1. No category

7. 2. 2014
M. Bauman,
A.Košak, Y.L. Zub,
M. Poberžnik, A. Lobnik
Inštitut za okoljevarstvo in senzorje, d.o.o.
Beloruska ulica 7, Maribor, Slovenija
R & D leader: Prof.dr. Aleksandra Lobnik, dipl.eng.text.  Sol-gel tehnologija – razvoj in aplikacije optičnih kem.
senzorjev za določevanje ekoloških in procesnih
Optical chemical sensors, Environmental protection
parametrov (npr. pH, kisik, T; amonijak, amini, anorg.
fosfat, )organo-fosfati, biogeni-amini, itd.) ;

Founded in 2006 : 22 employees (11 dr., 3 MR-Young researchers
 razvoj inteligentnih tekstilij, osebno in zaščito vojakov,
pakiranje in proizvodnjo hrane, okoljski monitoring,
•biotehnologija
Sinteze nanomaterialov,
površinska
in klinična kemija,…
RESEARCH AREAS and TEAMS
modifikacija/funkcionalizacija nanondelcev in koloidnih
Optical chemical sensors
•
•
•
Dr. Špela Korent Urek, dipl.eng.text.
Dr. Matejka Turel, dipl.eng.text.
Polonca Nedeljko, dipl.eng.chem. - Bio chemical sensors (MR)
Environmental protection
•
•
•
Dr. Mojca Poberžnik, dipl.eng.text.
Dr. Maja Bauman, dipl.eng.text.
Branka Viltužnik, dipl.eng.text. (MR)
Renewable resources and technologies
•
•
•
•
disperzij
• Razvoj tehnologij in študij naprednih anorganskih
nanomaterialov z unikatnimi fiz.-kem. lastnostmi
Assist.prof.dr. Gregor D. Zupančič, dipl.mech.eng.
Dr. Nina Novak, dipl.eng.text.
Dr. Simona Vajnhandl, dipl.biol.
Aljaž Klasinc, dipl.mech.eng. (MR)
 Implementacija in razvoj novih metod obdelave pitne,
bazenske,
industrijske/tehnološke
vode ter različnih
Nanomaterials
& Nanotechnologies
odpadnih voda.
•
Dr.filtracijskih
Aljoša Košak, materialov
dipl.eng.chem.z izboljšano
 Razvoj
selektivnostjo
Svetovanje ininraziskave
na področju
čiščenjaza AOP
dezinfekcijsko
sposobnostjo
Technical textiles
industrijskih
odpadnih
voda, analitike
ravnanja snakomunalnim
postopke in MF
ter izvajanje
osnovi
blatom
iz
ČN
in
komunalnih
odpadkov
standardiziranih
metod skladno
z zakonodajnimi
•
Dr. Andreja Gutmaher,
dipl.eng.text.
zahtevami.
 Razvoj naprav ki izjemno energijsko učinkovito
pretvorijo organske snovi v bioplin.
2
ACTIVE PROJECTS in the field of Environmental protection & Sensors:
 ACF system E!6461 »Absolute chlorine free system (ACF) for paper production using recycled
fibres - ACF system«
New advanced technology (CO2/O3/O2) for water treatment in the paper industry - more
effective with better economic and ecological impact. Develop closed water circuit with
absolute chlorine free technological process and lower amount of chemical additivies.
Total project budget: 0,6 mio € ; Duration: 01.09.2011 – 31.08.2014.
 “The development of mobile-modular water treatment plant “WaterCleanBox”
Design the mobile modular water treatment plant, testing and applying different technologies
(membrane filtration, advanced oxidation processes, adsorption and disinfection) to achieve
the optimal water quality and opportunity for water re-use.
Total project budget 1,4 mio € ; Duration: 01.01.2014 – 31.12.2014.
 “MULTI Nano Opti Sens “The development of multi nano optical chemical sensor for monitoring
of water”
Develop a prototype of optical chemical sensor system, for on-line mesure the water quality
(drinking, municipal, industrial waste) based on multiple parameters (e.g pH, T, oxygen,
ammonium, phosphate) in–situ.
Total project budget 0,4 mio €. ; Duration: 01.07.2013 – 27.09.2014.
 NATO - SPS.NUKR.SFP 984398 “ Removal of heavy metals and radionuclides from water using
ceramic and polymer membranes”
Develop a family of advanced NF and UF ceramic and polymer composite membranes containing functionalized mesoporous silica layers - capable of selective binding of heavy
metals (Hg, Cd, Cr) and uranium from surface and wastewaters.
3
Total project budget: 0,282 mio € ; Duration: 27.11.2012 – 27.11.2015.
INTRODUCTION

Water/Wastewater contamination (1-100 mg/L) by toxic heavy metals
(e.g. Zn2+, Cd2+, Hg2+, Pb2+, Cr6+ ... and radionuclides)


Conventional treatment methods - less selectivite, conatminated sludge
Membrane filtration process
-selective ion removal
-scaling prevention
Salts, CaSO4,
CaCO3,
Mg(OH)2,
other metal oxides

Functionalized amorphous silica (SiO2) particles promising for environmental applications
-
nontoxic nature, high specific surface area,
regular pore structure & surface modification
PROJEC GOALS
& EXPERIMENTAL PLAN
One-step sol formation & Surface coating:
SOL-GEL PRECURSOR + CATALYST+ ALCOHOL +
WATER
(Hydrolysis & Condensation)
- time;
T ; pH,
1
molar ratio R
(water:precursor)
2
Coating of LOOSE
conventional
MEMBRANE
Characterization
SOL
Characterization
3
 SEM + EDS analysis
 Zeta potential of planar
surface
SOL
APPLICATION on
conventional
MEMBRANE
COUPONE
 Zeta potencial - pH effect
 TEM + EDS
 IR – spectroscopy
 AAS – adsorption of
heavy metal ions
Test filtration on lab-scale pilot plant
 AAS analysis of model solutions (ion retention)
 SEM + EDS of membranes after filtration
5
1
SOL-GEL PRECURSOR + CATALYST + ALCOHOL + WATER
 One-pot synthesis / Sol-gel method (Stöber process)
of functionalized MPTMS - SiO2 nanoparticles
 Improved surface selectivity / functionality
- Alkoxysilanes (steric /electro-steric barier)
C2H5
CH3
O
C2H5
O
Si
O
methoxy group – afinity to
SiO2
O
C2H5
O
H3C
Si
SH
O
O
C2H5
Tetraethoxysilane (TEOS)
CH3
mercapto-propyl
group – donor S
(interaction with
heavy metals)
3-(mercapto-propyl) trimethoxysilane (MPTMS)
1
SOL-GEL PRECURSOR + CATALYST + ALCOHOL + WATER
One-pot synthesis conditions: TEOS, TEOS:MPTMS nanoparticles
pH ca. 4 ; ca. 10
PROJEC GOALS
& EXPERIMENTAL PLAN
One-step sol formation & Surface coating:
SOL-GEL PRECURSOR + CATALYST+ ALCOHOL +
WATER
(Hydrolysis & Condensation)
- time;
T ; pH,
1
molar ratio R
(water:precursor)
2
Coating of LOOSE
conventional
MEMBRANE
Characterization
SOL
Characterization
3
 SEM + EDS analysis
 Zeta potential of planar
surface
SOL
APPLICATION on
conventional
MEMBRANE
COUPONE
 Zeta potencial - pH effect
 TEM + EDS
 IR – spectroscopy
 AAS – adsorption of
heavy metal ions
Test filtration on lab-scale pilot plant
 AAS analysis of model solutions (ion retention)
 SEM + EDS of membranes after filtration
8
RESULTS – Sol characterization
1
Electrokinetic-potential of coloidal sols TEOS,
MPTMS
The IP near pH 3 (+ charge)
- no agglomeration at pH 4
 pH < 3; protonated site repulsion HM : adsorbent
 pH > 3; de-protonated site;
mercapto-groups available for HM
binding
RESULTS – Sol
characterization
1
TEM analysis of sols based on combination TEOS:MPTMS
precursor
T:M R 525/ P1 /14h/50 C/200 50 nm
T:M R 525/ P 0.5 /14h/50 C/1250 250 nm
T:M R 525/ P1 /14h/25 C/580 20 nm
T:M R 525/ P 0.5 /14h/25 C/950 500 nm
RESULTS – Sol
characterization
1
TEM + EDXS analysis of sols based on combination TEOS:MPTMS
precursor
50 nm
20 nm
RESULTS – Sol
characterization
1
ATR-FTIR spectroscopy of sols based on precursors
TEOS, MPTMS & combination TEOS:MPTMS
FTIR spectra of (a) TEOS precursor, (b) MPTMS precursor,
(c) sample TEOS R 525/14h/25 C/85 5 nm &
(d) sample T:M R 525/P1/14h/25 C/580 20 nm
RESULTS – Sol research
1
Adsorption (AAS analyses) of heavy metal ions on sol-gel
Nanoparticles:
T:M R 525/P1/14h/25 C
 Adsorption:
contact time 15-60 min
equilibrium 90 min
 Metal ion uptake:
99.9 % for Hg2+,
55.9 % for Pb2+,
50.2 % for Cd2+ &
4 % for Zn2+
PROJEC GOALS
& EXPERIMENTAL PLAN
One-step sol formation & Surface coating:
SOL-GEL PRECURSOR + CATALYST+ ALCOHOL +
WATER
(Hydrolysis & Condensation)
- time;
T ; pH,
1
molar ratio R
(water:precursor)
2
Coating of LOOSE
conventional
MEMBRANE
Characterization
SOL
Characterization
3
 SEM + EDS analysis
 Zeta potential of planar
surface
SOL
APPLICATION on
conventional
MEMBRANE
COUPONE
 Zeta potencial - pH effect
 TEM + EDS
 IR – spectroscopy
 AAS – adsorption of
heavy metal ions
Test filtration on lab-scale pilot plant
 AAS analysis of model solutions (ion retention)
 SEM + EDS of membranes after filtration
14
Results – membrane surface modification
2
SEM microscopy – Characterization of coated membranes by
TEOS, MPTMS & TEOS:MPTMS nanoparitcles
TEOS R 525/14h/25 C
T:M 1:1 R 525/14h/25 C
MPTMS R 525/14h/50 C
2 µm
TEOS R 174/14h/RT
MPTMS R 174/14h/25 C
T:M 1:1 R 525/14h/50 C
RESULTS – Characterization of modified membranes
2
Zeta potential
- non-modified vs. modified membrane
PROJEC GOALS
& EXPERIMENTAL PLAN
One-step sol formation & Surface coating:
SOL-GEL PRECURSOR + CATALYST+ ALCOHOL +
WATER
(Hydrolysis & Condensation)
- time;
T ; pH,
1
molar ratio R
(water:precursor)
2
Coating of LOOSE
conventional
MEMBRANE
Characterization
SOL
Characterization
3
 SEM + EDS analysis
 Zeta potential of planar
surface
SOL
APPLICATION on
conventional
MEMBRANE
COUPONE
 Zeta potencial - pH effect
 TEM + EDS
 IR – spectroscopy
 AAS – adsorption of
heavy metal ions
Test filtration on lab-scale pilot plant
 AAS analysis of model solutions (ion retention)
 SEM + EDS of membranes after filtration
17
Results – Filtration test
3
COATING OF MEMBRANE COUPONE &
FILTRATION
FILTRATION CONDITIONS:
• heavy metal salt solution:
Pb (NO3)2 & Hg (NO3)2 x H2O:
conc. 100 mg/L
• pH 4
• 5, 20 in 44 bar;
• T: room
• filtration time: 1h 30 min
• tangetional corssflow:1,6 L/min
• membrane filtration area: 80 cm2
PA layer: 0,3-0,1 µm
Lab-scale pilot plant
RO-NF-UF MSC80, OSMO Membrane Systems
PSO layer: 0,025 mm
PES layer: 0,12 mm
Surface area: 132 cm2;
dimension: 6 x 22 cm
Results – Filtration with modified membranes
3
AAS analysis – retention of Pb2+ ions from model wastewater
Results – Filtration with modified membranes
3
AAS analysis – retention of Hg2+ ions from model wastewater
Results – filtration with modified membranes
3
SEM microscopy images of membranes after filtration
NF2 loose membrane
TEOS R 525/14h/50 C
TEOS:MPTMS R 525/ P1/14h/50 C
Further investigations:
- adsorbtion for Cd, Crtotal & Hg ions
- apllication of sol-gel modificatio on UF membrane
- UF membrane testing on heavy metal ions adsorption
- filtration experiments with modif. UF membrane
- regeneration of adsorbent material
Kontakt:
Inštitut za okoljevarstvo in senzorje, d.o.o.
Beloruska ulica 7, Maribor, Slovenija
T: +386 2 333 5669
F: +386 2 333 5680
E-mail: [email protected]
Web-page: http://ios.si