1er Congreso Internacional de Agua y Sostenibilidad Terrassa, 26-27 Junio 2017 Biosorption for water treatment: Green technology for environment sustainability Prof. Isabel Villaescusa Chemical Engineering Department Metals and Environmental Research Group
Electroplating Mining and metal processing Electronic Tanneries Devices HEAVY METALS Natural pollution (arsenic in Bangladesh) Power Plants
Precipitation Ion Exchange Reverse osmosis METAL REMOVAL TECHNOLOGIES Adsorption Biosorption
Basic concepts and terminology Biosorption passive sequestration by non-metabolizing non-living biomass Bioaccumulation Metabolically mediated transport and deposition of chemical species in living cells Adsorption Involves the interface accumulation or concentration of substances at a surface or interface Sorption + Absorption Molecules or atoms of one phase interpenetrate among other of another phase to form a «solution» Davis TA, Volesky B, Mucci A. Water Research. 2003
Biosorption processes Non-living biomass thioethers amines carboxylates thiols Adsorption phosphates hydroxyls amides Cellular membrane binding Transport through the membrane Living biomass Biological + Processes Adsorption Reduction, oxidation, methylation
Abundant in nature Sub-products LOW COST SORBENT Waste Little or no pretreatment No need of regeneration
Agricultural biomass Shells: Green coconut Hazelnut Brazil nut Peels: Peas Broad bean Medlar Orange Citrus Mango Wood: Pinus sylvestris sawdust Yohimbe bark P.ruscifolia Juniper Cork bark Papaya Grape stalk Leaves: Tea Plants Saltbush Fig Nurchi & Villaescusa,Coord.Chem.Rev. 2008
Studies on heavy metals biosorption by agriculture biomass around the world Nurchi & Villaescusa, Coord.Chem.Rev., 2008)
Biosorption processes Solid phase Sorbent, biosorbent, adsorbent, biological material Sorbate sorbed on Solid Phase Interactions Equilibrium Liquid Phase Solvent (normally water) with Dissolved species to be sorbed (adsorbate, metal) Unsorbed sorbate in liquid phase
Incidence of binding groups on biomass surface Spectroscopic techniques Nurchi et al., Coord. Chem. Rev. 2010
Factors affecting biosorption processes CONTACT TIME between sorbent and sorbate (equilibrium achievement) ph (sorbent (biomass) ionisation and sorbate (metal) speciation) SORBENT PARTICLE SIZE (the least size the highest adsorption yield) SORBENT CONCENTRATION (concentration of active sites) SORBATE CONCENTRATION SOLUTION IONIC STRENGTH (other ions compete with metal ions) SORBENT PRETREATMENT (increase or blockage of active sites)) TEMPERATURE (no influence of temperature in the range 20-35 o C)
Vegetable wastes and sub-products investigated Olive oil extraction Wine production Cork taps manufacturing Soluble coffee production Alcaloid extraction Olive stones Grape stalks Cork bark Exhausted coffee Yohimbe bark Preparation process: Washing, drying, grinding and sieving
Grape stalks Summative chemical composition (% dry mass) of grape stalks and exhausted coffee Polyphenolic compounds 20.6% GAE,w/w Source of antioxidants Biosorption Pujol et al. Ind Crops & Products, 2013 Exhausted coffee 0,25 Ø 0,50 mm Lipids 88% of dichloromethane extract Biosorption Biodiesel 0,25 Ø 0,50 mm Pujol et al. Ind Crops & Products, 2013
Wastes characterization Porosity Grape stalks 84.14 % Exhausted coffee 57.05% ph of point zero charge 3.89 4.3 Determination of acidic groups phpzc 3.9 Elemental analysis Ashes
FTIR Wastes characterization Grape stalks Exhausted coffee 70 70 60 60 Transmittance (%) 50 40 30 3406 3322 1735 1720 1523 1442 1213 Transmittance (%) 50 40 30 1742 1523 1319 1242 1163 20 20 3500 3000 2500 2000 1500 1000 Wavenumbers (cm -1 ) GS Raw GS Raw with 300 ppm Cr(VI) 3500 3000 2500 2000 1500 1000 Wavenumbers (cm -1 ) EC Raw EC Raw with 300 ppm Cr(VI) 3450-3300 cm -1 O-H lignin, phenolic groups, celluloses 2856 cm -1 γs C-H aliphatic groups 1735 cm -1 C=O aliphatic esters 1523 cm -1 C=C lignin 3450-3300 cm -1 O-H lignin, phenolic groups, celluloses 2856 cm -1 γs C-H aliphatic groups 1742 cm -1 C=O aliphatic esters 1523 cm -1 C=C lignin 1065 cm -1 C=o lignin, phenolic groups
Biosorption of divalent metals
Vegetable wastes as sorbents of divalent metals Equilibrium studies (< 2 hours contact time, ph>4)) Grape stalks Olive stones Exhausted coffee 0,08 0,06 0,04 0,02 0,00 0,0 Cork bark 0,5 1,0 Ceq ( mmol/l) 1,5 Q eq ( mmol/g) 0,20 0,15 0,10 0,05 0,00 0,0 Yohimbe bark 0,5 1,0 Ceq ( mmol/l) 1,5 Q eq ( mmol/g) Sorption mechanisms: ion exchange, complexation and microprecipitation
Influence of ph and salts content in divalent metals sorption Ex. Grape stalks ph > 4 Presence of salts Decrease metal sorption Villaescusa et al. Water Research, 2004
Vegetable wastes as ion exchangers for divalent metals. Kinetics study Grape stalks Grape stalks Purolite-100 resin Olive stones metal ions metal sorbed (meq g -1 ) light metals released (meq g -1 ) metal sorbed (meq g -1 ) light metals released (meq g -1 ) metal sorbed (meq g -1 ) light metals released (meq g -1 ) Purolite-100 Cu 0.289 0.295 0.462 0.442 0.047 0.023 Ni 0.280 0.264 0.431 0.419 0.049 0.023 Pb 0.340 0.309 0.479 0.413 0.061 0.022 Cd 0.271 0.258 0.471 0.480 0.064 0.022 Olive stones Grape stalks: Ca and K Purolite-100 resin: Na Olive stones: Ca Fiol et al., IEX 2008, Ed. M. Cox
Vegetable wastes as ion exchangers for divalent metals Ex. Yohimbe bark Element Atomic % Mg 0.14 Ca 0.76 Na ND K 3.46 Cu ND Magnification 500 X Element Atomic % Mg 0.09 Ca 0.53 Na ND K 2.72 Cu 1.73 Ca, Mg i K Cu (a) deionized water (b) 100 mg/l Cu Villaescusa et al. J.ChemTech Biotech, 2000
Biosorption of Cr(VI)
EXPERIMENTAL PROCEDURE BATCH FTIR Metal solution SORBENT SEM-EDX Sorbent Fixed ph i FAAS Particle size: 0.63-0.75 mm Sorbent mass: 0.1 g Metal solution: 15 ml Agitation speed: 30 r.p.m. FILTRATE ICP DFC (Cr(VI)) ph f
Vegetable wastes as sorbents of Cr(VI) Equilibrium studies (> 24 hours) Sorption mechanisms: Cr(VI) reduction to Cr(III), Cr(VI) and Cr(III) sorption
Vegetable wastes reducing capacity for Cr(VI) Grape stalks Yohimbe bark ph 3.0 ph 6.6 ph 2.0 ph 5.6 Fiol et al. Biores.Tech, 2008
Electron Spin Ressonance (ESR) of Grape stalks chromium laden surface g=1.989 Cr(III) (3 unpaired e - ) g=1.998 Cr(V) (1 unpaired e - )
SEM/EDX analysis of exhausted coffee surface Cr laden
FTIR analysis of exhausted coffee 100 95 1521 90 1236 Transmitance (%) 85 80 75 2923 2852 1739 1725 1457 C 1376 L 1317 70 L 1162 65 4000 3750 3500 3250 3000 2750 2500 2250 2000 1750 C 1500 1058 1033 1250 1000 750 L 500 Wavenumber (cm -1 ) EC-Cr(VI) EC Cellulose and lignin moieties are involved in chromium sorption
Sorbents maximum capacity for divalent metals and Cr(VI) Langmuir isotherm qmax Cu(II) Pb(II) Cd(II) Ni(II Cr(VI) Sorbent (mmol/g) (mmol/g) (mmol/g) (mmol/g) (mmol/g) Grape stalks 0,16 0,22 0,24 0,18 1,13 Exhausted coffee 0,021 0,019 0,44 Yohimbe bark 0,15 0,15 0,82 Olive stones 0,037 0,052 0,072 0,04 0,18 Cork bark 0,047 0,07 0,33 Qmax range (Bibliography 2001-2014) 0,18-0,50 0,04-0,36 0,03-0,53 0,13-0,34 0,33-2,44
Biosorption of metals in binary mixtures
Divalent metal sorption by grape stalks waste from binary mixtures Cu-Ni Cu-Pb Cu-Cd Ni-Pb Ni-Cd Pb-Cd Concentration in solid phase with time Escudero et al. Chem. Eng. J, 2013
Modeling of divalent metal sorption by grape stalks waste from binary mixtures Homogeneous Surface Diffusion Model (HSDM) Equilibrium model Bed model: Transport across liquid film Diffusion across sorbent particle
Simultaneous metal sorption onto Exhausted Coffee from binary mixtures (Cr(VI)-Cu(II) and Cr(VI)-Ni(II)) Cr(VI) in the presence of Cu(II) Cr(VI) in the presence of Ni(II) ph 3.0 Competition between cations and protons Increase of protons in solution Cu(II) in the presence Cr(VI) Ni(II) in the presence Cr(VI) Reduction of Cr(VI) Formation of new sites Less competition
Biosorption of metals in quaternary mixtures
Continuous sorption/desorption cycles of divalent metals in a grape stalks packed column
Divalent metals sorption after desorption with HCl acid Sorption: 0.2 mm Equimolar solutions of the four metals Desorption: 0.05 M HCl Sorbent: Grape stalks ph i: 5.2 Flow rate: 30 ml/min
DIVALENT METALS SORPTION PERCENTAGE AFTER DIFFERENT SORPTION/DESORPTION CYCLES
Biosorption of metals in a batch reactor
Kinetic study of Cr(VI) sorption onto grape stalks in a stirred batch reactor du du du d t Variables: ph and Temperature Cr ( VI ) d t Cr ( III ) d t qt = k = k u 1 = k u u 1 Cr ( VI ) Cr ( VI ) k k 4 2 u u Cr ( VI ) ( 1 Q u ) + k R qt 3 Q R u Cr ( III )( 1 (1 QR ) uqt ) + k5 qt (1 Q R ) u ( 1 QRuqt ) k3qruqt + k4( ucr ( III )(1 (1 QR ) uqt ) k5(1 QRu 2 Cr ( VI ) qt qt ) ph Constant ph 3 Initial ph 3 and free evolution Temperature: 5 60 o C
Kinetics of Cr(VI) sorption onto grape stalks in a stirred batch reactor. Modeling Free ph ph 3.0 Sorption is faster when ph was maintained at ph 3.0 Sorption is faster when temperature increases ph has no effect at high temperatures Escudero et al., J Haz Mat, 2009
Simultaneous Cr(VI) and Cu(II) sorption by exhausted coffee from binary mixtures Cr(VI) totally reduced. Cr(III) accounted for 15% of initial Cr(VI) The presence of Cu(II) exerced a synergistic effect on Cr sorption Metal mixtures concentration ranges: 0.2-0.6 mm and 2.0-6.0 mm Liu et al. Sci of Total Env.,2016
Biosorption process for electroplating wastewater treatment
Electroplating wastewaters from rinsing baths
Scheme of a electroplating wastewaters treatment plant 1st step: Reducing agents + electrolysis : Cr(VI) reduction 2nd step: Flocculation/Precipitation: Addition of NaOH (ph 9.0) and flocculant 3er step: Filtration
Proposed Scheme of a electroplating wastewaters treatment plant 1st step: Biosorption (exhausted coffee) : Cr(VI) and Cr(III) reduction/sorption 2nd step: Flocculation/Precipitation: Addition of NaOH (ph 9.0) and flocculant 3er step: Filtration
1st Step Biosorption (Cr(VI) reduction Wastewaters electroplating industry ph conductivity Properties E1 E2 E3 Metal (mg L -1 ) Cr(VI) 112.49 108.50 147.18 Cr(III) 0.00 0.00 0.00 Cu 5.04 8.20 8.01 Ni 1.04 0.93 1.23 Fe 4.24 8.54 5.51 Al 0.90 0.66 0.99 Anions (mg L -1 ) 2- SO 4 93.84 98.81 132.49 3- PO 4 n.d. a n.d. a n.d. a Conductivity (ms cm -1 ) 3.46 3.38 3.29 ph 3.02 3.05 3.01 ST b (mg L -1 ) 677 653 820 SS c (mg L -1 ) 16 17 19 Experimental set-up Operation conditions: 8L electroplating wastewater Sorbent dose: 6.7 g/l ph 2.0 Temperature: 20 o C
120 (a) E1 Cr total 6 (b) E1 Cu Fe Al Ni Biosorption Results Samples E1-E3 Cr (mg L -1 ) Cr(VI) 90 Cr(III) 60 30 0 0 12 24 36 48 60 72 Time (h) Metal (mg L -1 ) 5 4 3 2 1 0 0 12 24 36 48 60 72 Time (h) Cr(VI) totally removed Cr(III) in solution 30% initial Cr(VI) Cr (mg L -1 ) 120 100 80 60 40 20 (c) E2 Cr total Cr(VI) Cr(III) Metal (mg L -1 ) 9 8 7 6 5 4 3 2 1 (d) E2 Cu Fe Al Ni Fe(III) partially sorbed 0 0 12 24 36 48 60 72 84 96 Time (h) 0 0 12 24 36 48 60 72 84 96 Time (h) Poor Cu, Ni and Al sorption 150 120 90 60 (e) E3 Cr total Cr(VI) Cr(III) Metal (mg L -1 ) 9 8 7 6 5 4 3 (f) E3 Cu Fe Al Ni 30 2 1 0 0 24 48 72 96 120 144 168 Time (h) 0 0 24 48 72 96 120 144 168 Time (h)
Monitoring of Cr(VI) reduction through conductivity and ph probes (a) 100,0 Cr total Cr(VI) 3,2 (a) (b) Cr (mg L -1 ) 80,0 60,0 40,0 Cr(III) Conductivity 3,0 2,8 2,6 Conductivity (ms cm-1) 20,0 2,4 (c) (d) 0,0 0 6 12 18 24 30 36 42 48 54 60 66 72 78 84 90 96 Time (h) 2,2 Cr (mg L -1 ) 100,0 80,0 60,0 40,0 20,0 0,0 (b) Cr total Cr(VI) Cr(III) ph 0 6 12 18 24 30 36 42 48 54 60 66 72 78 84 90 96 Time (h) 3,0 2,9 2,8 2,7 2,6 2,5 2,4 2,3 2,2 2,1 2,0 ph Constant ph Biosorption finished 2nd step Flocculation/Precipitation
2nd Step flocculation/precipitation Effluents from biosorption Coagulation/flocculation Jar test
Metal concentration of treated water Samples 1st step 2nd step Metal E1 (mg L -1 ) E2 (mg L -1 ) E3 (mg L -1 ) Industrial effluents Cr(VI) 112.49 108.50 147.18 Cr(III) n.d. a n.d. a n.d. a Cu 5.04 8.20 8.01 Ni 1.04 0.93 1.23 Fe 4.24 8.54 5.51 Al 0.90 0.66 0.99 After biosorption Cr(VI) 0.50 0.13 0.24 Cr(III) 1st 32.84 35.20 45.53 Cu 5.03 8.20 8.01 Ni 1.04 0.93 1.23 Fe 3.64 6.78 3.39 Al 0.90 0.66 0.99 After precipitation Cr(VI) 0.50 0.13 0.24 Cr(III) n.d. a n.d. a n.d. a Cu < LOD b < LOD b < LOD b Ni < LOD b < LOD b < LOD b Fe < LOD b < LOD b < LOD b Al < LOD b < LOD b < LOD b
Proposed Scheme of a electroplating wastewaters treatment plant
Biosorption of metals by sorbents entrapped in calcium alginate
Sorbent encapsulation in calcium alginate beads micropipette tip 1% sodium alginate solution 0,1 M CaCl 2 magnetic stirrer peristaltic pump magnetic stirrer column Cr(VI) solution Peristaltic pump Fractions collector
Simultaneous Cr(VI) and Cu(II) sorption by exhausted coffee from binary mixtures k 2 K 4 K 3 K 5 Metal mixtures concentration ranges: 0.2-0.6 mm and 2.0-6.0 mm 7 + 7 binary mixtures Liu et al. Sci of Total Env., 541 (2016) 101-108
Simulaneous sorption of Cr(VI) and Cu(II) from Cr(VI)-Cu(II) binary mixtures Cr(VI) Bench scale Pilot scale Cu(II) Cu(II) 0 0,2 0,4 0,6 0,2 0,4 0,6 0,2 x x 0,4 x x x x x x x 0,6 x x x x x x 0,8 x x x x
1 2 3 4 5 6 7 8 CA beads EC-CA beads 600 x 0,001 cps/ev 700 x 0,001 cps/ev 600 500 500 400 400 300 O Fe Na K Ca a 200 Fe K Cr 300 S C O S Ca K Ca Cr Cr(VI) sorption 200 100 100 0 kev 0 1 2 3 4 5 6 7 kev x 0,001 cps/ev cps/ev 600 2.4 2.2 500 2.0 1.8 400 1.6 300 O a Cu Ca Cu 1.4 1.2 S C O Cu Si S 1.0 Ca Ca Cu Cu(II) sorption 200 0.8 0.6 100 0.4 0.2 0 0.0 1 2 3 4 5 6 7 8 9 kev 2 4 6 8 kev cps/ev 4.0 cps/ev 3.0 3.5 2.5 3.0 2.0 2.5 2.0 1.5 1.0 Cr C O Cu Ca Ca Cr Cu 1.5 S Cr C O Cu Al Si S Ca 1.0 0.5 Ca Cr Cu Cr(VI) and Cu(II) sorption 0.5 0.0 0.0 2 4 6 8 10 kev 2 4 6 8 10 kev
Electron Spin Ressonance (ESR) of Exhausted coffee chromium laden surface Filename: F:\EPR\caec100l.spc 400 300 200 100 0-100 -200-300 2.6862 2.4420 2.2385 2.0663 1.9187 1.7908 1.6789 1.5801 g-factor Cr(III) and Cr(V) presence evidenced Cr(vI) reduction by exhausted coffee
Sorption mechanism
Acknowledgements Prof. J-C. Bollinger Prof.N. Fiol Prof.F. Torre PhD MA.Olivella Prof. J. Poch PhD C. Escudero PhD D. Pujol PhD C. Liu Prof. M.V. Nurchi Prof. G. Crisponii Prof. A. Bianchi Prof. C. Bazzicalupi Prof A. Florido Prof. M. Martínez Prof. H.Pereira PhD. A. Sen
Universitat de Girona location Departament d Enginyeria Química, Agrària i Tecnologia Agroalimentària Metals and Environment Laboratory