Pyrolysis of olive residue and sugar cane bagasse: non-isothermal thermogravimetric kinetic analysis.

Thermal degradation and kinetics for olive residue and sugar cane bagasse have been evaluated under dynamic conditions in the presence of nitrogen atmosphere, using a non-isothermal thermogravimetric method (TGA). The effect of heating rate was evaluated in the range of 2-50 K min(-1) providing significant parameters for the fingerprinting of the biomass. The DTG plot for the olive residue and sugar cane bagasse clearly shows that the bagasse begins to degrade at 473 K and exhibits two major peaks. The initial mass-loss was associated with hemicellulose pyrolysis and responsible for the first peak (538-543 K) whereas cellulose pyrolysis was initiated at higher temperatures and responsible for the second peak (600-607 K). The two biomass mainly devolatilized around 473-673 K, with total volatile yield of about 70-75%. The char in final residue was about 19-26%. Mass loss and mass loss rates were strongly affected by heating rate. It was found that an increase in heating rate resulted in a shift of thermograms to higher temperatures. Ozawa-Flynn-Wall and Vyazovkin methods were applied to determine apparent activation energy to the olive residue and sugar cane bagasse. Two different steps were detected with apparent activation energies in the 10-40% conversion range have a value of 153-162 kJ mol(-1) and 168-180 kJ mol(-1) for the hemicellulose degradation of olive residue and sugar cane bagasse, respectively. In the 50-80% conversion range, this value is 204-215 kJ mol(-1) and 231-240 kJ mol(-1) for the cellulose degradation of olive residue and sugar cane bagasse, respectively.

Synthesis and characterization of pillared stevensites: application to chromate adsorption.

The purpose of this work was to study the synthesis of pillared interlayered clays from Moroccan stevensite called locally 'Ghassoul'. This clay has been intercalated with cetyltrimethylammonium surfactant (CTA-Stv) and aluminium hydroxypolycation (Al13-Stv). Characterization studies were performed using XRF, XRD, FTIR and DTA/TG analysis. Basal spacing values of Al13-Stv and CTA-Stv increased respectively from 13.5 A for natural stevensite to 17.5 and 17.6 A with increasing Al13(7+)/clay and CTA+/clay ratios. The DTA/TG results showed that Al13-Stv has a relatively high thermal stability compared with CTA-Stv. A quasi-irreversible intercalation by exchanging the interlayer inorganic cations with voluminous pillars Al13(7+) or CTA+ was observed. Batch adsorption of chromate anions from aqueous solutions was investigated and the results showed that both pillared clays had great affinity for the chromate compared with untreated stevensite. The Dubinin-Kaganer-Radushkevich (DKR) model was selected to describe the adsorption isotherms. The maximum adsorption capacities for natural stevensite, Al13-Stv and CTA-Stv are 13.7, 75.4 and 195.6 mmol/kg, respectively.

Removal of Basic Red 46 dye from aqueous solution by adsorption onto Moroccan clay.

In this study, Moroccan crude clay of Safi, which was characterized by X-ray diffraction, is used as adsorbent for the investigation of the adsorption kinetics, isotherms and thermodynamic parameters of the Basic Red 46 (BR46) in aqueous solutions at various dye concentrations, adsorbent masses and pH values. The results showed that the adsorption capacity of the dye increased by initial dye concentration and pH values. Two kinetic models (the pseudo-first-order and the pseudo-second-order) were used to calculate the adsorption rate constants. The adsorption kinetics of the basic dye followed pseudo-second-order model. The experimental data isotherms were analyzed using the Langmuir, Freundlich and Dubinin-Radushkevish equations. The monolayer adsorption capacity for BR46 dye is 54 mg/g of crude clay. Nearly 20 min of contact time was found to be sufficient for the dye adsorption to reach equilibrium. Thermodynamical parameters were also evaluated for the dye-adsorbent system and revealed that the adsorption process is exothermic in nature.

Optimisation of biodegradation conditions for the treatment of olive mill wastewater.

The aim of the present paper was to optimise the conditions of aerobic treatment of olive mill wastewater. To do so, the waste was treated following the experimental optimal design methodology studying the set of factors susceptible to influence the treatment (pH, C/N ratio, aeration and temperature). The results of a first series of experiments showed a strong correlation between the reduction in the levels of polyphenols and three of the parameters studied, i.e. the C/N ratio, aeration and temperature. Optimised conditions led to a 94% drop in polyphenols. Then, for a finer study of the conditions, just two parameters were varied, the pH and the C/N ratio. The results showed that the conditions of pH modification (addition of lime or sodium hydroxide) and the C/N ratio (urea or ammonium nitrate) allowed the microbiological activity to be very significantly improved. This led to polyphenol reductions of 51% and 76%.

Application of a sequential batch reactor system for textile dyes degradation: comparison between azo and phthalocyanine dyes.

Photocatalysis on supported TiO2 was combined with aerobic biological treatment in a sequential batch reactor to compare the degradation of two textile dyes: a blue azo dye (DR KBL CDG) and a green phthalocyanine dye (DR K4GN). Three reactors were run in parallel. SBR1 was used as a reference and was fed with urban wastewater only. SBR2 and SBR3 were fed with the same urban wastewater combined with pretreated (for SBR2) and non-pretreated (for SBR3) dye solution. For an azo dye concentration of 12 mg/L decolouration yields of 78 and 27% were achieved, respectively, in SBR2 and SBR3. For the phthalocyanine dye, the decolouration yields decreased to 24 and 15%, respectively. Concerning COD removal it decreases for both dyes with and without pretreatment, when the dye concentration increases. Although a detrimental effect on biomass could be observed, bacteria were able to cope with the inhibitory effect of the dyes.

Discoloration of a red cationic dye by supported TiO(2) photocatalysis.

The degradation under UV, visible and sunlight irradiation of C.I. Basic Red 46 (BR 46) dye used for acrylic fibers dyeing has been studied in a lab-scale continuous system with two different immobilized TiO(2) systems. Catalyst I was based on TiO(2) particles deposited on cellulose fibers; Catalyst II combined TiO(2) particles deposited on a layer of cellulose fibers (as in Catalyst I) with a layer of carbon fibers and finally a layer of cellulose fibers. The treatment of aqueous dye solutions and industrial wastewater contaminated with the same dye has been evaluated in terms of color removal and chemical oxygen demand (COD) decrease. With UV light, aqueous solutions containing dye were decolorized slightly more rapidly with Catalyst II than with Catalyst I. Sunlight was also very effective and experiments involving sunlight irradiation showed Catalyst II to be the more efficient, giving more than 90% discoloration after 20 min of treatment. Comparing the discoloration yield by adsorption or under visible light for both catalysts, it was observed that the difference between them is below 5%. The adsorption kinetics was found to follow a second-order rate law for Catalyst I and a first-order rate law for Catalyst II. The kinetics of photocatalytic degradation under UV or sunlight were found to follow a first-order rate law for both catalytic systems. Under sunlight the COD removal yield for textile wastewater reaches 33% with Catalyst I against 93% with Catalyst II.

Improvement of paint effluents coagulation using natural and synthetic coagulant aids.

The coagulant iron chloride and the flocculants Polysep 3000 (PO), Superfloc A-1820 (SU) and Praestol 2515 TR (PR) have been used in this study to show the efficiency of coagulation flocculation process in the chemical precipitation method for the removal of organic and colouring matters from the paint industry wastewater. This study also includes the amount of produced sludge. The results indicate that FeCl(3) is efficient at pH range 8-9 and at optimal dose of 650 mgl(-1). Iron chloride allows the removal of 82% of chemical oxygen demand (COD) and 94% of colour. However, sequential addition of coagulant and polymeric additives enhance clearly pollutant removal and produces less decanted sludge compared to the results obtained when the coagulant is used alone. The removal efficiency of COD reaches 91% and that of colour 99%. Coagulation-biflocculation process is more effective than the coagulation-monoflocculation one. The sequential addition of iron chloride, Polysep 3000 (cationic flocculant) and Praestol 2515 TR (anionic flocculant) seems to be the most suitable combination for the treatment of the paint industry wastewaters.

Treatment of textile wastewater using a natural flocculant.

The physicochemical treatment of wastewater is of substantial interest, especially when conventional treatments by biological processes are not amenable. Among the current chemical processes used for industrial wastewater treatment, coagulation-flocculation has received a large attention for high pollutant removal efficiency. This paper summarizes the results of a textile wastewater treatment process aimed at the destruction of colour by coagulation-flocculation process and using an organic natural flocculant: tannic substances. Jar-test experiments were carried out in order to determine the optimum conditions for the removal of organic matter and color. Treatment with studied flocculent (Polysep3000) proved to be effective in a wide pH range (pH < or = 10), very effective in removing the color (96 %) and a fraction of the COD (40-50 %) from the textile wastewater. Polysep3000 is compared to Al2 (SO4)3 and FeCl3 for sludge production. Polysep3000 seems to be suitable for yielding a high removal of color (> 90%) and corresponding low volume of settled sludge.

Study of the removal of mercury(II) and chromium(VI) from aqueous solutions by Moroccan stevensite.

The objective of the present study was to investigate the adsorption of the heavy metals mercury(II) and chromium(VI), from aqueous solutions, onto Moroccan stevensite. A mineralogical and physicochemical characterization of natural stevensite was carried out. In order to improve the adsorption capacity of stevensite for Cr(VI), a preparation of stevensite was carried out. It consists in saturating the stevensite by ferrous iron Fe(II) and reducing the total Fe by Na(2)S(2)O(4). Then, the adsorption experiments were studied in batch reactors at 25+/-3 degrees C. The influence of the pH solution on the Cr(VI) and Hg(II) adsorption was studied in the pH range of 1.5-7.0. The optimum pH for the Cr(VI) adsorption is in the pH range of 2.0-5.0 while that of Hg(II) is at the pH values above 4.0. The adsorption kinetics were tested by a pseudo-second-order model. The adsorption rate of Hg(II) is 54.35 mmol kg(-1)min(-1) and that of Cr(VI) is 7.21 mmol kg(-1)min(-1). The adsorption equilibrium time for Hg(II) and Cr(VI) was reached within 2 and 12 h, respectively. The adsorption isotherms were described by the Dubinin-Radushkevich model. The maximal adsorption capacity for Cr(VI) increases from 13.7 (raw stevensite) to 48.86 mmol kg(-1) (modified stevensite) while that of Hg(II) decreases from 205.8 to 166.9 mmol kg(-1). The mechanism of Hg(II) and Cr(VI) adsorption was discussed.

Adsorption of metal ions onto Moroccan stevensite: kinetic and isotherm studies.

The aim of this paper is to study the adsorption of the heavy metals (Cd(II), Cu(II), Mn(II), Pb(II), and Zn(II)) from aqueous solutions by a natural Moroccan stevensite called locally rhassoul. We carried out, first, a mineralogical and physicochemical characterization of stevensite. The surface area is 134 m2/g and the cation exchange capacity (CEC) is 76.5 meq/100 g. The chemical formula of stevensite is Si3.78Al0.22Mg2.92Fe0.09Na0.08K0.08O10(OH)2.4H2O. Adsorption tests of Cd(II), Cu(II), Mn(II), Pb(II), and Zn(II) in batch reactors were carried out at ambient temperature and at constant pH. Two simplified models including pseudo-first-order and pseudo-second- order were used to test the adsorption kinetics. The equilibrium time and adsorption rate of adsorption were determined. The increasing order of the adsorption rates follows the sequence Mn(II) > Pb(II) > Zn(II) > Cu(II) > Cd(II). The Dubinin-Radushkevich (D-R), Langmuir, and Redlich-Peterson (R-P) models were adopted to describe the adsorption isotherms. The maximal adsorption capacities at pH 4.0 determined from the D-R and Langmuir models vary in the following order: Cu(II) > Mn(II) > Cd(II) > Zn(II) > Pb(II). The equilibrium data fitted well with the three-parameter Redlich-Peterson model. The values of mean energy of adsorption show mainly an ion-exchange mechanism. Also, the influence of solution pH on the adsorption onto stevensite was studied in the pH range 1.5-7.0.