recovery of humic substances from ion exchange brine

recovery of humic substances from ion exchange brine Elisabeth Vaudevire

recovery of humic substances from ion exchange brine overview origin of the brine specific adsorption of humic substances by IEX characterization of the humic substances technological aspects for compounds separation and recovery contamination with micropollutants applications opportunity for humic substances, business case and legal framework

origin and quality figures IEX process

NOM adsorption to IEX resin LC OCD profile OCD signal 8 7 6 5 4 3 2 1 0 0 10 20 30 40 50 60 70 80 retention time (minute) raw water ion exchange treated

NOM desorbed in the brine LC-OCD profile Humic s Building blocks Biopolymers LMW Acids and HS

characterization of the humic substances humic fraction as part of NOM Why characterization Prior step of purification Results from Fourier transform infra red characterization

characterization of the humic substances isolation protocol recommended by IHSS acidification to ph 1 to 2 precipitate neutralized, centrifuged and reacidified until inorganic ashes <1% = humic fraction supernatant passed through XAD-8 column = fluvic fraction

characterization of the humic substances isolation protocol recommended by IHSS SAMPLE Corg mg/l Humic C fractions IEX brine PWN total NOM 2112 non humic C 1070 52% humic acid 51% humic C 1093 fluvic acid 49% IEX brine DEWG total NOM 10409 non humic C 4707 48% humic acid 37% humic C 4978 fluvic acid 63% Waste Water treated total NOM 1328 non humic C 1079 24% humic acid 57% humic C 323 fluvic acid 43%

characterization of the humic substances FTIR spectra Fourier transform infra red spectrometry: qualitative molecular analysis method use infra red source as baseline of energy when a sample is expose to IR, absorbance of that sample is used to measure the bonds of the carbon atoms

characterization of the humic substances FTIR spectra FT-IR Spectra_CF150-200 FA1_CF150-200 HA1_CF150-200 100 90 80 70 60 50 %T 40 30 20 10 0 4000 3500 3000 2500 2000 1500 1000 500 wavenumber (cm -1 ) wavenumber (cm-1)

characterization of the humic substances FTIR spectra FT-IR Spectra_CF150-200 FA1_CF150-200 HA1_CF150-200 100 90 80 70 PWN 60 50 %T 40 FT-IR Spectra_IEX BRINE FA2_IEX BRINE HA2_IEX BRINE 100 30 20 80 10 0 4000 3500 60 3000 2500 wavenumber (cm -1 ) 2000 1500 1000 500 %T 40 20 de Watergoep 0 4000 3500 3000 2500 wavenumber (cm -1 ) 2000 1500 1000 500 SIMILAR CARBON BONDS

characterization of the humic substances FTIR spectra FT-IR Spectra_CF150-200 FA1_CF150-200 HA1_CF150-200 100 90 80 70 PWN 60 50 %T 40 30 20 FT-IR Spectra_TILBURG FA3_TILBURG 100 10 4000 HA3_TILBURG 3500 80 3000 2500 wavenumber (cm -1 ) 2000 1500 1000 500 0 60 40 %T waste water evides 20 0 4000 3500 3000 2500 2000 1500 1000 500 wavenumber (cm -1 )

characterization of the humic substances FTIR spectra FT-IR Spectra_CF150-200 FA1_CF150-200 HA1_CF150-200 C=O 100 90 80 70 60 50 %T 40 30 20 10 0 4000 3500 3000 2500 2000 1500 1000 500 wavenumber (cm -1 ) wavenumber (cm-1)

characterization of the humic substances FTIR spectra -CH2- -CH3 FT-IR Spectra_CF150-200 FA1_CF150-200 HA1_CF150-200 100 90 80 70 60 50 %T 40 30 20 10 0 4000 3500 3000 2500 2000 1500 1000 500 wavenumber (cm -1 ) wavenumber (cm-1)

characterization of the humic substances FTIR conclusions stretch of C=0 bond, indicates high polarity higher than in most commercially available samples stretch of C=0 in carbonyl linked to benzene ring higher proportion of aromatic rings in fulvic acids presence of CH3 and CH2 in aliphatic parts of the structure, indicates hydrophobicity HS from brine are more soluble and presumably have better chelating properties compared to other sources of commercial humic substances

separation of humic substances on industrial scale

mono-selective electrodialysis c SO 4 NO M a c a c a SO 4 NO M SO 4 NO M brine water brine water brine

mono-selective electrodialysis c SO 4 NO M a c a c a SO 4 NO M SO 4 NO M brine brine brine

electrodialysis standard c NO M a c a c a SO 4 SO 4 SO 4 NO M NO M brine water brine water brine

electrodialysis standard c NO M a c a c a SO 4 NO M SO 4 NO M SO 4 brine 2 SO 4 brine 2 SO 4 brine

separation of humic substances on industrial scale

contamination with organic micropollutants definition organic substances whose toxic, persistent and bioaccumulative properties may have a negative effect on the environment and/or organisms. They are present in many products that we consume daily (drugs, cosmetics, phytosanitary products, insecticides, etc.), at the home or in industry.

contamination with micropollutants micropollutants from IJssel lake concentrating in the brine 40% 35% 30% 25% 20% 15% 10% 5% 0% negative neutral zwitter positive

contamination with micropollutants passage from brine through mono selective electrodialysis 0,90 0,70 0,50 0,30 0,10-0,10 percentage remaining in the brine percentage adsorbed/ degrading percentage transferred to concentrate

contamination with micropollutants passage from ED effluent through electrodialysis standard 0,90 0,70 0,50 0,30 0,10-0,10 percentage remaining in the brine percentage adsorbed/ degrading Percentage transferred to concentrate

contamination with micropollutants conclusions confirms the retention onto ion exchange resin of negatively charged organic micro-pollutants specifically explains the passage through selective and standard ion exchange membranes by van der waals radius: smaller molecules only through selective membranes most organic micropollutants species passing standard membranes no standards available for organic micro-pollutants limits in NOM applications

Thank you!