Biosorption for water treatment: Green technology for environment sustainability

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1er Congreso Internacional de Agua y Sostenibilidad Terrassa, 26-27 Junio 2017 Biosorption for water treatment: Green

1 1er Congreso Internacional de Agua y Sostenibilidad Terrassa, Junio 2017 Biosorption for water treatment: Green technology for environment sustainability Prof. Isabel Villaescusa Chemical Engineering Department Metals and Environmental Research Group

2 Electroplating Mining and metal processing Electronic Tanneries Devices HEAVY METALS Natural pollution (arsenic in Bangladesh) Power Plants

3 Precipitation Ion Exchange Reverse osmosis METAL REMOVAL TECHNOLOGIES Adsorption Biosorption

4 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

5 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

6 Abundant in nature Sub-products LOW COST SORBENT Waste Little or no pretreatment No need of regeneration

7 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

8 Studies on heavy metals biosorption by agriculture biomass around the world Nurchi & Villaescusa, Coord.Chem.Rev., 2008)

9 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

10 Incidence of binding groups on biomass surface Spectroscopic techniques Nurchi et al., Coord. Chem. Rev. 2010

11 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 o C)

Alcaloid extraction Olive stones Grape stalks Cork bark Exhausted

12 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

6% GAE,w/w Source of antioxidants Biosorption Pujol et al.

13 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

14 Wastes characterization Porosity Grape stalks % Exhausted coffee 57.05% ph of point zero charge Determination of acidic groups phpzc 3.9 Elemental analysis Ashes

15 FTIR Wastes characterization Grape stalks Exhausted coffee Transmittance (%) Transmittance (%) Wavenumbers (cm -1 ) GS Raw GS Raw with 300 ppm Cr(VI) Wavenumbers (cm -1 ) EC Raw EC Raw with 300 ppm Cr(VI) 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 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

16 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

17 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

18 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.

Olive stones metal ions metal sorbed (meq g -1 ) light

metals released (meq g -1 ) Purolite-100 Cu 0.289 0.295 0.

023 Pb 0.340 0.309 0.479 0.413 0.061 0.022 Cd 0.271 0.258 0.

022 Olive stones Grape stalks: Ca and K Purolite-100 resin:

19 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 Ni Pb Cd Olive stones Grape stalks: Ca and K Purolite-100 resin: Na Olive stones: Ca Fiol et al., IEX 2008, Ed. M. Cox

20 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

21 Biosorption of Cr(VI)

22 EXPERIMENTAL PROCEDURE BATCH FTIR Metal solution SORBENT SEM-EDX Sorbent Fixed ph i FAAS Particle size: mm Sorbent mass: 0.1 g Metal solution: 15 ml Agitation speed: 30 r.p.m. FILTRATE ICP DFC (Cr(VI)) ph f

23 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

24 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

25 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 - )

26 SEM/EDX analysis of exhausted coffee surface Cr laden

27 FTIR analysis of exhausted coffee Transmitance (%) C 1376 L L C L 500 Wavenumber (cm -1 ) EC-Cr(VI) EC Cellulose and lignin moieties are involved in chromium sorption

28 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 ) 0,18-0,50 0,04-0,36 0,03-0,53 0,13-0,34 0,33-2,44

29 Biosorption of metals in binary mixtures

30 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

31 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.

32 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

33 Biosorption of metals in quaternary mixtures

34 Continuous sorption/desorption cycles of divalent metals in a grape stalks packed column

35 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

36 DIVALENT METALS SORPTION PERCENTAGE AFTER DIFFERENT SORPTION/DESORPTION CYCLES

37 Biosorption of metals in a batch reactor

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

38 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

39 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

40 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: mm and mm Liu et al. Sci of Total Env.,2016

41 Biosorption process for electroplating wastewater treatment

42 Electroplating wastewaters from rinsing baths

43 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

44 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.

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.

45 1st Step Biosorption (Cr(VI) reduction Wastewaters electroplating industry ph conductivity Properties E1 E2 E3 Metal (mg L -1 ) Cr(VI) Cr(III) Cu Ni Fe Al Anions (mg L -1 ) 2- SO PO 4 n.d. a n.d. a n.d. a Conductivity (ms cm -1 ) ph ST b (mg L -1 ) SS c (mg L -1 ) Experimental set-up Operation conditions: 8L electroplating wastewater Sorbent dose: 6.7 g/l ph 2.0 Temperature: 20 o C

46 120 (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) Time (h) Metal (mg L -1 ) Time (h) Cr(VI) totally removed Cr(III) in solution 30% initial Cr(VI) Cr (mg L -1 ) (c) E2 Cr total Cr(VI) Cr(III) Metal (mg L -1 ) (d) E2 Cu Fe Al Ni Fe(III) partially sorbed Time (h) Time (h) Poor Cu, Ni and Al sorption (e) E3 Cr total Cr(VI) Cr(III) Metal (mg L -1 ) (f) E3 Cu Fe Al Ni Time (h) Time (h)

47 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, 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 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

48 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.

49 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) Cr(III) n.d. a n.d. a n.d. a Cu Ni Fe Al After biosorption Cr(VI) Cr(III) 1st Cu Ni Fe Al After precipitation Cr(VI) 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

50 Proposed Scheme of a electroplating wastewaters treatment plant

51 Biosorption of metals by sorbents entrapped in calcium alginate

52 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

mixtures concentration ranges: 0.2-0.6 mm and 2.0-6.

53 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: mm and mm binary mixtures Liu et al. Sci of Total Env., 541 (2016)

54 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

55 CA beads EC-CA beads 600 x 0,001 cps/ev 700 x 0,001 cps/ev O Fe Na K Ca a 200 Fe K Cr 300 S C O S Ca K Ca Cr Cr(VI) sorption kev kev x 0,001 cps/ev cps/ev O a Cu Ca Cu S C O Cu Si S 1.0 Ca Ca Cu Cu(II) sorption kev kev cps/ev 4.0 cps/ev Cr C O Cu Ca Ca Cr Cu 1.5 S Cr C O Cu Al Si S Ca Ca Cr Cu Cr(VI) and Cu(II) sorption kev kev

56 Electron Spin Ressonance (ESR) of Exhausted coffee chromium laden surface Filename: F:\EPR\caec100l.spc g-factor Cr(III) and Cr(V) presence evidenced Cr(vI) reduction by exhausted coffee

57 Sorption mechanism

58 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

59 Universitat de Girona location Departament d Enginyeria Química, Agrària i Tecnologia Agroalimentària Metals and Environment Laboratory

PREFACE About the Author

Contents / vii CONTENTS PREFACE About the Author CONTENTS v vi vii INTRODUCTION Sorption and Biosorption Share the Methodology 1 1. POTENTIAL OF BIOSORPTION 5 1.1 METALS: ENVIRONMENTAL THREAT 5 1.2 BIOSORPTION