and the adsorption, a fraction of the tanning wastewater passes through an adequate membrane under sufficient pressure to overcome the osmotic pressure. The fraction that passes through the membrane (permeate) is constituted basically by water with a low content of dissolved salts and the fraction retained by the membrane (concentrate) contains most of the dissolved salts in the original effluent [13–16]. 2. Experimental The tanning wastewater was obtained from a typical tanning process. The suspended solids were separated by ultrafiltration (UF). Table 1 shows the chemical analysis of the tanning wastewater without suspended solids. Chemical analyses were performed by atomic absorption/emission (AA/AE), volumetry and gravimetry. Analyses by AA/AE were made with Jarell Ash equipment. UF tests were carried out with Millipore equipment using a membrane of polysulfone Pellicon Cassette PTGC00005 of 10.000 NMWL, with a surface of 0.46 m2 and operable between pH 2.0 and 12.0. RO tests were performed using Osmo equipment, model 19E-HR 500, with a membrane of polyamide Osmonics 192 HR, with a surface of 1.68 m2 and operable between pH 2.0 and 12.0.

The high-pressure pump and the membrane of the equipment allowed us to work with a maximum pressure of 1.3 MPa and with recycling flow of 156 L/h. The cleaning of the RO membrane was carried out with water without salts and chlorine, H3PO4 solution at pH 2.0–2.5, NaOH solution at pH 11.0–11.5 and a sodium lauryl sulfate solution 0.001 w/w. The cleaning operation was finished when the initial permeate flux was recovered using distilled water as feed. The chromium species in solution were determined by absorption within the visible range (340–800 nm) with a Hewlett Packard 8453 spectrophotometer. 3. Results and discussion 3.1. UF and RO tests At the beginning of the RO operation, the convective flow of the solute associated with the global flow of the dissolution originates an accumulation of those species that do not pass through the membrane (rejected species). The accumulation of rejected species is produced near the membrane. Under the effect of the concentration gradient so generated, the diffusion of these substances is produced towards the interior of the dissolution in the opposite direction to that of the convective flow. As the operation occurs, the concentration of the rejected species continues increasing up to reaching a certain equilibrium value. This value remains constant and the solute forms a layer over the membrane (boundary layer). The boundary layer is formed during the first moments of the operation and disappears after interrupting the operation pressure. According to the system nature and under determined operative conditions, a second layer of rejected molecules may be formed on the membrane surface. This formation occurs for some materials like proteins or silica at a certain

Table 1 Chemical analysis of the tanning wastewater without suspended solids Component
= SO4 Cl Na+ Cr3+

g/L 17.60 24.80 17.80 0.75

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A. Pérez Padilla, E.L. Tavani / Desalination 126 (1999) 219–226 Table 2 Permeate fluxes obtained with and without pretreatment of the effluent by UF Permeate flux, L/m2 h Effluent

concentration level. The layer near the membrane surface is very stable and the other is more dynamic. When the pump is disconnected, most of the solute molecules disappear, although some of them remain for some time. Thus, an additional resistance to the transport through the membrane is added. The use of the pressure to overcome the osmotic pressure induces the species of smaller molecular size to pass through the membrane and thus those species which are larger are concentrated. In order to prevent any accumulation of particles on the membrane surface, the feed is performed by means of a tangential flow with a high rate. If this action is not sufficient, pretreatment of the feed must be performed to remove the different particles of suspended solids that may affect the system behaviour [13]. In our case, the particles of suspended solids were almost all of them proteins released from the collagen during the tanning process. The protein content in the tanning wastewater was 0.007 w/w, and its separation was performed by UF at room temperature using a transmembrane pressure of 0.15 MPa. Thus, it was possible to separate more than 80% of the proteins contained in the effluent. To determine the influence of the suspended solids on the permeate flux (L/m2h), tanning wastewaters with and without proteins were used. In each case the test was performed with an effluent volume of 12 L, an applied pressure of 1.3 MPa and a feed temperature of 298 K. The time required to obtain 1.8 L of permeate was measured, and thus it was possible to determine the corresponding flux. This determination was performed six times (1–6) resulting in a final concentrate volume of 1.2 L. Table 2 shows three permeate fluxes (1, 3 and 6) obtained for tests performed with and without pretreatment of the effluent by UF. These values indicate that the permeate flux was in each aliquot slightly higher for the effluent without proteins, and this allowed

With pretreatment by UF 1 3 6 0.84 0.81 0.59

Without pretreatment by UF 0.69 0.64 0.50

us to decrease the working time to obtain the same final permeate volume. The low protein content in the tanning wastewater would explain the scarce difference of the permeate fluxes obtained with and without pretreatment of the effluent by UF. The permeate flux depends on the applied pressure and on the feed temperature. In order to study the behaviour of both variables, tests were made using three different pressures (0.9, 1.1 and 1.3 MPa) at constant temperature (288 K). With these conditions, the permeate flux changed in a linear way with the applied pressure (0.17 L/m2h at 0.9 MPa, 0.34 L/m2h at 1.1 MPa and 0.50 L/m2h at 1.3 MPa). When the tests were made using three different temperatures (288, 298 and 308 K) at constant pressure (1.0 MPa), the permeate flux changed according to a parabolic law with the feed temperature (0.27 L/m2h at 288 K; 0.54 L/m2h at 298 K and 0.71 L/m2h at 308 K). Taking into account the results mentioned above, a new RO test was carried out using the effluent without proteins, an applied pressure of 1.3 MPa and a feed temperature of 298 K. The test was performed with an effluent volume of 24 L and was finished when the concentrate volume was 2.4 L. From each 1.8 L of permeate obtained, an aliquot of 0.15 L was taken for chemical analysis. In total, 12 aliquots of

A. Pérez Padilla, E.L. Tavani / Desalination 126 (1999) 219–226 Table 3 Chemical analyses and pH of permeates and pH of the respective concentrates Aliquot Permeate
= SO4 , g/L

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Concentrate pH Cl , g/L 8.5 10.9 13.7 Na+, g/L 5.3 8.4 9.7 Cr3+, mg/L 10.4 7.5 6.8 pH 4.42 4.61 4.72 pH 4.50 4.67 4.75

1 6 12

0.9 1.9 3.3

permeate (1–12) were analyzed. The characterization was completed with the pH measurement of each permeate aliquot and of the respective concentrate. Table 3 shows the chemical analyses and the pH of three permeate aliquots (1, 6 and 12) and the pH of the concentrates. The low chromium (III) content in all permeate aliquots shown in Table 3, similar to the values mentioned by other authors [13–16], confirms that the RO method is a valid alternative for the treatment of the tanning wastewater. 3.2. Identification of chromium (III) species present in the tanning wastewater and in the concentrates obtained by RO The separation of species by RO depends on the difference of molecular size of the feed components to be treated, among other aspects [15]. The medium conditions (pH and concentration of soluble species) are modified as consequence of this separation, which may affect the molecular size (structural changes) of some component. Under the experimental conditions used in this work, chromium (III) is the most propitious component to present structural changes [17–21]. According to these considerations, the physicochemical characterization of different solutions (chromium (III) content, storage temperature and time) was made in order to obtain evidence to explain the results attained by RO.

The absorption spectrum of a diluted solution of chromium (III) nitrate recently prepared and maintained at room temperature has two bands at 408 and 575 nm. The anion nitrate is a weak ligand, and it is very difficult that in diluted solutions it may penetrate into the coordination sphere of the chromium (III) complex. At the same time, the possibility of hydrolytic polymerization of this cation (structural changes) in fresh solutions and maintained at room temperature is negligible. The above-mentioned facts suggest the only presence of water groups into the sphere of the complex [18–21]. Then the bands at 408 and 575 nm show the presence of a chromium (III) mononuclear complex [Cr(H2O)63+]. The absorption spectrum of a solution recently prepared from a commercial tanning salt (Chromosal-BA Bayer), with a chromium (III) concentration similar to the one of nitrate and maintained at room temperature, has two bands at 432 and 594 nm. A shift of the absorption maxima towards longer wavelengths was attributed to the presence of hydroxide groups and sulfate groups into the sphere of the complex. The hydroxide groups produce chromium (III) polymerization, and the sulfate groups (with a ligand strength higher than the one of nitrate) act as monodentate and bidentate ligands [17–21]. Species in solution are polynuclear (dimer), and they remain without structural changes for some time when the commercial salt is dissolved in cold water [17].

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The tanning reagents of mineral origin react with carboxylic groups of the collagen between pH 2.9 and 4.1. A tanning improvement may be achieved when the process is performed at a temperature of 10 to 20 C higher than the room one [22,23]. The pH of a fresh solution of the commercial tanning salt (150 g/L) and maintained at room temperature was ~2.7. When the pH and the temperature of this solution were similar to the usual values of the tanning process, certain structural changes were produced, and at the end the maxima of absorption bands decreased. These changes originated from hydroxide groups that act as ligands among central atoms of chromium (III), which leads to a decrease in the initial sulfate concentration into the sphere of the complex. Hydroxide groups (as bridge or as monodentate ligand) produce a shift of the absorption bands lower than the sulfate groups [17]. The pH of the tanning wastewater was ~4.3, and the absorption spectrum of this effluent without suspended solids, obtained under equal operation conditions than the above-mentioned spectra, has two bands at 414 and 582 nm. Both maxima were increased when the pH was decreased with successive additions of sulfuric acid. The shift of the absorption maxima obtained when lowering the medium pH (from 4.3 up to 2.7), while the sulfate concentration did not present changes, was used as evidence of the participation of hydroxide groups in the structural changes produced in soluble chromium (III) complexes. Despite the reversible character of the shift, in none of the cases was it possible to obtain an absorption spectrum of the tanning wastewater similar to the absorption spectrum of a fresh tanning solution. This behaviour was attributed to the different chemical composition of both liquids. The transport of H2O from the concentrate (the tanning wastewater at the test start) towards the permeate produced an increase in the

chromium (III) concentration of the concentrate. At the same time, the pH of each permeate was lower than the pH of the respective concentrate. According to these pH values, it is possible to assume that during RO test, the transport of H+(H3O+) was also produced in a similar direction (from the concentrate to the permeate). The increases of both parameters (concentration of cation and pH) are aspects that favor the hydrolytic polymerization of chromium (III) [18,19]. At pH >4.7 a chromium (III) complex salt started its precipitation (16% of Cr2O3), and as the RO test occurred, the amount of precipitate increased. The addition of sulfuric acid impeded the precipitation progress and made possible the start of the redissolution of the solid phase already formed. However, the redissolution was not complete, and an important part remained retained in the filter placed previous to the highpressure pump. The chemical analysis of the concentrate supernatant so obtained is indicated in Table 4. The formation of the precipitate during the RO test and its subsequent redissolution with sulfuric acid was a new evidence of the participation of hydroxide groups in the chromium (III) polymerization. The absorption spectra of concentrates obtained in the successive stages of the RO test maintained the band maxima at wavelengths lower than those mentioned for the commercial tanning salt recently dissolved. The aspects above analyzed indicate that the chromium (III) forms polynuclear complexes in the tanning wastewater and in the concentrates obtained by RO. These chromium (III) polynuclear complexes have sizes larger than the = other ionic species (SO4 , Cl , Na+) present in the system [17–21]. Consequently, chromium (III) polymers would be the components of the system with higher difficulty to pass through the polyamide membrane used, and this would explain the results obtained.

A. Pérez Padilla, E.L. Tavani / Desalination 126 (1999) 219–226 Table 4 Chemical analysis of the concentrate supernatant obtained in this work by RO Component
= SO4 Cl Na+ Cr3+

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Acknowledgements The authors thank N.A. Lacour (CIC–CITEC) and J.A. Rodríguez (UNSL–INTEQUI) for their collaboration in the development of this work.

g/L 35.90 16.67 14.35 4.09

References
[1] F.H. Rutland, J. Amer. Leather Chem. Ass., 86 (1991) 364. [2] R.J. Langlais, J. Amer. Leather Chem. Ass., 86 (1991) 413. [3] J. Harte, C. Holden, R. Schneider and C. Shirley, Guía de las sustancias contaminantes, Editorial Grijalbo, México, 1995. [4] R. Barlett and B. James, J. Environ. Qual., 8 (1979) 31. [5] V.G. Schmid and W. Pauckner, Das Leder, 86 (1984) 165. [6] K.T.W. Alexander, D.R. Conning, N.J. Coy, V.J. Donohue and R.L. Sykes, J. Soc. Leather Technol. Chem., 76 (1992) 17. [7] B.G.S. Prasad, J. Amer. Leather Chem. Ass., 86 (1991) 87. [8] H. Toprak, J. Amer. Leather Chem. Ass., 89 (1994) 339. [9] H.L. Bohn, B.L. McNeal and G.A. O’Connor, Química del suelo, Editorial Limusa, México, 1993. [10] C. Volzone and E.L. Tavani, J. Soc. Leather Technol. Chem., 79 (1995) 148. [11] E.L. Tavani and C. Volzone, Cerámica, in press. [12] I.D.R. Mackinnon, Proc., International Workshop of Activated Clays, La Plata, Argentina, 1998, pp. 55– 64. [13] M. Aloy and B. Vulliermet, J. Soc. Leather Technol. Chem., 82 (1998) 140. [14] E. Drioli, Wat. Sci. Tech., 25 (1992) 107. [15] M. Galán, C. González, J. Llorena and C. Mans, Proc., 21st Congress of the International Union of Leather Technologists and Chemists Societies, Barcelona, Spain, 2 (1991) 457.

4. Conclusions The polyamide membrane used allowed us to perform an efficient separation of chromium (III) contained in the tanning wastewater, but the = other components of the system (SO4 , Cl and + Na ) could not be separated satisfactorily. It was determined that a low protein content (0.007 w/w) in the tanning wastewater had little influence on the permeate flux. On the other hand, it was established that the pressure changes applied to overcome the osmotic pressure produced variations of the permeate flux higher than the temperature changes of the feed. The presence of chromium (III) polymers in the tanning wastewater and in the concentrates obtained by RO was identified. These chromium (III) polymers have a more complex molecular structure than the other ionic species present in the system which originates a size difference among effluent components, and this would contribute to explain results obtained in this work. It was determined that a transport of H+(H3O+) from the concentrate towards the permeate was produced. This ionic transfer was analyzed in detail since the medium acidity affects the chromium (III) polymerization (molecular structure).

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[16] R. Molinari and E. Drioli, Proc., International Workshop on Chemistry and Technology of Tanning Processes, S. Miniato, ed., F. Perghem, Italy, 1988, pp. 129–150. [17] E. Heidemann, Fundamentals of Leather Manufacturing, Eduard Roether KG, Darmstadt, 1993. [18] H. Stünzi, L. Spiccia, F.P. Rotzinger and W. Marty, Inorg. Chem., 28 (1989) 66. [19] H. Stünzi and W. Marty, Inorg. Chem., 22 (1983) 2145.

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