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IMPROVED EFFICIENCY IN THE TREATMENT OF INDUSTRIAL WASTEWATERS

Prof Ulla LassiProf. Ulla LassiUniversity of Oulu/Kokkola University Consortium Chydenius

Kokkola Material Week, KMW, 24.9.2014

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CONTENTCONTENT

1. Introduction

2 Ad d t l ti id ti th d i th t t t f i d t i l2. Advanced catalytic oxidation methods in the treatment of industrialwastewaters

3 Chemical precipitation as a method for mine water treatment3. Chemical precipitation as a method for mine water treatment

4. Industrial residues as novel (ad)sorbentsfor the heavy metal removal from wastewatersfor the heavy metal removal from wastewatersfor the removal of nitrates and phoshatesfor sulphate removal

5. Conclusions

Prof. Ulla LassiKokkola Material Week, KMW, 24.9.2014

RESEARCH GROUP OF APPLIED CHEMISTRY

T t ll 27 h • Main projects on that topic :• Totally 27 researchers• Researchers in the field of water

treatment:M Sc (Chem ) Hanna Runtti

• Main projects on that topic :

Moniwater/Tekes 2009-2011Valokata/Tekes 2008-2010M.Sc. (Chem.) Hanna Runtti

M.Sc. (Chem.) Sari Tuomikoski (defense14.11.2014)

M.Sc. (Eng.) Laura RahikkaM Sc (Chem ) Tero Luukkonen

Valokata/Tekes 2008 2010AOPI/Academy of Finland, 2012-2016Teollisuuden jätevesien käsittely, 2009-SULKA/EU, 2012-2014

M.Sc. (Chem.) Tero LuukkonenM.Sc. (Chem.) Emma-Tuulia TolonenM.Sc. (Chem.) Anne HeponiemiM.Sc. (Eng.) Ville Kuokkanen

Several projects with industry

B.Sc. (Chem.) Mikko NiskanenB.Sc. (Chem.) Sara Lopez

• Senior researchers:D.Sc. Pekka Tynjälä (advisor, until 1.5.2014)D.Sc. Tao HuD.Sc. Saïd Azalim (until 31.12.2013)D Sc Jaakko Rämö (advisor)D.Sc. Jaakko Rämö (advisor)D.Sc. Teija Kangas (advisor)Prof. Ulla Lassi

SOME EXAMPLES OF INDUSTRIAL CO-OPERATIONCO OPERATION

SOME EXAMPLES OF INDUSTRIAL CO-OPERATIONCO OPERATION

•Industrial collaboration: Cabb Oy (Kemfine), Kemira, Snellman, Eskopuu, UPM, Stora Enso, JP Analysis, Yara, Sachtleben Pigments, Freeport, PAC Solution, Rautaruukki, Outokumpu, Talvivaara, Keliber, Gasek, Arizona Chemical, OWA etc.

•Some significant references of industrial co operation:•Some significant references of industrial co-operation:HEPONIEMI, A., RAHIKKA, L., KUOKKANEN, T. & LASSI. U. (2011) Catalytic oxidation of industrial wastewater under mild conditions, Topics in Catalysis, vol. 54, 1034-1041.LUUKKONEN, T, HUKKANEN, R., PELLINEN, J., RÄMÖ, J. & LASSI, U. (2012) Reduction of total

i b i b il k i h i d b fil P Pl t Ch i torganic carbon in recovery boiler make-up with activated carbon filter, PowerPlant Chemistry14(2): 112-119.KUOKKANEN, V., LASSI, U., KUOKKANEN, T. & RÄMÖ, J. (2013) Recent applications of electrocoagulation on treatment of water and wastewater – A review, Green and Sustainable Chemistry, 3, 89-121.KILPIMAA (TUOMIKOSKI), S. RUNTTI, H., KANGAS, T., LASSI, U. & KUOKKANEN, T. (2014) Removal of phosphate and nitrate over a modified carbon residue from biomass gasification, Chemical Engineering Research and Design (in press)Engineering Research and Design (in press)RUNTTI, H., KILPIMAA (TUOMIKOSKI), S., KANGAS, T., LASSI, U., KUOKKANEN, T. & RÄMÖ, J. (2014) Activated carbon residue from biomass gasification as an adsorbent for the removal of iron(II), copper(II) and nickel(II) ions, Journal of Water Process Engineering (in press)TOLONEN E SARPOLA A RÄMÖ J & LASSI U (2014)TOLONEN, E., SARPOLA, A., RÄMÖ, J. & LASSI, U. (2014)Chemosphere 117, 419-424.

Preparation of catalysts for catalyticwet oxidationwet oxidation

Preparation of support 1 0

0

S2

by sol-gel method

Ce(NO3)3,6 H2O Zr(OC3H7)

5 0

4 0

3 0

2 0

3 7

solution 2 was added to solution 1 drop-wise at RT

under vigorous stirringS1

water C3H7OHS1 S2

Ce Zr O

Dried in oven at 120 °C for 12h

Ce0.2Zr0.8O2Ce0.85Zr0.25O2

60°C

Evaporation in a sand bath at 60°C for 1 hour

Dried in oven at 120 C for 12h

Heat treatment at 650 °C for 5h

Advanced oxidation processes in industrial wastewater treatment (AOPI)

Remark: CeO2 and ZrO2 commercial catalysts (Sigma-Aldrich)

Preparation of catalysts for catalyticwet oxidationwet oxidation

Impregnation of active

Rotary evaporator

Impregnation of active metals to the supports

AgNO3

+

Acidic water

+

support

Time 4h

Speed 25%

Temperature 40°C

Ag/ZrO2Ag/CeO2

Ag/Ce0.2Zr0.8O2Ag/Ce0.85Zr0.25O2

Dried in oven at 120 °C for 12h

Heat treatment at 650 °C for 5h & reduced at 350°C for 3hTh l f

Advanced oxidation processes in industrial wastewater treatment (AOPI)

& reduced at 350°C for 3hThe target metal content for silver 2.5 wt -%.

CERIUM OXIDE BASED CATALYSTS FOR WET AIR OXIDATION OF BISPHENOL A (BPA)

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WET AIR OXIDATION OF BISPHENOL A (BPA)

in the production of polycarbonate and epoxy resins

method for refractory organic effluents

adhesives

Temperature 130-200 °CPressure 5-50 bar

protective coatings

powder paints etc. Homogeneous catalysts

Metal salts (Cu, Fe)Heterogeneous catalysts

C b t i l (AC CNT)

induce feminization in several animals and possibly humans

Carbon materials (AC, CNT)Transition metals (Cu, Mn, Co, Cr, V, Ti)Supported noble metals

• Active metal (0.1-5 wt%): Pt, Ru, Ir, Aganimals and possibly humans ( ) , , , g• Supports: CeO2, TiO2, ZrO2, Al2O3, SiO2

CWAO OF BISPHENOL A9

S l l 160 l• Sample volume 160 ml BPA 60 mg l-1

• Temperature 160 °CPressure of air 20 bar• Pressure of air 20 bar

• Reaction time 180 min• Catalyst concentration 4 g l-1

sol-gel method wet impregnation

(w) complexation (c)(w), complexation (c) Ag/CeO2 (Sigma Aldrich)w Ag/Ce0.85Zr0.15O2 w & c Ag/Ce Zr O w & c Ag/Ce0.2Zr0.8O2 w & c

Pt/CeO2 w Pt/Ce0.8Ti0.2O2w0.8 0.2 2 Pt/Ce0.2Ti0.8O2w

Toxicity measurements with model compoundscompounds

Assay Target Importantp53 protein (immunoblotting)

Cell stress SemiquantitativeIntervillous flow(immunoblotting)

Reactive oxygen species

Oxidativestress

ROS induce macromolecular (DNA, protein,

P

PLACENTALLOBULEM( , p ,

lipids) damageComet assay DNA

damageDetects DNA-breaks

Pump Fetal arterial flow

Fetal venous flow

Maternal venous flow

Pump

MTT-assay Cell viability Detects mitochondrial

damage

Maternalreservoir

Fetalreservoir

Caspase-3 activity Apoptosis Enzyme not present in all cell lines

O /CO2 N /CO2 2 2

Placental perfusion equipmentSelected methods for molecular toxicity

In co-operation with Prof. Kirsi Vähäkangas, University of Eastern Finland (toxicity) and Prof. RiittaKeiski (photocatalysis)

Selected methods for molecular toxicity

Toxicity measurements with modelcompoundscompounds

Assay Bisphenol A

MCF-7

Diuron

MCF-7

Phthalicanhydride

MCF-7

Perfluorooctanoicacid

BeWo Bewo Bewo

MTT X X X X X X -

Propidium X - - - X - -Propidiumiodide & digitonin

X X

ROS - - - -

Comet assay - X - X - -

p53 X - - - X -

Phospho-p53 X - - - X - -

Sphere assay X - X - - -

In co-operation with Prof. Kirsi Vähäkangas, University of Eastern Finland (toxicity) and Prof. RiittaKeiski (photocatalysis)

RESULTS FROM CWAO OF BPA12

a)100

b)100

a)

60

80

al [%

]

b)

60

80

al [%

]

20

40 Ag/CeO2w Ag/Ce0.85Zr0.15O2w Ag/Ce0.2Zr0.8O2wB

PA re

mov

a

20

40

BPA

rem

ova

Pt/CeO2

0 20 40 60 80 100 120 140 160 180 2000

20 Ag/Ce0.85Zr0.15O2c Ag/Ce0.2Zr0.8O2c

Oxidation time [min]0 20 40 60 80 100 120 140 160 180 200

0

20

Oxidation time [min]

2

Pt/Ce0.8Ti0.2O2

Pt/Ce0.2Ti0.8O2

BPA removal as a function of oxidation time with Ag (a) and Pt catalysts (b).

• Both Ag and Pt catalysts were active in the removal of BPA from wastewaters Adding of silver has no effect on the catalytic activity

Too lo acti e metal content (leaching of the Ag)

[ ]

• Heponiemi , Azalim, Hu, Lassi (2014) Cerium oxide based catalysts for wet air oxidation of bisphenol A, Topics in Catalysis (submitted)

Too low active metal content (leaching of the Ag) Highest removal of BPA (97 %) with Pt/CeO2 and Pt/Ce0.8Ti0.2O2 catalysts

p , p y ( )• Heponiemi , Azalim, Hu, Lassi (2014) Catalytic wet air oxidation of bisphenol A with platinum

catalysts supported on cerium and cerium-titanium oxides, Applied Catalysis B: Environmental(submitted)

RESULTS13

C l d ff h d f h f • Catalytic oxidation is an efficient method for the treatment of ww with high organic concentration, e.g. pharmaceuticalindustryindustry

• Catalytic reaction mechanism and kinetics has to be known, b li id f d i t di t ( d )carboxylic acids are formed as intermediates (rds)

• Catalytic treatment of industrial ww affects also the toxicityy yand biodegradability of these compounds, which is currentlystudied

14MINE WATER TREATMENT WITH CHEMICALPRECIPITATIONPRECIPITATION

• SULKA-project (Sulphur Compounds in Mining Operations – Environmental Impact Assessment, Measurement and Emission Abatement)

• Our response in WP6: Treatment of mine waters

• The enhancement of lime precipitation for sulphate removal from mine p p f p fwaters is investigated

• Lime precipitation is also used as a pretreatment step before other treatment methods such as adsorption which is also studied for sulphate and metals removal from mine waters (so called hybrid method)

10.10.2014http://www.oulu.fi/sites/default/files/content/Poster_SULKA.pdf

15CHEMICAL PRECIPITATION USING LIME AND POLYMERSPOLYMERS

• Different coagulants and flocculants are studied for the improvement of the settling characteristics of the improvement of the settling characteristics of the sludge

• Precipitation experiments are done using the jar p p g jtest

• Modelling of chemical precipitation is done by MINEQL+ software

Tolonen, E-T., Tynjälä, P., Runtti, H., Luukkonen, T, Rämö, J. & Lassi, U. (2013), Mine water treatment with chemical precipitation using milk of lime and polymers, In: Proceedings of WaRes conference, August 15th Oulu, Finland (Eds. E. Pongraczand H. Pruikkonen), pp. 129-131..

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CHEMICAL PRECIPITATION USING BY-PRODUCTS

• By-products from quicklime manufacturing have By products from quicklime manufacturing have been tested successfully for mine water treatment as low-cost substitutes for commercial lime products

• All tested by-products removed over 99 % of Al, As, Cd, Co, Cu, Fe, Mn, Ni, Zn from AMD

• All tested by-products removed approximately 60 % of sulphate from AMD

Tolonen, E-T., Sarpola, A., Hu, T., Rämö, J., Lassi, U. Chemosphere 117 (2014), 419-424.

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CONCLUSIONS

• By-products from quicklime manufacturing can be used for mine water treatment By products from quicklime manufacturing can be used for mine water treatment as low-cost substitutes for commercial lime products

• Over 99% removal of metals (and 60% removal of sulphates) from AMD was obtained• Sulphate removal efficiency is limited by gypsum solubility• Therefore, some hybrid system is required for sulphate removal

Tolonen, E-T., Sarpola, A., Hu, T., Rämö, J., Lassi, U. Chemosphere 117 (2014), 419-424.

INDUSTRIAL RESIDUES AS NOVEL (AD)SORBENTS

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(AD)SORBENTS

Development process for utilisation of carbon residue formed in gasification process (wood chips).

Sari Tuomikoski: Carbon residues from biomass gasification: Activation, characterization and use as an adsorbent, Doctoral dissertation, 14.11.2014

chips).

ADSORPTION EXPERIMENTS20

• Adsorption capacity can be clearly enhanced by chemical (ZnCl ) and physical • Adsorption capacity can be clearly enhanced by chemical (ZnCl2) and physical (CO2) activation or chemical modification (FeCl3) methods

• Adsorption of heavy metals (e g Fe Cu Ni) phosphate nitrate and Adsorption of heavy metals (e.g. Fe,Cu,Ni), phosphate, nitrate and sulphate were studied

• Laboratory experiments (batch method) were carried out in order to examineLaboratory experiments (batch method) were carried out in order to examineeffect of

- initial pH- initial solution concentration isotherm studies- adsorption time kinetic modeling

Isotherm studies Kinetic modeling Error analysis

• Langmuir• Freundlich• Dubinin-Raduschevich (D-R)• Temk

•Pseudo-first-order•Pseudo-second-order•Elovich

• RMSE

Parameter Unit PACR1 CACR2 MCR3 AC 14 AC 25 Kinetic model

Carbon content % 52 1 61 8 61 0 77 6 91 9

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Carbon content % 52.1 61.8 61.0 77.6 91.9 -

BET m2 g-1 590 285 52.4 603 786 -

LangmuirNi removal qm mg g-1 - 62.9 - 3.1 - Pseudo-second-order

Cu removal qm mg g-1 - 23.3 - 4.4 - Pseudo-second-orderm

Fe removal qm mg g-1 - 21.4 - 12.1 - Pseudo-second-order

PO 2- removal q mg g-1 30 2 20 5 4 43 8 70 Pseudo second orderPO42- removal qm mg g-1 30.2 20.5 - 4.43 8.70 Pseudo-second-order

NO3- removal qm mg g-1 11.2 7.97 - 10.0 14.6 Pseudo-second-order

SO42− removal qm mg g-1 - - 19.5 - 15.0 Pseudo-second-order

1PACR: Physically activated carbon residue, 2CACR: Chemically activated carbon residue, 3MCR: Chemically modified carbon residue,4AC 1: Activated carbon (Merck), 5AC 2: Activated carbon (Norit).

References: Kilpimaa (Tuomikoski), Runtti, Kangas, Lassi, Kuokkanen (2014) Removal of phosphate and nitrate over a modified carbon residue from biomass gasification, Chemical Engineering Research and Design (in press)Kil i (T ik ki) R tti K L i K kk (2014) Ph i l ti ti f b id f bi Kilpimaa (Tuomikoski), Runtti, Kangas, Lassi, Kuokkanen (2014) Physical activation of carbon residue from biomass gasification: Novel sorbent for the removal of phosphates and nitrates from aqueous solution, Journal of Industrial and Engineering Chemistry (in press). Runtti, Tuomikoski, Kangas, Lassi, Kuokkanen, Rämö (2014) Chemically activated carbon residue from biomass gasification as a sorbent for iron(II), copper(II) and nickel(II) ions, Journal of Water Process Engineering (in press).

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CONCLUSIONS

• Industrial by-products (or waste material) can be modified to low-cost (ad)sorbentsfor the removal of (heavy) metals and some anions from industrial wastewaters

• E.g. carbon residues from energy production, silica-based minerals (mine by-products) and biopolymers (saw dust, peat, straw) are used in our study

• Modification can be done physically or chemically (addition of functional groups) to Modification can be done physically or chemically (addition of functional groups) to increase the selectivity

• Adsorbents can also be used for passive purification (e.g. closed mines), importance of biodegrability

• Biodegradation of sorbents enables their future use e.g. as fertilizers

Thank you for your kind attention!

More information:htt // h d i fi/t tki / lt k ihttp://www.chydenius.fi/tutkimus/soveltava-kemia

Contactinformation:ProfessorUllaLassi,UniversityofOulu/KokkolaUniversityConsortiumChydeniuseMail:ulla.lassi@oulu.fi,orulla.lassi@chydenius.fitel:+358400294090