Wrocław University of Science and Technology Faculty of Chemistry

PROCEEDINGS

OF THE IVth

INTERNATIONAL CONFERENCE ON METHODS AND MATERIALS FOR SEPARATION PROCESSES

SEPARATION SCIENCE

– THEORY AND PRACTICE 2016

4-8 SEPTEMBER, 2016, BRUNÓW (LWÓWEK ŚLĄSKI), POLAND

Oficyna Wydawnicza Politechniki Wrocławskiej Wrocław 2016

EDITORS

Anna Jakubiak-Marcinkowska

Andrzej W. Trochimczuk

PREPARATION FOR PRINTING

Anna Jakubiak-Marcinkowska

Printed in the camera ready form

All rights reserved. No part of this book may be reproduced, stored in a retrival system, or transmitted in any form or by any means,

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© Copyright by Oficyna Wydawnicza Politechniki Wrocławskiej, Wrocław 2016

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ISBN 978-83-7493-949-2

Druk i oprawa: beta-druk, www.betadruk.pl

IVth INTERNATIONAL CONFERENCE ON METHODS AND MATERIALS FOR SEPARATION PROCESSES

SEPARATION SCIENCE – THEORY AND PRACTICE 2016

BRUNÓW (LWÓWEK ŚLĄSKI) POLAND

4-8 SEPTEMBER 2016

organized by:

Faculty of Chemistry

Wrocław University of Science and Technology

INTERNATIONAL ADVISORY BOARD

Prof. S. D. Alexandratos, USA Prof. N. Kabay, Turkey Prof. J. L. Cortina, Spain Dr D. J. Malik, UK Prof. G. Cote, France Prof. K. Ohto, Japan Prof. E.S. Dragan, Romania Prof. M. Streat, UK Prof. A.K. Frolkova, Russia Prof. F. Svec, USA Prof. E. Guibal, France Prof. G. Sulaberidze, Russia Prof. A. de Haan, The Netherlands Prof. V.V. Tepliakov, Russia Prof. Z. Hubicki, Poland Prof. K. Yoshizuka, Japan

ORGANIZING COMMITTEE

Prof. Andrzej W. Trochimczuk - Chairman Dr Anna Jakubiak-Marcinkowska Dr Sylwia Ronka Małgorzata Kujawska Magdalena Legan

Address: Faculty of Chemistry

Wroclaw University of Science and Technology Wybrzeże Wyspiańskiego 27,

50-370 Wrocław, Poland Phone: +4871 320 3173

Fax: +4871 320 2152

5

CONFERENCE PROGRAM

4.09. Sun

5.09. Mon

6.09. Tue

7.09. Wed

8.09. Thu

9:00 - 9:15 Opening

9:15 - 9:55 L1 J. Love

9:15 - 9:55 L3 N. Kabay

9:15 - 9:55 L5 M. Maciejewska

09:30 Bus departure for Wrocław

9:55 - 10:35 L2 K. Ohto

9:55 - 10:35 L4 R. Wickramasinghe

9:55 - 10:15 S12 E. Reyhanitash

10:35 - 10:55 S1 S. Nishihama

10:35 - 10:55 S6 W. Kujawski

10:15 - 10:35 S13 Ł. Pazdur

10:35 - 10:55 S14 B. Schuur

10:55 - 11:20 Coffee Break

10:55 - 11:20 Coffee Break

10:55 - 11:20 Coffee Break

11:20 - 11:40 S2 M. Regel-Rosocka

11:20 - 11:40 S7 C. Ghierasim

11:20 - 11:40 S15 M. Bogdanov

11:40 - 12:00 S3 J. Mikeš

11:40 - 12:00 S8 S. Koter

11:40 - 12:00 S16 M. Grochowicz

12:00 - 12:20 S4 M. Campos Assuncao

12:00 - 12:20 S9 M. Turek

12:00 - 12:20 S17 I. Polowczyk

12:20 – 12:40 S5 L. Sprakel

12:20 - 12:40 S10 M. Bryjak

12:20 - 12:40 Closing Remarks

12:40 - 13:00 S11 S18 M. Wenzel K. Rychlewska

12:40 - 14:00 Lunch

13:00 – 14:20 Lunch

12:40 - 14:00 Lunch

15:00 - 19:00 Registration

14:00 - 16:00 Poster Session

14:00 - 18:30 Excursions

19:00 - 21:00 Welcome Reception

20:00 - 23:00 Grill Dinner

19:30 - 02:00 Banquet

18:30 - 19:45 Dinner

6

7

I. LECTURES L1 Jason Love (University of Edinburgh, UK)

UNDERSTANDING THE CHEMISTRY THAT UNDERPINS THE RECOVERY OF PRECIOUS METALATES

21

L2 Keisuke Ohto, J.-Y. Kim, S. Morisada, H. Kawakita, M. Maeki, R.R. Sathuluri, M. Miyazaki (Saga University, Japan) PRECIOUS METAL SEPARATION WITH CALIXARENE DERIVATIVES USING MICROREACTOR SYSTEM

22

L3 Nalan Kabay (Ege University, Izmir, Turkey) APPLICATION OF MEMBRANE SEPARATION PROCESSES FOR INDUSTRIAL WASTEWATER RECLAMATION AND REUSE

26

L4 S. Ranil Wickramasinghe, Xianghong Qian (University of Arkansas, USA) MULTIFUNCTIONAL MEMBRANES FOR ADVANCED SEPARATIONS

27

L5 Małgorzata Maciejewska (Maria Curie-Skłodowska University, Poland) POLAR POLYMERIC ADSORBENTS AND THEIR APPLICATIONS

28

8

II. SHORT LECTURES S1 Syouhei Nishihama, Taihei Harano, Kazuharu Yoshizuka

PREPARATION OF SILICA-BASED SOLVENT IMPREGNATED ADSORBENT FOR SEPARATION OF RARE EARTH METALS

33

S2 Martyna Rzelewska, Maciej Wiśniewski, Magdalena Regel-Rosocka SEPARATION OF PGM IONS FROM THEIR MIXTURES WITH ORGANIC SOLUTIONS OF QUATERNARY PHOSPHONIUM SALTS

35

S3 Jiri Mikeš, Maria P. Pinheiro, Ludek Jelínek SEPARATION OF LITHIUM ISOTOPE BY STRONG ACID ION EXCHANGE RESIN

37

S4 Mariana Campos Assuncao, Alexandre Chagnes, Hubert Halleux, Gérard Cote PURIFICATION OF PHOSPHORIC ACID BY LIQUID-LIQUID EXTRACTION

40

S5 Lisette M.J. Sprakel, Boelo Schuur AFFINITY BASED LIQUID-LIQUID EXTRACTION OF CARBOXYLIC ACIDS ANALYZED BY ISOTHERMAL TITRATION CALORIMETRY

41

S6 Wojciech Kujawski, Anna Kujawska, Katarzyna Knozowska, Marcin Cichosz, Roman Buczkowski, Joanna Kujawa IMPLEMENTATION OF MEMBRANE SEPARATION TECHNIQUES IN THE PRODUCTION OF BUTANOL BY FERMENTATION PROCESS

44

S7 Cristina V. Gherasim, Tobias Luelf, Hannah Roth, Matthias Wessling NOVEL HOLLOW FIBER MEMBRANES FOR LOW PRESSURE NANOFILTRATION

45

S8 Stanisław Koter, Paulina Cytarska, Leszek Stobiński RETENTION PROPERTIES OF GRAPHENE OXIDE MEMBRANES IN THE FILTRATION OF ELECTROLYTE SOLUTIONS

47

S9 Dorota Babilas, Marian Turek, Krzysztof Mitko, Piotr Dydo, Marek Słowik, Ewa Laskowska ELECTRODIALYSIS AS AN ALTERNATIVE EDI PRETREATMENT METHOD

51

S10 Marek Bryjak, Anna Siekierka, Jan Kujawski EXTRACTION OF LITHIUM FROM AQUEOUS SOLUTIONS BY MEANS OF SELECTIVE CAPACITIVE DEIONIZATION

55

9

S11 P74

Katarzyna Rychlewska, Krystyna Konieczny, Wojciech Kujawski APPLICATION OF PERVAPORATION FOR SULFUR COMPOUNDS REMOVAL FROM GASOLINE

58

S12 Ehsan Reyhanitash, Sascha R. A. Kersten, Boelo Schuur VOLATILE FATTY ACID RECOVERY FROM FERMENTED WASTEWATER VIA ADSORPTION

59

S13 Lukasz Pazdur, Serge Tavernier, Kourosch Abbaspour Tehrani SEPARATION OF PRIMARY AND SECONDARY FATTY ALCOHOLS AND THEIR DERIVATIVES AND SUBSEQUENT DETERMINATION OF THE POSITION OF HYDROXYL GROUP IN SECONDARY ALCOHOLS

63

S14 Sandra Corderi, Erik Heeres, Boelo Schuur KINETIC EXTRACTIVE RESOLUTION

65

S15 Ivan Svinyarov, Rozalina Keremedchieva, Anely Nedelcheva, Milen G. Bogdanov IONIC LIQUIDS AS ALTERNATIVE EXTACTIVE SYSTEMS FOR QUANTITATIVE DETERMINATION OF NATURAL PRODUCTS IN PLANTS

66

S16 Marta Grochowicz, Przemysław Pączkowski, Barbara Gawdzik MODIFIED METHACRYLATE POLYMER PARTICLES AND THEIR APPLICATION AS COLUMN PACKINGS IN HPLC

67

S17 Izabela Polowczyk, Anna Bastrzyk, Tomasz Koźlecki HYDROPHOBIC AGGREGATION OF TALC IN AQUEOUS SOLUTION IN RELATION TO THE OIL AGGLOMERATION PROCESS

68

S18 Added: Marco Wenzel, Karsten Gloe, Jan J. Weigand TRIPODAL POLYAMINE – AMBIVALENT RECEPTORS FOR CATION AND ANION EXTRACTION

157

10

III. POSTERS P1 Dženita Avdibegović, Mercedes Regadìo, Koen Binnemans

PRECONCENTRATION OF SCANDIUM FROM BAUXITE RESIDUE LEACHATES BY SUPPORTED IONIC LIQUID PHASE

71

P2 Piotr Dydo, Dorota Babilas, Agata Jakóbik-Kolon, Andrzej Milewski, Danuta Bentkowska, Aneta Franczak, Ryszard Nycz A STUDY ON THE ELECTRODIALYTIC NICKEL SALTS CONCENTRATION

72

P3 Dorota Babilas, Piotr Dydo THE INFLUENCE OF CHELATING AGENTS ON THE ELECTRODIALYTIC ZINC RECOVERY FROM SPENT ELECTROPLATING BATH

73

P4 Nagaphani Kumar Batchu, Koen Binnemans SOLVOMETALLURGICAL SEPARATION OF RARE-EARTH IONS BY EXTRACTION WITH TWO MUTUALLY IMMISCIBLE ORGANIC PHASES

74

P5 Helena Bendova, Hana Dvorakova, Tomas Weidlich HYDROMETALLURGICAL SEPARATION OF NICKEL FROM SPENT RANEY Ni CATALYST USING DIFFUSION DIALYSIS FOR RECYCLING OF SULPHURIC ACID

75

P6 Joanna Bok-Badura, Agata Jakóbik-Kolon, Krzysztof Karoń, Dorota Babilas, Artur P. Herman, Sławomir Boncel PREPARATION AND CHARACTERIZATION OF SORBENT BASED ON PECTIN AND CARBON NANOTUBES

76

P7 Joanna Bok-Badura, Agata Jakóbik-Kolon, Andrzej K. Milewski, Krzysztof Mitko SORPTION STUDIES OF CADMIUM AND LEAD IONS ON HYBRID POLYSACCHARIDE BIOSORBENTS

77

P8 Anton K. Bonarev, Andrei Yu. Smirnov, Georgy A. Sulaberidze, Shi Zeng, Valentin D. Borisevich, Dongjun Jiang CASCADES WITH ADDITIONAL OUTGOING FLOWS FOR SIMULTANEOUS CONCENTRATION OF INTERMEDIATE COMPONENTS FROM MULTICOMPONENT ISOTOPE MIXTURES

78

P9 Laura Cocheci, Lavinia Lupa ADSORPTION OF MOLYBDATE ANION (MoO42-) by Zn/Al LAYERED DOUBLE HYDROXIDE OBTAINED FROM ZINC ASH

79

11

P10 Corneliu Mircea Davidescu, Andreea Gabor, Adina Negrea,

Mihaela Ciopec, Petru Negrea THE USE OF NATURAL POLYMER IN THE REMOVAL OF RARE EARTH ELEMENTS CANCELLED

80

P11 Mustafa Gazi, Akeem A. Oladipo EFFICIENT BORON ABSTRACTION USING HONEYCOMB-LIKE POROUS MAGNETIC HYBRIDS: ASSESSMENT OF TECHNO-ECONOMIC RECOVERY OF BORIC ACID

81

P12 Mustafa Gazi, Kola A. Azalok, Akeem A. Oladipo REMOVAL OF NICKEL(II) IONS FROM AQUEOUS SOLUTION BY MAGNETIC BIOCHAR PALM SEEDS

82

P13 Paulina Gęca, Agata Góźdź, Marzena Gęca, Dorota Kołodyńska, Zbigniew Hubicki PARAMETERS OPTIMIZATION FOR ADSORPTION OF HEAVY METAL IONS AND DYES FROM WASTEWATERS

83

P14 Paulina Gęca, Agata Góźdź, Marzena Gęca, Dorota Kołodyńska, Zbigniew Hubicki REMOVAL OF HEAVY METAL IONS AND PHENOL FROM AQUEOUS SOLUTIONS

84

P15 Anna Jakubiak-Marcinkowska, Agnieszka Głowińska INVERSE SUSPENSION POLYMERIZATION AS A NEW TOOL FOR OBTAINING OF MOLECULARLY IMPRINTED POLYMERS FOR BIOLOGICALLY ACTIVE COMPOUNDS UPTAKE

85

P16 Małgorzata Gnus, Gabriela Dudek, Roman Turczyn, Krystyna Konieczny APPLICATION OF HYBRID CHITOSAN MEMBRANES CONTAINING METAL OXIDES IN PERVAPORATIVE DEHYDRATION OF ETHANOL/WATER MIXTURE

86

P17 Joanna Kluczka, Małgorzata Gnus, Gabriela Dudek, Roman Turczyn REMOVAL OF BORON FROM AQUEOUS SOLUTION BY COMPOSITE CHITOSAN BEADS

87

P18 Agata Góźdź, Paulina Gęca, Marzena Gęca, Dorota Kołodyńska, Zbigniew Hubicki SURFACE ACTIVATED HYDROTHERMAL FLY ASH AND ITS COMPOSITES FOR SIMULATANEOUS HEAVY METALS AND DYE REMOVAL

88

12

P19 Agata Góźdź, Paulina Gęca, Marzena Gęca, Dorota Kołodyńska, Zbigniew Hubicki CHITOSAN-ZEOLITES COMPOSITES FOR MICROELEMENTS ADSORPTION

89

P20 Marta Grochowicz, Łukasz Szajnecki SORPTION OF SELECTED PESTICIDES ON POLY(MAA-CO-EGDMA) POLYMERIC SORBENT

90

P21 Yusuke Imamura, Tadashi Okobira REMOVAL OF PPCPS BY MOLECULAR STACKING

91

P22 Mateusz Sambor, Krzysztof Mitko, Agata Jakóbik-Kolon RECOVERY OF PRECIOUS METALS FROM ELECTRONIC WASTE

92

P23 Agata Jakóbik-Kolon, Dominik Zdybał, Andrzej K. Milewski, Krzysztof Mitko, Ewa Laskowska, Joanna Bok-Badura KINETICS OF ZINC IONS REMOVAL ON HYDROLYSED PMMA SORBENTS

93

P24 Dorota Kołodyńska, Alicja Skiba, Bożena Górecka, Zbigniew Hubicki UPTAKE OF METAL IONS IN THE PRESENCE OF BIODEGRADABLE EDDS ON SUPERABSORBENTS

94

P25 Dorota Kołodyńska, Agata Góźdź, Paulina Gęca, Marzena Gęca, Zbigniew Hubicki CHARACTERISTICS OF SYNTHETIC ZEOLITE FOR REMOVAL OF Cr(VI) IONS

95

P26 Przemyslaw B. Kowalczuk FACILE DETERMINATION OF FROTHER FOAMABILITY INDEX

96

P27 Marta Kołodziejska, Jolanta Kozłowska, Iwona Zawierucha, Cezary Kozłowski HIGHLY SELECTIVE AND EFFICIENT TRANSPORT OF Au(III), Pt(IV), Pd(II) FROM HYDROCHLORIC ACID ACROSS POLYMER INCLUSION MEMBRANES CONTAINING IONIC LIQUID AS ION CARRIER

97

P28 Anna Nowik-Zając, Cezary Kozłowski APPLICATION OF CALIXPYRROLES FOR Ag(I) AND Cu(II) SEPARATION FROM ELECTRONIC WASTE SOLUTIONS

98

P29 Justyna Krukowska, Dorota Kołodyńska INVESTIGATIONS OF COPPER(II) AND CADMIUM(II) IONS SORPTION USING MAGNETIC BIOCHAR

99

13

P30 Justyna Krukowska, Dorota Kołodyńska

REMOVAL OF ARSENIC(V) AND CHROMIUM(VI) FROM AQUEOUS SOLUTIONS WITH BIOCHAR APPLICATION

100

P31 Małgorzata Kujawska, Andrzej W. Trochimczuk INFLUENCE OF VARIOUS SILICA MODIFICATIONS ON THE SELECTIVITY OF HARD-TEMPLATED MOLECULARLY IMPRINTED POLYMERIC ADSORBENTS

101

P32 Wojciech Kujawski, Andrzej Kraslawski, Karolina Jarzynka, Katarzyna Knozowska, Edyta Rynkowska, Marek Bryjak, Jan Kujawski, Joanna Kujawa IMPACT OF ORGANIC COMPONENT ON SEPARATION EFFICIENCY OF HYDROPHILIC PERVAPORATION WITH POLYMERIC MEMBRANES

102

P33 Magdalena Legan, Andrzej Trochimczuk THE INFLUENCE OF pH ON THE SORPTION OF ORGANIC ACIDS ON NOVEL POLYMERIC ION EXCHANGE RESIN

103

P34 Agnieszka Miśkiewicz, Grażyna Zakrzewska-Kołtuniewicz, Anna Abramowska, Sylwia Pasieczna-Patkowska MEMBRANE FOULING INVESTIGATION - A COMPARISION OF DIFFERENT TECHNIQUES

104

P35 A. Abramowska, D. K. Gajda, K. Kiegiel, A. Miśkiewicz, P. Drzewicz, G. Zakrzewska-Kołtuniewicz PURIFICATION OF FLOWBACK FLUIDS AFTER HYDRAULIC FRACTURING OF POLISH GAS SHALES BY HYBRID METHODS

105

P36 Tomoya Nishioka, Tadashi Okobira THE FUNCTIONALIZATION OF POROUS MATERIAL BY IMMOBILIZED ENZYME

106

P37 Tadashi Okobira, Tomoya Ueda, Koudai Ikesue, Yusuke Sanada, Shota Fujii, Kazuo Sakurai 3D STRUCTURAL ANALYSIS OF SUPERMOLECULES IN AQUEOUS SOLUTION BY X-RAY SCATTERING AND COMPUTATIONAL CHEMISTRY METHODS

107

P38 Magdalena Pilśniak-Rabiega, Katarzyna Wejman-Gibas SELECTIVE RECOVERY OF SILVER FROM CHLORIDE SOLUTIONS ON FUNCTIONALIZED RESINS

108

P39 I. Polowczyk, R. Sawicki, A. Bastrzyk, E. Lorenc-Grabowska THE USE OF ACTIVATED CARBON OBTAINED FROM WASTE BLEACHING EARTH TO REMOVAL OF CHROMIUM(VI)

109

14

P40 B. Pośpiech, J. Gęga, W. Kujawski, P. Czuprynski, T. Janda

APPLICATION OF THIOSALICYLATE-BASED IONIC LIQUID FOR HEAVY METAL REMOVAL FROM MODEL WASTEWATER USING POLYMER INCLUSION MEMBRANES

110

P41 Beata Pośpiech RECOVERY OF PLATINUM(IV) FROM AQUEOUS SOLUTIONS BY TRANSPORT ACROSS POLYMER INCLUSION MEMBRANES WITH THIOSALICYLATE-BASED IONIC LIQUID AS CARRIER

111

P42 Ie. V. Pylypchuk, D. Kołodyńska, P. P. Gorbyk DEVELOPMENT OF HYBRID CHITOSAN/Fe3O4 NANOCOMPOSITES FOR Gd3+ AND Gd DTPA ADSORPTION

112

P43 Łukasz Radosiński, Karolina Labus MOLECULAR MODELLING STUDIES OF POLY(VINYL ALCOHOL) HYDROGEL SWELLING PROCESS AS A TEMPLATE FOR A QSPR ANALYSIS

113

P44 Elżbieta Radzymińska-Lenarcik, Agnieszka Michalak STUDIES ON PERMEATION OF SOME TRANSITION METALS USING 1,2,4-TRIMETHYLIMIDAZOLE AS SELECTIVE ION CARRIER

114

P45 Mercedes Regadío, Koen Binnemans EXTRACTION OF RARE EARTHS FROM CHLORIDE SOLUTIONS TO A NITRATE IONIC LIQUID BY THE NEUTRAL EXTRACTANT CYANEX 923

115

P46 Francisco J. Alguacil, Magdalena Regel-Rosocka Co(II) REMOVAL FROM CHLORIDE AND SULFATE SOLUTIONS WITH ACIDIC AND BASIC EXTRACTANTS

116

P47 Sylwia Ronka, Sara Targońska REMOVAL OF PRECIOUS METALS FROM AQUEOUS SOLUTIONS BY POLYMERIC MATERIAL CONTAINING SULFUR ATOMS

117

P48 Handan Usta, Fatih Bildik, Gülçin Torunoglu Turan, Bahire Filiz Senkal PREPARATION OF POLY(ACRYLAMIDE) GRAFTED ONTO CROSSLINKED POLY(HEMA-co-MMA) BEADS FOR REMOVAL OF PHENOLS

118

P49 Andrei Yu. Smirnov, Anton K. Bonarev, Shi Zeng, Georgy A. Sulaberidze, Valentin D. Borisevich, Dongjun Jiang OPTIMIZATION OF CASCADES FOR BINARY ISOTOPE SEPARATION USING VARIOUS EFFICIENCY CRITERIA

119

15

P50 W. Sofińska-Chmiel, D. Kołodyńska, Z. Hubicki, E. Mendyk APPLICATION OF ION EXCHANGERS DOWEX M 4195 AND LEWATIT® MONOPLUS TP 220 FOR REMOVAL OF Zn(II) AND Cu(II) IONS FROM GALVANIC WASTEWATERS

120

P51 W. Sofińska-Chmiel, D. Kołodyńska, Z. Hubicki, E. Mendyk APPLICATION OF ION EXCHANGERS FOR PURIFICATION OF GALVANIC WASTEWATER FROM HEAVY METALS

121

P52 Georgy A. Sulaberidze, Andrei Yu. Smirnov, Shi Zeng, Valentin D. Borisevich, Dongjun Jiang COMPARISON OF VARIOUS SEPARATION POTENTIALS FOR MULTI-ISOTOPE MIXTURE SEPARATION

122

P53 Yuki Ueda, Shintaro Morisada, Hidetaka Kawakita, Keisuke Ohto EXTRACTION OF PLATINUM GROUP METALS WITH NITROGENOUS EXTRACTANTS AND ITS EXTRACTION MECHANISM ANALYSIS

123

P54 Lavinia Lupa, Bianca Maranescu, Aurelia Visa EQUILIBRIUM AND KINETIC STUDIES OF CHROMIUM IONS ADSORPTION ON Co(II) BASED PHOSPHONATE METAL ORGANIC FRAMEWORKS

124

P55 Bianca Maranescu, Adriana Popa, Lavinia Lupa, Aurelia Visa USE OF CHITOSAN COMPLEX WITH AMINOPHOSPHONIC GROUPS AND COBALT FOR Sr(II) IONS REMOVAL

125

P56 Lavinia Lupa, Raluca Voda, Adriana Popa ADSORPTION BEHAVIOR OF CESIUM AND STRONTIUM ONTO CHITOSAN IMPREGNATED WITH IONIC LIQUID

126

P57 Raluca Voda, Lavinia Lupa, Laura Cocheci COMPARATIVE ADSORPTION OF PHENOL AND LEAD FROM AQUEOUS SOLUTIONS ONTO Co3O4

127

P58 Monika Wawrzkiewicz, Zbigniew Hubicki STRONGLY BASIC ANION EXCHANGER LEWATIT MONOPLUS SR-7 FOR ACID, REACTIVE AND DIRECT DYES REMOVAL FROM WASTEWATERS

128

P59 Monika Wawrzkiewicz, Małgorzata Wiśniewska, Zbigniew Hubicki, Stanisław Chibowski, Vladimir M. Gun’ko, Vladimir I. Zarko COMPARISON OF EFFICIENCY OF SILICA-ALUMINA OXIDES IN C.I. DIRECT BLUE 71 REMOVAL FROM AQUEOUS SOLUTIONS

129

P60 T. Weidlich, M. Frantíková, L. Nováková, M. Štěpánková SEPARATION OF CHLORINATED BIOCIDES FROM AQUEOUS EFFLUENTS USING IONIC LIQUIDS

130

16

P61 Katarzyna Wejman-Gibas, Magdalena Pilśniak-Rabiega THE UPTAKE OF SILVER(I) FROM CHLORIDE LEACHING SOLUTIONS BY AMINE EXTRACTANTS

131

P62 Katarzyna Witt, Elżbieta Radzymińska-Lenarcik SEPARATION OF SOME TRANSITION METALS BY SOLVENT EXTRACTION USING 3-SUBSTITUTED DERIVATIVES OF β-DIKETONES AS SELECTIVE EXTRACTANTS

132

P63 Joanna Wolska, Małgorzata Kujawska pH-RESPONSIVE MOLECULARLY IMPRINTED POLYMER FOR SORPTION AND RAPID DESORPTION OF DIBUTYL PHTHALATE

133

P64 Joanna Wolska, Katarzyna Jackiewicz, Małgorzata Kujawska REMOVAL OF DIETHYL PHTHALATE BY MEANS OF HYBRID MEMBRANE-SORPTION PROCESS

134

P65 Anna Wołowicz, Zbigniew Hubicki COMPARISON OF STRONGLY BASIC ION EXCHANGERS APPLICABILITY FOR PALLADIUM(II) IONS REMOVAL

135

P66 Anna Wołowicz, Zbigniew Hubicki STUDIES ON REMOVAL OF HEAVY METAL(II) IONS BY ION-EXCHANGE METHOD

136

P67 Grzegorz Wójcik, Zbigniew Hubicki INVESTIGATIONS OF CHROMIUM(VI) IONS SORPTION AND REDUCTION ON STRONG BASIC ANION EXCHANGER

137

P68 Grzegorz Wójcik, Zbigniew Hubicki, Bogdan Tarasiuk INVESTIGATIONS OF A NEW EXTRACTION AGENT FOR CHROMIUM(VI) IONS REMOVAL FROM WATER

138

P69 Gülcemal Yildiz, Filiz Şenkal, Zeynep Aydogmus DETERMINATION OF EUGENOL IN CLOVES WITH VOLTAMMETRIC TECHNIQUE BY USING A RESIN MODIFIED CARBON PASTE ELECTRODE

139

P70 Ebru Tekneci, Gulcin Torunoglu Turan, Gülcemal Yıldız, Bahire Filiz Senkal REMOVAL OF DYES FROM WATER BY POLY(3-SULFOPROPYL ACRYLATE POTASSIUM SALT-co-2-DIETHYLAMINOETHYL METHACRYLATE) HYDROGEL

140

P71 Iwona Zawierucha, Cezary Kozłowski, Jolanta Kozłowska, Michał Michalak SEPARATION OF LITHIUM FROM SPENT LIQUORS USING THE MALIC ACID COPOLYMERS

141

17

P72 Liang Zhao, Andrzej G. Chmielewski SEPARATION OF CESIUM-137 FROM SPENT NUCLEAR FUEL AND STORAGE POOL

142

P73 Luděk Jelínek, Helena Parschová, Richard Seydl, Jiří Mikeš, Eva Mištová LABSCALE AUTOMATION OF CYCLIC ION EXCHANGE PROCESSES

143

NOTES

144

AUTHORS INDEX 153

I. LECTURES

21

UNDERSTANDING THE CHEMISTRY THAT UNDERPINS THE RECOVERY OF PRECIOUS METALATES

Jason Love

School of Chemistry, University of Edinburgh, David Brewster Road, Edinburgh

EH9 3FJ, UK e-mail: jason.love@ed.ac.uk

Solvent extraction processes are used extensively in the recovery of metals from primary ores and secondary waste electronic and electrical equipment (WEEE), yet a detailed understanding of the chemical interactions that occur during these processes is only recently becoming evident (1,2). This is important, as better understanding of the chemical modes of action of extraction processes (Figure 1) can lead to enhanced and selective metal recovery, leading to cost, safety, energy, and environmental benefits. In this presentation, the recovery of precious metals as their anions from acidic chloride media will be described. In particular, the design of new reagents for the selective recovery of platinum and palladium will be exemplified, along with the development of simple reagents for the selective extraction of gold from metal mixtures representative of WEEE. These processes have been studied extensively using a variety of chemical characterisation techniques, and have led to insight into the important factors for reagent design.

Fig. 1. Chemical species formed during metal recovery by solvent extraction References 1. A.M. Wilson et al., Chem. Soc. Rev., 43 (2014) 123-134. 2. J.R. Turkington et al., Chem. Commun., 49 (2013) 1891-1899.

22

PRECIOUS METAL SEPARATION WITH CALIXARENE DERIVATIVES USING MICROREACTOR SYSTEM

K. Ohto1, J.-Y. Kim1, S. Morisada1, H. Kawakita1,

M. Maeki2, R.R. Sathuluri3, M. Miyazaki1,2,3

1Saga University, 1-Honjo, Saga 840-8502, Japan 2Kyushu University, Kasuga, Fukuoka 816-8580, Japan

3AIST, Shuku, Tosu 841-0052, Japan e-mail: ohtok@cc.saga-u.ac.jp

Metal recycling can play an important role for a stable supply of the metal resource, for Japan is a just poor country for such resource. So-called “urban mine” is defined as apparent mine consisting of valuable metal resources in spent and wasted small home appliance products. The urban mine contains sufficient amounts of valuable elements, but mostly in different varieties and in trace amounts, which cause the difficulty of mutual separation and recovery. Solvent extraction is one of the most versatile techniques and the nature of solvent extraction reagent affects the extraction and separation efficiencies. Macrocyclic calixarenes are three-dimensionally arranged and can discriminate certain target elements (1). In our previous work, methyl ketonic derivative of calix[4]arene exhibited high silver selectivity over divalent palladium in nitric acid media (2). However, it showed some drawbacks such as low lipophilicity and slow extraction rate. Such disadvantages should be improved for commercial use. Using microreactor system is one of the candidates to overcome because it would contribute to reduced amounts of reagent and solvent employed, extremely larger interfacial area for fast extraction rate, laminar flow for smooth operation (3,4). In our recent work, parallel two phases flow (PTPF) type and slug flow (SF) type of microreactors were employed for the silver extraction with the tetraketonic derivative of calix[4]arene in nitric acid media and the extraction rates were compared. The results showed the availability of both microreactors with the utmost improvement of the extraction rate compared to that of the conventional batch-wise method. In the present work, stepwise separation of silver, palladium and platinum with three types of calix[4]arene derivatives using batch-wise method and droplet type microreactor. The methylketonic (1), 2-quinolyl (5), and 2-pyridyl (6) derivatives of calix[4]arene shown in Fig. 1 were prepared from unmodified p-t-octylcalix[4]arene in similar manners to the previously described procedures. The batch-wise extraction was carried out by the conventional method. Organic solutions were prepared by diluting the extraction reagent with analytical grade chloroform to 5 mM (M = mol dm-3). Aqueous solutions were prepared by dissolving each

Fig. 1. Structures and abbreviation of

p-t-octylcalix[4]arene derivatives

23

metal nitrate to 0.1 mM in 0.1 M or 5 M nitric acid. They were arbitrarily mixed to adjust the nitric acid concentration. Equal volumes of both phases were mixed and shaken at 303 K for more than 72 h, which was sufficient to attain equilibrium. After phase separation, metal concentrations in the aqueous phase were measured by ICP-AES (Shimadzu, ICPS-8100). The amounts of the extracted metal ions were calculated from the differences of the metal concentrations in the aqueous phase before and after equilibrium. The stepwise metal extraction from real waste solutions was carried out by diluting the original waste solution (1.0 M nitric acid) by 1000 times with 1.0 M nitric acid and by stepwise extracting with optimal reagent for silver, palladium and platinum. The contents of silver, palladium, platinum, and coexisting copper and sodium in the original waste solution were 1.20 M, 0.200 M, 0.0200 M, 0.818 M, 1.87 M, respectively. The concentrations of silver, palladium and platinum in examined solution were adjusted to 1.20 mM, 0.200 mM, 0.0200 mM. The stripping from the metal-loaded extractant was also carried out. Fabrication of both type microreactors together with single metal extraction were described and shown in the previous paper (7). The stepwise metal extraction from real waste solutions was carried out in a similar manner to the batch-wise extraction by diluting the original waste by 1200 times and by stepwise extracting with optimal reagent for silver, palladium and platinum using SF type microreactor system. The concentrations of silver, palladium and platinum in examined solution were adjusted to 1.00 mM, 0.167 mM, 0.0167 mM. The stripping from the metal-loaded extractant was also carried out with 2 M ammonium thiocyanate and 1 M thiourea. The schematic showing the droplets of aqueous and organic in the microchannel and glass microreactor employed in the metal ion extractions were shown in the previous work (8). It was found that the required times of silver extraction with tOct[4]CH2COCH3 by batch-wise method, PTPF and SF types of microreactors were 72 h, 15 s, and 4 s, respectively (7,8). The stepwise separation of silver, palladium and platinum from real waste solution with three types of calix[4]arene derivatives using batch-wise method and SF type microreactor were carried out. The results are shown in Figs. 2 and 3. For both systems, although the silver extraction with tOct[4]CH2COCH3 was not completely effective probably due to suppression of high sodium concentration. Multiple extractions led the effective silver extraction. However, the loaded-silver was not effectively stripped with thiourea solution. At the 2nd step, divalent palladium was effectively extracted with tOct[4]CH2

2Qu and stripped with thiourea by batch-wise system, while not sufficiently extracted by SF microreactor system. At the 3rd step, tetravalent platinum was effectively extracted with tOct[4]CH2

2Py and not effectively stripped with thiourea by batch-wise system. Since each metal was not completely extracted at each step in the microreactor system, platinum extraction was not sufficient. Although the results using microreactor system was not successfully achieved, there are some advantages using the microreactor system. The main problems are not related to the microreactor system itself, but the metal selectivity and stripping efficiency of the reagents employed. Thus, the extraction condition including types of the extraction reagent and the stripping reagents should be improved and optimal.

24

Ag Recovery

Precious Metals (Ag, Pd, Pt)

Step 2 tOct[4]CH2

2Qu

Step 3 tOct[4]CH2

2Py

Pt Recovery

Step 1 tOct[4]CH2COCH3

Pd Recovery

Waste Aqueous P

hase O

rganic P

hase

Stripping reagent

62.0 % (1st)　

97.0% (2nd)

Stripping 1 M Thiourea

95.0% (1st) 96.0% (2nd)　

91.0 %

7.5 %

95.0%

12.0 %

Stripping 1 M Thiourea

Stripping 1 M Thiourea

Initial Conc. [Ag] = 1.20 mM [Pd] = 0.200 mM [Pt] = 0.0200 mM

[HNO3]=1.0 M

Fig. 2. Stepwise recovery of silver, palladium and platinum from real waste solution

with calix[4]arene derivatives and the stripping reagents by batch-wise system

Ag Recovery

Precious Metals (Ag, Pd, Pt)

Step 2 tOct[4]CH2

2Qu

Step 3 tOct[4]CH2

2Py

Pt Recovery

Step 1 tOct[4]CH2COCH3

Pd Recovery

Waste Aqueous P

hase O

rganic P

hase

Stripping reagent

34.0% (1st)　 48.8% (2nd) 63.0% (3rd)

Stripping 1 M Thiourea

41.1%

7.44%

84.0%

Unclear

Stripping 2 M NH4SCN

31.0% 1 M Thiourea

16.9%

Stripping 1 M Thiourea

Initial Conc. [Ag] = 1.00 mM [Pd] = 0.167 mM [Pt] = 0.0167 mM

[HNO3]=1.0 M

Fig. 3. Stepwise recovery of silver, palladium and platinum from real waste solution with calix[4]arene derivatives and the stripping reagents by SF type of microreactor

system

25

Acknowledgements: This work was financially supported by “The Environment Research and Technology Development Fund, No. 3K-123022, from the Ministry of the Environment, Government of Japan”.

References 1. K. Ohto, Ion Exch. Solvent Extr., 21 (2014) 81-127. 2. K. Ohto et al., Anal. Chim. Acta, 341 (1997) 275-283. 3. T. Kitamori, T. Manabu, H. Akihide, K. Sato, Anal. Chem., 76 (2004) 52-60. 4. M. Tokeshi, T. Minagawa, T. Kitamori, Anal. Chem., 72 (2000) 1711-1714. 5. T. Yoneyama, K. Ohto, H. Harada, H. Kawakita, Solvent Extr. Res. Dev., Jpn., 17 (2010) 187-194. 6. K. Ohto, H. Higuchi, K. Inoue, Solvent Extr. Res. Dev., Jpn., 8 (2001) 37-46. 7. K. Ohto et al., J. Soc. Mater. Eng. Resour., 20 (2014) 92-96. 8. S. Ramachandra Rao et al., Proc. Asia Pacific Confederation of Chemical Engineering Congress 2015: APCChE 2015, (2015) 2014-2019.

26

APPLICATION OF MEMBRANE SEPARATION PROCESSES FOR INDUSTRIAL WASTEWATER RECLAMATION AND REUSE

Nalan Kabay

Ege University, Chemical Engineering Department, Faculty of Engineering

35100 Izmir, Turkey e-mail: nalan.kabay@ege.edu.tr

In terms of quantity, quality and sectoral usages, water resources faced with many problems nowadays. Different practical solutions are needed for sustainable protection of water resources since increasing the fresh water resources is limited in terms of technical and economical aspects. Our water resources have been polluted and cannot be used as a result of discharging wastewater, especially from industrial zones to the receiving environments without enough treatment. Currently, advanced technologies in wastewater treatment become important due to the fact that discharge standards are decreased and there is a need for water recovery and reuse. Recently, membrane bioreactor (MBR) systems have been used for the treatment of municipal and industrial wastewater. MBR systems seem to be good alternatives for re-using the treated wastewater as they provided a good quality of product water. However, decreasing the salinity of product water is needed in some cases if the product water will be recovered and re-used as irrigation water and process water. For this purpose, advanced membrane treatment processes such as nanofiltration (NF) and reverse osmosis (RO) are employed. Electrodialysis (ED) could be employed for the post-treatment of concentrate streams of NF/RO processes for valorization of RO brines. Electrodeionization (EDI) could be also another alternative method for boiler feed water production from RO permeate. In this presentation, importance of membrane technologies for the utilization of wastewater as an alternative water resource will be discussed. Some data obtained will be presented. Acknowledgements: The author would like to thank Professor Andrzej W. Trochimczuk and the Organizing Committee of the 4th International Conference on Methods and Materials for Separation Processes (SSTP-2016) for the kind invitation to present this lecture. The financial support of TÜBİTAK (Project no: 114Y500) for doing research in this area is greatly acknowledged. The author thanks to her post-graduate students G. Sert, S. Bunani, E. Altıok, A. Arianfar, M. Gündoğdu, H. Serez, Y.A. Jarma, M. Hacıfazlıoğlu, H. Tomasini, N.J. Falizi, S. Ersen, İ. Parlar for the collaborations. References 1. Membranes in Clean Technologies-Theory and Practice, Vol.1-2, Eds. A.B. Koltuniewicz, E. Drioli; Wiley-VCH, Weinheim 2008. 2. Advanced Membrane Technology and Applications, Eds. N.N. Li, A.G.Fane, W.S.W. Hu, T. Matsuura; John Wiley & Sons, New Jersey 2008. 3. Emerging Membrane Technology for Sustainable Water Treatment, Eds. N.Hankins, R. Singh; Elsevier, Amsterdam 2016.

27

MULTIFUNCTIONAL MEMBRANES FOR ADVANCED SEPARATIONS

S. Ranil Wickramasinghe1, Xianghong Qian2

1Ralph E Martin Department of Chemical Engineering, University of Arkansas,

Fayetteville, AR 72701, USA 2Department of Biomedical Engineering, University of Arkansas, Fayetteville,

AR 72701, USA e-mail: swickram@uark.edu

Multifunctional membranes that perform more than one function simultaneously, are being developed today. Here two categories of multifunctional membranes will be discussed. Responsive membranes represent a new class of advanced membranes that respond to an external stimulus. They are a subset of multifunctional membranes where the membrane performs more than one function simultaneously. Biological membranes are frequently multifunctional. The development of responsive membranes has been inspired by biological membranes such as skin and epithelial tissue. The barrier properties of biological membranes can be modulated by environmental conditions such as temperature, humidity, presence of a specific ion etc. Responsive membranes mimic this behaviour allowing for modulation of membrane performance by environmental conditions. Here a review of responsive membranes in terms of the types of stimuli that are used to modulate their performance is presented. Specific examples based on research being conducted at the University of Arkansas will be presented. Catalytic membranes represent a second class of multifunctional membranes. A catalytic membrane catalyzes a reaction and enables the simultaneous removal of a product or group of products. Numerous types of catalytic membranes have been described in the literature. Here, we focus on development of a membrane where the surface of the membrane acts as a catalyst that enables the hydrolysis and dehydration of lignocellulosic biomass and the separation of the reaction products simultaneously. Keywords: Catalytic Membranes, Environmentally Responsive, Fouling Resistant, Hydrolysis, Tailored Membranes, Surface Modification

28

POLAR POLYMERIC ADSORBENTS AND THEIR APPLICATIONS

Małgorzata Maciejewska

Faculty of Chemistry, Maria Curie-Skłodowska University,

pl. M. Curie-Skłodowskiej 3, 20-031 Lublin, Poland e-mail: mmacieje@umcs.pl

Polymeric adsorbents with highly developed internal structure has been the subject of intensive scientific research. In comparison with the commonly used adsorbents based on silica gel, polymers are stable throughout the whole pH range, they can be easily functionalized, have the ability to create specific sorption spaces. They combine in their structure the most desirable characteristics of porous materials and polymers. The traditional, but still exhaustively explored, polymeric adsorbent is macroporous polystyrene-divinylbenzene (PS-DVB). Due to its hydrophobic nature PS-DVB interacts with analytes basically through van der Waals’ forces and the Π-Π interactions of the aromatic rings that make up the sorbent structure. The hydrophobic interactions with the adsorbates lead to low adsorption capacity. This drawbacks could be largely overcome by introducing polar functional groups into the adsorbent matrix. This purpose can be achieved by two main approaches:

(i) the chemical modification of hydrophobic polymer skeleton with a suitable polar moiety;

(ii) direct synthesis polar adsorbents from a balanced ratio of a hydrophilic monomer and a crosslinker.

Chemical modification mainly involves electrophilic aromatic substitution and ring opening reactions. However, in many cases low degree of modification is responsible for still high degree of hydrophilicity. In a consequence, direct synthesis of hydrophilic sorbents is desirable. Polar monomer promotes hydrophilic interactions and favors interactions with water, whereas crosslinking agent increases the specific surface area, thermal and mechanical resistance and promotes hydrophobic interactions. As polar monomers acrylonitrile, methacrylonitrile cyanomethyl styrene N-vinylimidazole, 4-vinylimidazole, 1-vinyl-2-pyrrolidone, 2-hydroxyethyl methacrylate, 4-vinylpyridine are commonly used. Among crosslinking agents divinylbenzene holds the prominent position, but more polar crosslinkers from methacrylate family, both commercially available (ethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, 1,4-dimethacryloyloxybenzene) as well as synthesized in laboratories e.g. 1,3,5-trimetharyloylxybenzene, 1,4-di(methacryloyloxymethyl)naphthalene, 2,3-bis(2-hydroxy-3-methacryloyloxypropoxy)naphthalene, bis[4-(2-hydroxy-3-methacryloyloxypropoxy)phenyl]sulfide, 4,4’-bis(maleimido)diphenylmethane are applied. The polar character of the adsorbents improve the interaction with polar compounds and ensure a good retention of analytes. Additionally, polymeric adsorbents can be designed in such a way that they selectively interact with the target compound but remove all other analytes, including interferents. They can be used in column or batch operations. The adequate

29

usage of polar adsorbents requires an in-depth characterization of these material in terms of polarity as well as porous structure. However, results obtained from different research methodologies can differ significantly. Even the value of surface area occupied by a single molecule of nitrogen (0.162 nm2) accepted in adsorption method is still the subject of scientific discourse and depends on the polarity of adsorbents. Despite the questions that arise during the synthesis and characterization of polar polymeric materials, they are the most important group of sorbents used in SPE, HPLC, GC, ion chromatography and other separation techniques. Integrated polarity, large specific surface area and stability under a broad range of analysis conditions make polar polymeric adsorbents an ideal choice for adsorption processes.

II. SHORT LECTURES

33

PREPARATION OF SILICA-BASED SOLVENT IMPREGNATED ADSORBENT FOR SEPARATION OF RARE EARTH METALS

Syouhei Nishihama, Taihei Harano, and Kazuharu Yoshizuka

Department of Chemical Engineering, The University of Kitakyushu,

Hibikino 1-1, Kitakyushu 808-0135, Japan e-mail: nishihama@kitakyu-u.ac.jp

Solvent impregnated adsorbent is an adsorbent combining the advantages of solvent extraction and ion exchange. Although polymeric resins are widely used as supports for extractant impregnated, polymeric resins are affected by pH of the aqueous solution so that pressure drop is occurred by swelling or shrinking of the support resin. Therefore in the present work, silica-based solvent impregnated adsorbent has been developed by focusing as a support due to its rigid structure. By using this adsorbent, separation of Nd and Dy with the adsorbent was investigated. Two types of silica, (a) silica which surface was covered by 11.8 ± 1.0 wt% of styrene-divinylbenzene copolymer and (b) silica modified by poly-dichlorodimethylsiloxy group, were used as support materials. Impregnation of the extractant, 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester (PC-88A), in each support material was carried out by immersing the support into the dichloromethane solution of PC-88A, and then the diluent was evaporated. Maximum impregnated amount of PC-88A on the support materials was (a) = 2.40 and (b) = 2.41 mmol/g, respectively. Batchwise adsorption of Nd and Dy was carried out by mixing the adsorbent and aqueous solution at 25°C for 48 h. Column adsorption of Nd and Dy was carried out by feeding the aqueous solution containing both metals to the column packed with the adsorbent (a). Concentrations of Dy, Nd, P, and Si were measured by ICP-AES.

pH

0 1 2 3 4 5

q (

mm

ol/g

)

0.0

0.1

0.2

0.3

Adsorbent (a) Adsorbent (b)

Lea

kage

ofP

C-8

8A

0

1

2

3

Dis

solu

tion

of S

i

0.0

0.5

1.0

1.5

Fig. 1. Effect of pH on adsorption amount of Dy, leakage of PC-88A, and dissolution of

Si with batchwise adsorption of Dy in single metal system

34

Figure 1 shows the effect of pH on adsorption amount of Dy in single metal system, together with leakage of extractant and dissolution of Si. The adsorption of Dy was increased with pH and became constant in pH > 1.5 with both adsorbents. The leakage of the extractant and the dissolution of Si from the adsorbents, during the adsorption, were quite low, and thus the new solvent impregnated adsorbents based on silica support were successfully prepared. Separation of Nd and Dy with the adsorbent (a) was then carried out. Figure 2 shows effect of pH on the adsorption amounts of the metals with batchwise adsorption. Effective adsorption of Dy was achieved especially at pH > 2.5, while almost no adsorption of Nd was occurred. The adsorbent (a) was thus applied for column separation of Nd and Dy. Figure 3 shows breakthrough and elution curves of the metals. Although replacement of Nd adsorbed in the beginning of the operation with Dy in the aqueous solution was progressed, both metals were contained in the eluent. The optimization of the operational conditions for the separation of the metals should be investigated as future work.

Bed Volume ( - )

0 100 200 300 400 500

[ Ln

] (

mm

ol/L

)

0.0

0.5

1.0

1.5

NdDy

pH

1.7

1.8

1.9

2.0

0 10 20 30 40 500

10

20

30

40

50

60

Fig. 3. Breakthrough and elution curves of Nd and Dy with column operation

pH

0 1 2 3 4q (

mm

ol/g

)0.0

0.1

0.2

0.3

NdDy

Fig. 2. Effect of pH on adsorption amount of Nd and Dy in binary metal system

35

SEPARATION OF PGM IONS FROM THEIR MIXTURES WITH ORGANIC SOLUTIONS OF QUATERNARY PHOSPHONIUM

SALTS

Martyna Rzelewska, Maciej Wiśniewski, Magdalena Regel-Rosocka

Poznań University of Technology, Faculty of Chemical Technology, Institute of Chemical Technology and Engineering, Berdychowo St. 4, 60-965 Poznań,

Poland e-mail: magdalena.regel-rosocka@put.poznan.pl

Natural ores contain small amounts of PGMs, moreover, technological process of platinum ore processing is very energy-consuming and also causes environmentally damaging activities. For example: obtaining 1 kilogram of platinum requires extraction of about 150 tons of ore from a depth of 1000 meters. In comparison to the manufacturing process, content of precious metals in secondary sources is quite high, for example from 1 kilogram of platinum can be obtained from 2 tons of spent catalytic converters. Demand for PGMs is still growing and products containing PGMs are surrounding us and improve our lives. The main areas of PGM application are presented in Fig. 1.

Autocatalyst

51%

Jewellery

16%

Investment

9%

Electrical

9%

Chemical

5%

Dental

3%Glass

3%

Other

2%

1%

1%

Fig. 1. Areas of PGM applications in 2010 (according to International Platinum Group

Metals Association, www.ipa-news.com)

Recovery of PGMs from solutions after leaching spent catalysts or other end-of-life products can be realized with liquid-liquid extraction. Up to now various extractants were proposed for PGM extraction, i.e. aliphatic amines or

PPGGMM aapppplliiccaattiioonnss

Petroleum

refining

Medical

& biomedical

36

quaternary ammonium salts (1,2), pyridine derivatives (e.g. ACORGA CLX 50, pyridinecarboxamides) (3,4), or dialkyl sulfides (5). Ionic liquids (ILs), e.g. methyltrioctylammonium or alkylphosphonium salts have been proposed as novel extractants of PGMs for the last ten years (6-8). Preliminary results of extractive recovery of Pd(II) from multicomponent chloride solution of Pd(II), Ni(II), Pb(II), Fe(III), Rh(III), Ru(III) and Pt(IV) by aid of trihexyl(tetradecyl)phosphonium chloride (Cyphos IL 101) or bis(2,4,4-trimethylpentyl)phosphinate (Cyphos IL 104) were presented by Cieszynska and Wisniewski (9). As PGMs (Pd(II) and Pt(IV) particularly) are related chemically it is complicated to separate them selectively. Moreover, they form various hydrated and non-hydrated chlorocomplexes in the aqueous phases, and also they can change the oxidation state (e.g. Ru(III)). Thus, the aim of this work is to investigate separation of Pd(II), Pt(IV), Ru(III) and Rh(III) from two- and four-component solutions by multistage extraction with organic solutions of various phosphonium ionic liquids (Cyphos IL 101, 102 or 104) and stripping with various strippants. The following issues are investigated:

i. the effect of IL content in the organic phase on the selectivity of PGM extraction,

ii. the effect of IL type in the organic phase on the selectivity of PGM extraction,

iii. the effect of volume ratio of aqueous to organic phase on extraction efficiency of PGMs,

iv. the effect of strippant type on PGM stripping and selectivity of separation, v. recycling of the organic phases to extraction of PGMs.

The results of PGM extraction do not depend on the type of phosphonium IL used, and indicate quantitative extraction of Pt(IV) and Pd(II) ions, while less than 20% of Rh(III) is extracted (e.g. with Cyphos IL 102). The best extractant for Ru(III) seems to be Cyphos IL 101 that transfers to the organic phase up to 60% of Ru(III). Cyphos IL 102 or 104 extract up to 35% of Ru(III). Selection of efficient stripping phase allows us to propose a process for selective separation of Pd(II) from Pt(IV) and from Rh(III) and Ru(III) based on extraction and stripping.

Acknowledgements: The research was supported by the 03/32/DS-PB/0601 grant. References 1. V.V. Belova et al., Proc. Intern. Solv. Extr. Conf. ISEC'02, Sole K.C., Cole P.M., Preston J.S. and Robinson D.J. (Eds), Cape Town, 2002, 916-921. 2. J.Y.Lee et al., J. Hazard. Mater., 168 (2009) 424-429. 3. I. Szczepanska et al., Hydrometallurgy, 68 (2003) 159-170. 4. M. Regel-Rosocka et al., Sep. Purif. Technol., 53 (2007) 337-341. 5. L. Pan et al., Chinese J. Inorg. Chem., 24 (4) (2008) 520-526. 6. A. Stojanovic et al., Aust. J. Chem., 63 (2010) 511-524. 7. A. Cieszyńska et al., Pol. J. Chem. Technol., 9 (2) (2007) 99-101. 8. M. Rzelewska et al., Chem. Pap., 70 (4) (2016) 454-460. 9. A. Cieszynska and M. Wisniewski, Sep. Purif. Technol., 80 (2011) 385-389.

37

SEPARATION OF LITHIUM ISOTOPE BY STRONG ACID ION EXCHANGE RESIN

J. Mikeš, M. P. Pinheiro, L. Jelínek

Department of Power Engineering, University of Chemistry and Technology,

Technická 5, 166 28 Prague, Czech Republic e-mail: mikesi@vscht.cz

In nature, two stabile isotopes of the lithium occur. The relative abundance of these isotopes is 92.41 % of 7Li and 6.59 % of 6Li (1). Isotope 7Li has a small cross section, only 0.045 barns, in contrary to this, 6Li has a large cross section of 940 barns (2). This feature determines utilizations of lithium isotopes in nuclear power industry, for example lithium hydroxide contained isotope 7Li is useable for the alkalization of coolant in pressurized water reactors (3) or lithium fluoride contained isotope 7Li could be used to decreases the temperature of melting point of coolant in molten salt cooled reactor (4). Large cross section determines the utilization of 6Li isotope as a source material for production of tritium in nuclear fusion reactors (5). Various methods for lithium isotope separation, such as solvent extraction using macrocycles, ion exchange membranes, laser excitation, radiofrequency spectroscopy, distillation and electro-migration were investigated, and their applicability has been evaluated (6). One of the suitable methods for lithium isotope separation is also ion exchange on strong acid ion exchange resin (7).

Fig. 1. Chromatographic peak of enrichment process Each lithium isotope cation shows different extent of electrostatic interaction with sulfonic acid groups of ion exchange resin. The separation process can be described as elution chromatography. First part of peak (Fig. 1 – A) contains higher portion of lithium isotope 6 than natural solution, top part of this peak (Fig. 1 – B) has approximately the same isotope ratio and last part (Fig. 1 – C) of the chromatographic peak contain higher portion of lithium isotope 7. For this reason, most important factor for isotope separation is form of chromatographic

38

peak. For determination of its form and position under given conditions, fractions were collected (Fig. 2 – E) and their lithium contend analysed by atomic emission spectroscopy. Determination of profile of chromatographic peak and own separation process was executed in the automatized apparatus, see Fig. 2. Initial lithium solution (Fig. 2 – A) ion was then passed through the column. Flow of mobile phase (Fig. 2 – B) and lithium solution (Fig. 2 – A or C) was controlled by peristaltic pump (Fig. 2 – H) and multiple-way solenoid valves (Fig. 2 – F). Enriched solution of lithium isotope 6Li was collected in front fraction (Fig. 2 – C) and enriched solution of lithium isotope 7Li was collected in edge fraction. Fraction of middle part of peak was collected to waste beaker (Fig. 2 – D).

ABC

H

D

E

G

F

F

Fig. 2. Scheme of enrichment apparatus: A – E are beakers with solutions (A – initial solution of lithium; B – ammonium chloride, mobile phase; C – enriched solution of 6Li lithium isotope; D – waste beaker; E – enriched solution of lithium isotope 7Li for the

followings experiments; F are multiple-way input solenoid valves; H is peristaltic pump and G is chromatographic glass column

Our work is also focused on type, concentration and flow rate of mobile phase (eluent) and production of narrow particle fraction of ion exchange resin. As a stationary phase was used narrow particle fraction of Dowex 50 WX 2 cation exchanger having diameter of 150 – 200 µm and total exchange capacity of 1.31 mmol·mL-1 packed in glass column. To obtain narrow fraction of the resin, wet screening using vibratory sieve shaker was necessary because of irregular swelling of dry-sieved resin. The total capacity of ion exchanger, was determined converting the ion exchanger to magnesium form, displacement magnesium ions by sodium chloride and hydrochloric acid and determination of magnesium by chelatometric titration (8). The chromatographic peaks were evaluated for three different columns of inner diameter of 5 mm and different

39

heights - 350 to 2000 mm. For determination of isotope ratio after isotope separation, ICP – MS was used.

Based on the measurement of chromatographic peak, optimal concentration of ammonium chloride mobile phase was 0.5 mol·L-1. For practical use, isotope separation process must have more separations steps. The initial isotope ratio (7Li/6Li) of lithium nitrate 18.66, changed after first separation step to 18.37 and after eighth separation step the value was 15.9. The separation factor S calculated by equation [1] was found to be 1.015. Acknowledgements: This research was supported by the financial support from specific university research (MSMT No 20/2015). Isotope ratios were determined in cooperation with Department of geological process, Institute of geology CAS, v. v. i. References 1. T.B. Coplen et al., IUPAC Technical Report, 74 (2002)1987-2017. 2. V.F. Sears, Neutron News, 12 (1992) 29-37. 3. K. Nishizawa et al., J. Nucl. Sci. Technol. (Tokyo, Jpn.), 21 (1984) 133-138. 4. M. Zaghoul et al., Fusion Sci. Technol., 44 (2003) 344-350. 5. G. Casini, Nucl. Technol./Fusion 4 (1983) 1228-1232. 6. E.A. Symons, Sep. Sci. Technol., 20 (1985) 633-651. 7. Z. Hagiwaraet et al., J. Nucl. Sci. Technol. (Tokyo, Jpn.), 6 (1969) 326-329. 8. M.M. Osman, Fresenius Zeitschrift für Anal. Chem., 284 (1977) 43-43.

�76 =�[ ��7 ][ ��6 ]�� ������[ ��7 ][ ��6 ]�������

[1]

40

PURIFICATION OF PHOSPHORIC ACID BY LIQUID-LIQUID EXTRACTION

Mariana Campos Assuncao1,2, Alexandre Chagnes1, Hubert Halleux2,

Gérard Cote1 1PSL Research University, Chimie ParisTech - CNRS, Institut de Recherche de

Chimie Paris, 11 rue Pierre et Marie Curie, 75005 Paris, France 2Prayon, Gansbroekstraat 31, B2870 Ruisbroek, Belgium

e-mail: m.campos-assuncao@chimie-paristech.fr

Phosphoric acid is a weak oxyacid with many industrial applications depending on its degree of purification including surface treatments or fertilizer production (merchant grade Phosphoric Acid, MPA), salt production for animal feeding or acidification of food and drinks for human consumption (Food grade Phosphoric Acid, FPA), and pharmaceutical industry (Pharmaceutical grade Phosphoric Acid, PPA). In order to produce these different grades, various purification technologies can be implemented including hydrometallurgical processes as it is the case in the Prayon’s process based on the selective liquid-liquid extraction of phosphoric acid. The current solvent implemented in the Prayon’s process for purifying phosphoric acid is a mixture of 90 wt.% di-iso-propylether (DIPE) and 10 wt.% tri-n-butylphosphate (TBP). The extraction properties of this mixture has been largely reviewed in the literature. The main interest of this solvent concerns its high selectivity towards impurities and its high ability to extract phosphoric acid. There is very few information about the physicochemistry involved in the purification of wet phosphoric acid by liquid-liquid extraction because wet phosphoric acid is a very complex medium (highly concentrated medium which can reach 14 M, high complexing power, only few data on metal speciation in phosphoric acid, etc.). Furthermore, liquid-liquid extraction of phosphoric acid involves very complex phenomena such as phase splitting and third phase formation which can be explained by the presence of supramolecular species in solution as well as coextraction of large amount of water. In the present paper, the physicochemistry involved in phosphoric acid and water extraction by DIPE-TBP mixture will be presented by decrypting the role of the supramolecular organization. Furthermore, a model based on mass-balance equations will be introduced to predict water and phosphoric acid extraction, as well as the huge variation of phase volume ratio all along the extraction process caused by water and phosphoric acid extraction.

41

AFFINITY BASED LIQUID-LIQUID EXTRACTION OF CARBOXYLIC ACIDS ANALYZED BY ISOTHERMAL TITRATION

CALORIMETRY

Lisette M.J. Sprakel, Boelo Schuur

University of Twente, Sustainable Process Technology Group, PO Box 217, 7500 AE Enschede, The Netherlands

e-mail: l.m.j.sprakel@utwente.nl

Keywords: isothermal titration calorimetry (ITC), liquid-liquid extraction, carboxylic acids Introduction In industry there are both production and wastewater streams containing low concentrations of carboxylic acids. Because of the low concentrations, economic recovery of these acids is challenging. Because the acid is typically the high boiler and water the low boiler, affinity based separation processes are preferred over direct distillation. Liquid-liquid extraction is an efficient, economical and environmentally friendly method for separating acids (1,2). For several carboxylic acid – extractant combinations, the influences of process conditions such as concentration, diluent and temperature have been studied (3), however the fundamental and general understanding of the mechanism of extraction is not complete. In order to find better extractants, better understanding on mechanisms is required, and therefore we conducted a study using Isothermal titration calorimetry (ITC) to characterize the thermodynamics of acid-base complexations. In general, the complexation reaction can be described by , where A is the acid and B the extractant. This reaction takes place in the organic phase, see Figure 1. Therefore also the distribution of the acid over the organic phase ( and dissociation of the acid in the aqueous phase ( are involved.

Fig. 3. Schematic overview of the equilibria involved in the extraction of an acid into the

organic phase

With the use of ITC, for a large number of acid-base combinations and in various diluents, ΔH, ΔS, ΔG and the stoichiometry N of the complexation were determined.

Results and discussion In a typical ITC experiment as displayed in Figure 2, the acid is titrated to the extractant and diluent in the sample cell. The heat released by the reaction of

42

the compounds is measured. After integrating the curve, the ‘S-curve’ in figure 2b is obtained from which the thermodynamic parameters can be obtained.

Fig. 4. ITC Experiment: Titrating Acetic acid to trioctylamine (0.24 M TOA) in toluene

(left) heat released by reaction, (right) integrated curve at 20°C

The results for the ITC experiments with pure acetic acid and 0.24 M trioctylamine (TOA) in several diluents are shown in Table 1. These experiments were performed at 20°C and at 60°C. From the table it is clear that the value of the complexation constant decreases strongly with temperature, which is also expected based on lower distribution coefficient at higher temperatures. The number of acids per amine complex N is lower for more active solvents such as 1-octanol and larger complexes are formed for the inactive heptane. The enthalpy and entropy of complexation are almost constant with respect to temperature, except for the case of 1-octanol. Table 1. ITC results for complexation of acetic acid and 0.24 M TOA in several diluents

at 20°C and 60°C

Diluent K N ΔS (J/mol) ΔH (kJ/mol)

T=20°C T=60°C T=20°C T=60°C T=20°C T=60°C T=20°C T=60°C

heptane 61 17 3.6 3.8 -114 -106 -12 -11

MIBK 39 16 3.2 4.0 -144 -139 -16 -14

toluene 51 14 3.0 3.0 -144 -145 -17 -19

1-octanol 56 6.3 1.2 1.0 -85 -103 -29 -40

To determine the differences between active and inactive diluents, experiments were carried out for complexation of acetic acid – 1M TOA in a mixed 1-octanol/toluene diluent with varying composition. The shape of the resulting ‘S-curves’ in Figure 3 shows the effect of active and inactive diluent. With an increasing fraction of 1-octanol in the diluent, the steep part of the curve shifts towards lower molar ratios. This indicates formation of complexes with a lower number of acids per amine. The presence of the active 1-octanol molecules prevents formation of higher complexes, indicating competition between 1-octanol and acetic acid for binding with the complex.

43

Fig. 5. Integrated ITC data for complexation of acetic acid with 1M TOA in mixed diluents composed of 1-octanol and toluene in different compositions at 20°C

Similar results were obtained for complexation of acetic acid with trioctylphosphine oxide (TOPO), for which the bond with the acetic acid is even weaker and the presence of 1-octanol prevents the formation of TOPO-acid complexes in general. Conclusions and outlook For a range of basic extractants, we are coupling the molecular structure to the thermodynamics of the acid-base complexation with the goal to be able to design new generations of extractants that have good extraction capacity at low temperature, but also have a strong temperature effect, allowing effective temperature-swing back-extraction. Acknowledgement: This project is an Institute for Sustainable Process Technology (ISPT) project. References 1. J.M. Wardell and C.J. King, J. Chem. Eng. Data., 23 (1978) 144-148. 2. Z. Li, W. Qin and Y. Dai, J. Chem. Eng. Data., 47 (2002) 843-848. 3. A.M. Eyal and R. Canari, Ind. Eng. Chem. Res., 34 (1995) 1789-1798.

44

IMPLEMENTATION OF MEMBRANE SEPARATION TECHNIQUES IN THE PRODUCTION OF BUTANOL BY

FERMENTATION PROCESS

Wojciech Kujawski, Anna Kujawska, Katarzyna Knozowska, Marcin Cichosz, Roman Buczkowski, Joanna Kujawa

Nicolaus Copernicus University in Toruń, Faculty of Chemistry, 7 Gagarina str.,

87-100 Toruń, Poland e-mail: kujawski@chem.umk.pl

The interest in the production of biofuels was promoted by restricted fossil fuel resources as well as by the environmental concerns and tightening of legislation. Ethanol and biodiesel are already commonly used biofuels in transportation, but also new alternatives are needed to fulfill the increasing fuel demand in the future. On the other hand, it was proved that the bioethanol programme in Europe resulted in the raise of the food prices. The Polish market of bioethanol is estimated for 100 mln L per year. Ethanol is produced in a number of small distilleries and subsequently transported to the dehydration plants for the final treatment. The dehydration of ethanol is performed uniquely by using molecular sieves technology. The first industrial dehydration plant based on membrane pervaporation was implemented in 2005, but the pervaporation unit was destroyed by the untrained staff. Butanol, having better fuel properties than ethanol, is a potential choice for the renewable transportation fuel and feedstock chemical in the future. Changes of EU law regarding renewable fuels should shift the interest of biofuel producers from ethanol towards butanol. The presentation will present the results on the application of vacuum pervaporation, thermopervaporation and membrane distillation to the removal of acetone, butanol and ethanol (ABE) from binary and multicomponent aqueous streams. Results on the dehydration of butanol reach aqueous phase using polymeric and ceramic hydrophilic membranes will be also demonstrated. Finally, the concept of the utilization of membrane separation processes in the production of butanol will be outlined.

Acknowledgements: This research was supported by statutory funds of Nicolaus Copernicus University in Toruń, Poland (Faculty of Chemistry NCU, T-109) and by TANGO1/266441/NCBR/2015 grant from the National Centre for Research and Development and the National Science Centre.

45

NOVEL HOLLOW FIBER MEMBRANES FOR LOW PRESSURE NANOFILTRATION

Cristina V. Gherasim1,2, Tobias Luelf1,2, Hannah Roth1,2, Matthias

Wessling1,2

1DWI Leibniz Institute for Interactive Materials Research at RWTH Aachen, Forckenbeckstrasse 50, 52074 Aachen, Germany

2Department of Chemical Process Engineering, RWTH Aachen University, Turmstr. 46, 52064 Aachen, Germany

e-mail: cristina.gherasim@avt.rwth-aachen.de

Safe drinking water became a problem of increasing importance in a world with a growing population, and the occurrence of various pollutants in the water sources has become a serious concern nowadays (1). Membrane processes are non-polluting water treatment techniques applied in water production and reclamation plants. Nanofiltration (NF) has gained importance because it requires lower operating pressure and achieves higher water flux compared to reverse osmosis (RO), hence can clean higher amounts of polluted water with lower energy consumption (2). Hollow fiber membranes have the most favorable surface area to volume ratio, good mechanical stability and easy operation, require less pretreatment and easy maintenance. Therefore, there is a growing interest to develop novel efficient NF hollow fiber membranes for water separations (3). This work reports the development of novel charged NF hollow fiber membranes with enhanced NF performance determined by the addition of charged polymers (polyelectrolytes) to the membrane material. Thus, the novel NF hollow fibers contain polyether sulfone as base polymer together with the polyelectrolytes poly(styrenesulfonate) (PSS), polyethylene imine (PEI) and poly(diallyldimethylammonium chloride) (PDADMAC). The innovative fabrication procedure also newly developed here allows setting both the porous support of the hollow fiber and the NF separation layer during a single-step procedure consisting of single layer dry-jet wet spinning. These results into highly permeable hollow fiber membranes with a particular membrane architecture achieved for the first time, and with separation performances similar to the membranes reported in literature obtained by multistep processes. The novel NF hollow fibers developed are characterized in terms of morphology and charge properties by using field emission scanning electron microscopy (FESEM), Fourier transform infrared (FTIR), X-ray photoelectron spectroscopy (XPS) and zeta potential measurements. The permeability and retention performance for salts and uncharged solutes are investigated by NF transport experiments, and the results are correlated with the findings regarding the membranes structure and chemistry. The novel NF hollow fibers reach performance of high flux and ~90% rejection of MgCl2, MgSO4, Na2SO4 at 2-6 bar pressure, thus being able to perform highly effective and energy efficient separations. The advantages and the innovative character of the NF hollow fibers prepared might result in interesting potential applications and open new directions regarding designing efficient NF hollow fibers for water desalination.

46

Acknowledgements: Cristina Veronica Gherasim gratefully acknowledges the financial support for the research provided by the Alexander von Humboldt Foundation.

References 1. J.A.G. Fane, Desalination, 106 (1996) 1-9. 2. R.W. Baker, „Membrane Technology and Applications“, Wiley, Chichester, 2004. 3. B. Van der Bruggen et al., Sep. Purif. Technol., 31 (2003) 193-201.

47

RETENTION PROPERTIES OF GRAPHENE OXIDE MEMBRANES IN THE FILTRATION OF ELECTROLYTE SOLUTIONS

Stanisław Koter1, Paulina Cytarska1, Leszek Stobiński2

1Nicolaus Copernicus University in Toruń, Faculty of Chemistry, ul. Gagarina 7,

87-100 Toruń, Poland 2Warsaw University of Technology, Faculty of Chemical and Process

Engineering, ul. Waryńskiego 1, 00-645 Warszawa, Poland e-mail: skoter@umk.pl

Recently, carbon nanomaterials like nanotubes (1), graphene and graphene oxide (2,3), graphyne (4) have attracted attention of membranologists. The application of such materials is advantageous because of high water flow (5), good retention properties (6), reduced fouling tendency (7). Their chemical structure enables functionalization and thus modification of filtration characteristics of membranes prepared from those materials. The number of works, both experimental and theoretical ones, on new kind of membranes containing graphene oxide (GO; Fig. 1) is growing very fast. The different variations can be met: the GO layers deposited onto microporous support without any modification (8), the crosslinked GO layers (6,9,10), or covalently bound to a support (11), the GO dispersed inside the membrane matrix (7,12), etc. In spite of many works, still the number of works concerning filtration properties of these membranes in electrolytes solutions is small (6,8,9,11).

Fig. 1. Graphene oxide (GO) structure according to (13)

In this work, the characteristics (hydrodynamic permeability and retention) of membranes obtained by deposition of a few layer-graphene oxide (FL-GO) onto a polyamide support in the filtration of electrolytes is presented. Two kinds of membrane are examined – the first one is of high FL-GO loading and treated with borate (Fig. 2), the second one is of low FL-GO loading without borate treatment. In the filtration experiments, the solutions of electrolytes (Na2SO4, NaCl, MgSO4, MgCl2) in the concentration range 1 – 300 mM are used. The

48

retention of two dyes of ionic character – bromophenol blue, eriochrome black T – is also examined.

Fig. 2. Image of the FL-GO layer deposited by vacuum filtration on a polyamide support and treated with borate (the digital microscope VHX-5000, Keyence)

The observed order of electrolytes retention:

Na2SO4 > NaCl > MgSO4 > MgCl2 is qualitatively described by the ideal Donnan equation describing the electrolyte sorption in a negatively charged membrane:

−

+

−

+ −

−+

−

−+ = z

z

z

z

cccc (1)

where ci, ic denote the concentrations of ions outside, inside a charged

membrane, respectively, zi is the charge number of ion i.

0.00 0.05 0.10 0.15 0.20 0.25 0.30

0.0

0.2

0.4

0.6

0.8

1.0

cfeed M

R

Xm 0.20 M

fit R 1Kp

Na2SO4, FLGOB PA

Fig. 3. Dependence of the observed retention coefficient of Na2SO4 on the feed concentration; solid line – fit of Eq. (2) to the experimental data, Xm is the fitted

concentration of negative fixed charges of the FL-GO layer

49

However, a simplified expression for retention coefficient based on the Donnan exclusion and mentioned in some papers (e.g. (8,14)):

coion

coion

c

cR −= 1 (2)

fails in the description of the observed concentration dependence of the observed retention, as it is demonstrated in the case of the filtration of sodium sulfate solutions (Fig. 3). In this work, other filtration models, among others the phenomenological Spiegler-Kedem-Katchalsky model and the fixed charge model developed by Hoffer and Kedem (15), later used e.g. by Tsuru et al. (16), will be also tested. Regarding the dyes, in the experiments without stirring eriochrome black T is practically completely rejected, whereas the retention of bromophenol blue decreases with time (Fig. 4). To some extent, this phenomenon can be explained by the time evolution of the concentration profile at the membrane on the feed side (concentration polarization layer) (Fig. 4).

0.0

0.2

0.4

0.6

0.8

1.0

0 50 100 150 200

t /min

R

BPB pH10

FL-GO-B /PA

R int = 0.98

R int = 0.99

EBT

Fig. 4. Retention of eriochrome black T (EBT, 1 mM) and bromophenol blue (BPB, 0.2

mM) at pH 10 by the FL-GO-B/PA membrane treated with borate; filtration without stirring, ∆p = 10 bar; solid lines represent theoretical calculations based on the

continuity equation for two assumed values of the real retention coefficient Rint = 0.98 and 0.99

The experiments with stirring performed on the FL-GO membrane (no borate treatment) confirmed a nearly complete rejection of eriochrome black T, whereas the retention of bromophenol blue reached ca. 85 %. Summarizing, the membranes with active layer prepared from graphene oxide show properties typical for nanofiltration membranes. Their hydrodynamic permeability can be controlled by the deposition of adequate number of GO nanosheets. However, their mechanical stability should be increased by e.g. crosslinking the nano-sheets of GO.

50

Acknowledgements: This work was financially supported by the Statutory Funds, Task No. 106.

References 1. B. Zhao et al., New Carbon Mater., 26 (2011) 321-327. 2. A. Aghigh et al., Desalination, 365 (2015) 389-397. 3. H.M. Hegab, L.D. Zou, J. Membr. Sci., 484 (2015) 95-106. 4. J.L. Kou et al., J. Chem. Phys., 139 (2013) 064705. 5. J. Wang et al., ACS Appl. Mater. Interfaces, 8 (2016) 6211-6218. 6. Y. Zhang, S. Zhang, T.S. Chung, Environ. Sci. Technol., 49 (2015) 10235-10242. 7. S. Bano et al., J. Mater. Chem. A, 3 (2015) 2065-2071. 8. Y. Han, Z. Xu, C. Gao, Adv. Funct. Mater., 23 (2013) 3693-3700. 9. M. Hu, B.X. Mi, Environ. Sci. Technol., 47 (2013) 3715-3723. 10. Z. An et al., Adv. Mater., 23 (2011) 3842-3846. 11. J. Wang et al., ACS Appl. Mater. Interfaces, 7 (2015) 4381-4389. 12. M. Safarpour, A. Khataee, V. Vatanpour, J. Membr. Sci., 489 (2015) 43-54. 13. Y. Cao et al., J. Power Sources, 196 (2011) 8377-8382. 14. J. Wang, et al., ACS Appl. Mater. Interfaces, 8 (2016) 6211-6218. 15. E. Hoffer, O. Kedem, Desalination, 2 (1967) 25-39. 16. T. Tsuru, S.-I. Nakao, S. Kimura, J. Chem. Eng. Jpn., 24 (1991) 511-517.

51

ELECTRODIALYSIS AS AN ALTERNATIVE EDI PRETREATMENT METHOD

Dorota Babilas, Marian Turek, Krzysztof Mitko, Piotr Dydo, Marek Słowik,

Ewa Laskowska

Silesian University of Technology, Faculty of Chemistry, ul. B. Krzywoustego 6, 44-100 Gliwice, Poland

e-mail: marian.turek@polsl.pl

The electrodeionization (EDI), a hybrid process combining electrodialysis and ion exchange, is commonly used in ultra-pure water (UPW) production in power, semiconductor, pharmaceutical industries and in laboratory practice. Electrodeionization requires high quality feed water and a sophisticated pretreatment. Reverse osmosis (RO) is commonly used before the EDI; however, electrodialysis (ED) may be used as an alternative EDI pretreatment method, given that ED can outperform RO in brackish water desalination. Another beneficial effect of applying electrodialysis instead of reverse osmosis as and electrodeionization pretreatment may be the change in sulfate to chloride ratio. Typically, RO permeate is used as the feed of all EDI module compartments (diluate, concentrate, electrode rinsing solution). In the anode compartment of the EDI module, chloride ions can be oxidized to free chlorine, which substantially decreases the life time of ion exchange membranes. In some EDI devices, the electrode stream is combined with the reject stream. If this is the case, this stream may contain chlorine, which must be removed prior to contact with RO membranes and EDI modules. The ED diluate should have higher sulfate to chloride ratio compared to RO permeate of the same salinity; increasing the ratio of sulphate to chloride concentrations in the EDI feed should decrease the chlorine evolution and increase the ion exchange membranes life time. In this work three different intermembrane spacers have been tested to find the best one in terms of ultra-pure water production in an integrated ED-EDI system, as presented in Fig. 1. Ratio of chloride to sulphate in the produced diluate was compared with a commercial RO-EDI unit. A batch-mode electrodialysis of tap water – see Table 1 – was performed using electrodialyzer equipped with four pairs of Neosepta CMX/AMX membranes of effective area of 4.5 cm2. Three different kinds of spacers were tested: 0.26 and 0.35 mm thin spacers of novel geometry, as well as 0.40 mm thin commercial spacer. The voltage drop on membrane stack was kept constant at 4 V (1 V per membrane pair).

Table 1. Conductivity and composition of tap water used in the experiments

Conductivity [μS/cm] Concentration [mg/dm3]

Cl- SO42-

Na+ K+

Mg2+ Ca2+

762 52.0 80.9 24.7 2.73 24.4 81.2

52

Fig. 1. A scheme of integrated ED(R)-EDI system for ultra-pure water production

Costs of ultra-pure water production in an integrated electrodialysis-electrodeionization system were estimated using previously described methodology (1), based on the results for each of the spacers. Parameters taken into account in cost estimation of ED-EDI system were as follows:

1. in case of ED: membrane cost of $100/m2, effective membrane area of 70%, membrane durability period of 35000 h, energy costs of $0.06/kWh of AC current, AC/DC rectifier electric efficiency of 95%, a pumping efficiency of 85%. Laboratory-obtained current, voltage and concentration data were used for estimation. The contribution of membranes in the total ED cost was assumed to be 30%.

2. in case of EDI: four EDI modules, total ultra-pure water production of 16 m3/h, working pressure of 3 bars, pump efficiency of 85%, voltage drop of 50 V per module, apparatus cost $1500 per module, apparatus life-time of 3 years with 350 working days per year, being 20% of total maintenance and investment costs, 85% water recovery.

Change in diluate conductivity during the ED experiments with three different spacers is presented in Fig. 2. Application of thinner spacers allowed reaching the desired diluate conductivity quicker – most likely the effect of enhanced mass transfer in the boundary layer due to shortened intermembrane distance; moreover, the stack electric resistance was lower in case of thin spacers, as the thickness of low salinity diluate compartment was smaller. Fig. 3 presents the ratios of sulfate to chloride concentrations for each of the experiments, as well as in the RO permeate. It is clearly visible that ED diluate has more sulphate than chloride ions when compared to RO permeate of the same TDS. The sulfate to chloride concentrations ratio is only 0.13 in case of RO permeate, but is always at least order of magnitude higher (up to 21 times higher in case of 0.35 mm thin spacer) in case of ED diluate. It can be explained as a result of different basis of the both processes. In ED, the ions have to be removed from the cleaned water by electromigration and diffusion through ion-exchange membranes. The more mobile ions are removed in a greater extent than the less mobile ones, which means the produced water (diluate) contains particles which are least likely to migrate through the membrane. In RO, the water is transferred through the membrane, the more mobile ions are transferred as well in a greater extent than the less mobile ones, which means the produced water (permeate) contains particles which are most likely to migrate through the membrane.

Electrode compartment

ED(R)

Electrode compartment

Electrode compartment

EDIElectrode compartment

ED diluate

EDI diluate(UPW)

EDI concentrate Electroderinsesolution

ED concentrate

Feed

Waste water

53

Fig. 2. Change in diluate conductivity (log scale) during the experiments with three different spacers; RO permeate conductivity added for comparison

Fig. 3. Changes in sulfate to chloride diluate concentrations ratio during ED; ratio in RO

permeate added for comparison Fig. 4 presents the estimated water production costs as a function of ED diluate salinity. The estimation results show that thin (0.26 and 0.35 mm) spacers of novel geometry result in much lower UPW production costs than a commercial 0.40 mm spacer. Lack of significant difference between the 0.26 and 0.35 mm spacer can be explained as a result of almost three times larger pressure drop at the same linear flow velocity when using thinner spacer (2189 vs. 793 Pa), which generates higher pumping costs despite lower DC energy consumption caused by decreased electric resistance and enhanced mass transfer.

54

Fig. 4. Estimated UPW production costs in ED-EDI system In conclusion, it was found that ED produces water of similar conductivity to RO, but the ratios of sulphate concentration [mg/dm3] to chloride concentration [mg/dm3] in the ED diluates are substantially higher than in RO permeate. This suggests that if the produced water is used as EDI feed, there should be less chlorine produced by the chloride oxidation, which should increase the life-time of ion-exchange membranes. Application of thin intermembrane spacers can improve the mass transfer conditions in the boundary layer of the diluate compartment, decreasing the concentration, polarization and allowing demineralization in shorter time. Moreover, thin intermembrane spacers can decrease the overall UPW production costs. 0.26 and 0.35 mm spacers of novel geometry was found to be more economical than commercially-available 0.40 mm spacer. When 0.26 mm spacer is applied and ED desalinates tap water down to 25 mg/dm3 of total dissolved salts (TDS), UPW production costs can be as low as $0.587/m3. Acknowledgements: The research leading to the presented results, performed within the EDRIM project (PBS3/B1/9/2015), were financed by the Polish National Science for Research and Development (NCBiR).

References 1. M. Turek et al., Membr. Water Treat., 4 (2013) 237-249.

55

EXTRACTION OF LITHIUM FROM AQUEOUS SOLUTIONS BY MEANS OF SELECTIVE CAPACITIVE DEIONIZATION

M. Bryjak, A. Siekierka, J. Kujawski

Department of Polymer and Carbon Materials, Wrocław University of Science

and Technology, Wyb. Wyspiańskiego 27, 50-370 Wrocław, Poland e-mail: marek.bryjak@pwr.edu.pl

The request for lithium has grown rapidly due to its use in lithium-ion batteries installed to electrical cars. Due to the fact that almost 80% of world documented lithium resources are located in five countries this element has been found to be critical raw materials for European economy (1,2). It is the reason why a search for new methods to get it from brackish or geothermal water and from recycling fluids of spent batteries has gained the attention of many research groups. The paper summarizes our efforts to find robust, efficient and cheap method for extraction of lithium salts from diluted aqueous solutions. It seemed to us that selective capacitive deionization, SCDI, could be an alternative method that can compete with other separations. Our studies were inspired by few published papers (3,4) and were focused on preparation of selective electrodes and selective membranes to be used in SCDI. CDI system with lithium selective membranes Lithium selective membranes containing copolymer of acrylic acid and poly(glycidyl methacrylate) modified with hydroxymethyl-12-crown-4 were prepared by polymerization of monomers in Celgard 2400 support. The Celgard samples, activated by plasma treatment, were impregnated with mixture of glycidyl methacrylate (GLY), acrylic acid (AA), ethylene glycol dimethacrylate (EGDMA), and monomers were polymerized. We obtained pore-filled membranes. Glycidyl functionalities allowed us to anchor 4-crown ether that participated in lithium transport while carboxylic functionalities created the suitable microenvironment. More details on the synthesis procedure can be found in our papers (5,6). The prepared AA and AA-GLY-crown ether membranes were tested in extraction of LiCl and KCl from their aqueous solutions. The data are shown in Fig. 1. The synergy between presence into membrane of acrylic acid and crown ether units allowed to reach adsorption capacity of 30 mg LiCl per 1 gram of activated carbon.

The stability of PAA-GLY-crown membrane was the next feature of the CDI system that was evaluated. To do it the sorption/desorption processes were repeated five times. Electrosorption kinetics for three cycles is shown in Fig. 2.

Hence, it is noted that wrapping carbon electrodes with lithium selective membranes duplicate electrosorption of lithium chloride. However, the gap between selective membrane and carbon electrode can reduce the efficiency of separation. It is the reason why we turned our attention to electrodes that selectively adsorb lithium ions.

56

CDI system with lithium selective electrode Lithium selective electrode was prepared via solid-state reaction from Li2CO3, MnCO3 and in-situ formed TiO2. The Li/Mn molar ratio was set as 1:3 for all samples while the amount of titanium dioxide was kept as 0%, 5%, 10% or 20 wt.% for particular samples. More details on electrode syntheses are shown in our paper (7). The SCDI studies allowed to show that the best materials for building of lithium selective electrode was mixture with 5% of titanium oxide. The SCDI system was able to adsorb about 35 mg/g of LiCl and its sorption properties were stable in the repeated cycles sorption/desorption.

The sorption properties of SCDI system with cation selective electrode could be improved when carbon electrode was covered by anion exchange membrane. In that case, the reversing of voltage could not facilitate the sorption of cations on carbon electrode and a ‘ping-pong’ phenomenon was reduced.

Fig. 1. LiCl and KCl adsorption in MCDI system with PAA and PAA-

GLY-crown membranes

Fig. 2. Cyclic adsorption for PAA-GLY-

crown (round) and PAA (diamond) membranes

Fig. 3. Electrosortion in SCDI equiped with lithium selective

electrode to catch cations and carbon electrode to catch anions

57

CDI system with lithium selective electrode and membrane wrapped counter-electrode To test the efficiency of such system, carbon electrodes were wrapped with PVC membranes modified with ethylenediamine. More details on properties of synthesized membranes can be found in our paper (8). The assembled CDI stack was able to adsorb more than 45 mg/g of LiCl and, what is important for lithium salt extraction, the regeneration of the system by reversing electrode polarity allowed to get 75% of adsorbed salt in few minutes (see Fig. 4). The careful inspection of Fig. 4 shows that efficiency of PVC membranes (both of them had similar contents of amine groups) were related to kind of solvent used for their preparation. Membranes obtained from tetrahydrofuran were more effective than their counter partners obtained from cyclohexanone. Their sorption kinetic was faster and the system extracted more lithium chloride than potassium or sodium chlorides. Hence, such system can be used for extraction of lithium salts from aqueous solutions.

The presented evaluations of lithium selective CDI systems lead to the conclusion that capacitive deionization can be the useful tool in extraction of lithium chloride from aqueous solution. However, more intensive studies on optimization of the system are needed. The last papers related to the practical use of CDI in desalination allow to believe that flowing electrodes (9) or fluidized bed electrodes (10) can be easily adapted for selective extraction of lithium salts from aqueous solutions in some continuous CDI systems.

References 1. H. Vikstrom, S. Davidsson, M. Hook, Appl. Energy. 110 (2013) 252-266. 2. Report on Critical Raw Materials for the EU, May 2014, http://ec.europa.eu/enterprise/policies/raw-materials/files/docs/crm-critical-material-profiles_en.pdf. 3. T. Ryu et al., Hydrometallurgy, 151 (2015) 78-83. 4. T. Ryu et al., Ind. Eng. Chem. Res., 52 (2013) 13738-13742. 5. M. Bryjak et al., J. Membr. Sep. Technol., 4 (2015) 110-115. 6. K. Smolinska-Kempisty et al., Mater. Chem. Phys., 148 (2014) 548-553. 7. A. Siekierka, J. Kujawa, M. Bryjak, Hydrometallurgy, March 2016. 8. A. Siekierka et al., Desal. Water Treat., submitted May 2016. 9. S. Porada et al., J. Mater. Chem. A, 2 (2014) 9313-9321. 10. G. Doornbusch et al., J. Mater. Chem. A, 4 (2016) 3642-3647.

Fig. 4. Adsortion and desortion of LiCl, NaCl and KCl salts in the SCDI system equipped with lithium selective electrode and anion exchange membrane

58

APPLICATION OF PERVAPORATION FOR SULFUR COMPOUNDS REMOVAL FROM GASOLINE

Katarzyna Rychlewska1, Krystyna Konieczny1, Wojciech Kujawski2

1Silesian University of Technology, Faculty of Energy and Environmental Engineering, 2 Akademicka str., 44-100 Gliwice, Poland

2Nicolaus Copernicus University in Toruń, Faculty of Chemistry, 7 Gagarina str., 87-100 Toruń, Poland

e-mail: katarzyna.rychlewska@polsl.pl

Pervaporation separation (PV) of organic-organic mixtures is receiving nowadays an increasing attention (1). Especially, removal of sulfur compounds from gasoline represents one of the most challenging pervaporation applications, since gasoline is a multi-component mixture consisting of hundreds of components. Studies carried out so far in this field has gained a number of promising findings (2). Nevertheless, still a lot of work needs to be done to augment the knowledge and create efficient industrial applications. It seems, that the consecutive investigations on new membrane materials for gasoline desulfurization are essential, knowing that separation efficiency in case of membrane technologies depends mainly on the proper selection of an active layer material. The short lecture will present the investigations of hydrophobic poly(ether-block-amide) and poly(dimethylsiloxane) based membranes, their selective and transport properties, and their applicability in pervaporation used for removal of sulfur compounds from gasoline. The interactions between typical hydrocarbons and sulfur species present in gasoline and tested membranes will be shown. The influence of organic components structure and physico-chemical properties on their transport across the membrane and desulfurization process efficiency will be discussed as well. Eventually, an impact of pervaporation process parameters on separation yield and efficiency will be exposed. Acknowledgements: Studies were supported by National Centre of Science – Project Number 2013/09/B/ST8/04065. References 1. B. Van der Bruggen, P. Luis, in “Progress in Separation and Filtration”, Eds. E. S. Tarleton; Academic Press 1 edition, 2014, 101-153. 2. H.R. Mortaheb et al., Chem. Eng. Res. Des., 90 (2012) 409-432.

59

VOLATILE FATTY ACID RECOVERY FROM FERMENTED WASTEWATER VIA ADSORPTION

Ehsan Reyhanitash, Sascha R. A. Kersten, Boelo Schuur

University of Twente, Sustainable Process Technology group, PO Box 217,

7500 AE, Enschede, The Netherlands

e-mail: e.reyhanitash@utwente.nl

Key words: fermented wastewater, volatile fatty acid, adsorption Introduction Large production and consumption of petroleum-based chemicals across the world has raised concerns on climate change. Instead of a linear production – consumption – waste economy, aiming at a circular economy where there is no waste appears more sustainable. Extensive research is in progress to discover or improve technologies by which chemicals can be produced from renewable resources and waste rather than petroleum resources. Fermentation enables production of various chemicals at low cost and high efficiency (1) and since numerous types of microorganisms are available to be used for fermentation, a wide variety of chemicals can be produced by fermentation (2,3). Volatile fatty acids (VFAs, fatty acids of six or fewer carbon atoms (4)) are among the most important chemicals to produce via fermentation, as they are widely used as platform chemicals for synthesis of value-added chemicals (4). An important obstacle for commercializing VFA production by fermentation is the low VFA concentration in fermentation broth. Therefore, effective separation techniques must be deployed to recover VFAs from fermentation broth. Fermented wastewater contains less VFA compared to conventional fermentation broths purposely made for VFA production, as the carbon content of wastewater is much lower. Next to VFAs, fermented wastewaters typically contain significant amounts of various dissolved salts. Na+, K+, H2PO4

-/HPO42-, Cl-, and SO4

2- are the most common ions originating from these salts. Due to the low concentration of VFAs and the presence of salt-originating ions, the typical pH of a fermented wastewater ranges from 4 to 6. Straight distillation, extractive distillation, membrane filtration and crystallization are the well-known techniques used for separation of VFAs from aqueous solutions (5-10). However, due to the low concentration of VFAs, any separation technique attempting to remove the water content of fermentation broth is economically impractical, and therefore, separation techniques targeting VFAs rather than the accompanying water are more efficient. Affinity separation techniques, which are able to target VFAs with no/minimal interaction with the accompanying water, are ideal for this purpose. Any form of physical or chemical interaction with VFA molecules induced through these techniques is referred to as affinity. The affinity is induced by external chemical agents specifically tuned to attract VFA molecules. Adsorption is among the most common affinity separation techniques. It is a reliable technique to recover compounds of interest from dilute and complex solutions (11). The technique comprises two stages: (I) separation of the compound of interest from a

60

gaseous or liquid solution often referred to as feed, (II) regeneration of the affinity inducing agent to recover the separated compound and recycle the agent. Various adsorbents have been reported for carboxylic acid recovery from aqueous solutions, including strong base, weak base and non-functionalized adsorbents (12). In the case of strong base adsorbents, since the anion of a carboxylic acid of interest is attached to a counter ion provided on the adsorbent (e.g. quaternary amine) after adsorption, regeneration of the adsorbent is impossible without introducing an alkaline solution (e.g. NaOH), which is not very sustainable. To avoid this drawback, this study has focused on weak base adsorbents, reported to attract organic acids by hydrogen bonding (i.e. Lewis bases), and on non-functionalized adsorbents. We report here on the use of four different adsorbents. Experimental The adsorbents used for this study are shown in Table 1. The composition of the fermented wastewater model solution used for this study is shown in Table 2. Here, for convenience, lactic acid is also referred to as a VFA, although it does not comply with the above VFA definition.

Table 1: Adsorbents used

Adsorbent Functional group Polymer Lewatit VP OC 1065 Primary amine Crosslinked polystyrene Amberlite IRA96 RF Secondary amine Crosslinked polystyrene Amberlite IRA96 SB Tertiary amine Crosslinked polystyrene Lewatit VP OC 1064 MD PH Non-functionalized Crosslinked polystyrene

Table 2: Fermented wastewater model solution composition

Model solution name Concentration [wt%] Concentration [mol/L] pH

Feed HAca HPrb HBuc HLad KCl Na2SO4 Na2HPO4 5.0 0.25 0.25 0.25 0.25 0.05 0.05 0.1

a: Acetic acid, b: Propionic acid, c: Butyric acid, d: Lactic acid

To compare the VFA capacity of the above adsorbents at equilibrium VFA concentrations comparable with the VFA concentrations in Feed, a concentrated version of Feed was prepared with all the species present in five times higher concentrations than those shown in Table 2, while maintaining the same ratio of the concentrations (with respect to each other). Afterwards, various dilutions of this concentrated solution were prepared by adding various amounts of water. Adsorption experiments were then performed in batch mode with ~ 20 g of a model solution and ~ 1 g of an adsorbent. Results Figures 1a – 1d show the capacity of the adsorbents for all the species involved in the equilibrium.

61

Fig. 1a and 1b. Multi-component adsorption isotherm of Lewatit VP OC 1065 (primary amine, left) and Amberlite IRA96 RF (secondary amine, right)

Fig. 1c and 1d. Multi-component adsorption isotherm of Amberlite IRA96 SB (tertiary amine, left) and Lewatit VP OC 1064 MD PH (non-functionalized, right)

As can be seen in Figures 1a – 1d, interestingly, the non-functionalized adsorbent had the highest adsorption capacity and selectivity for the VFAs. Measuring the Na+ and K+ content of the aqueous phases before and after adsorption showed that no K+ or Na+ is adsorbed by none of the adsorbents, and the salt-originating anions are adsorbed in their acidic form formed with the H+ originating from the VFAs. Despite the other three amine-containing adsorbents, the non-functionalized adsorbent had a very low capacity for mineral acids, and in the case of HCl and H2SO4, no adsorption was observed. This is advantageous both for adsorption, as it saves the adsorbent capacity for VFAs, and for desorption, as desorption of adsorbed mineral acids may be challenging and they may accumulate on the adsorbent over time with further adsorption/desorption cycles.

62

Outlook To examine this adsorbent in a more realistic adsorption/desorption process, an adsorption column setup will be applied, and additional results using the column setup will also be presented on the conference. References 1. A. Corma, S. Iborra, A. Velty, Chem. Rev., 107 (2007) 2411-2502. 2. A. J.J. Straathof, Chem. Rev., 114 (2014) 1871-1908. 3. L.T. Angenent, K. Karim, M.H. Al-Dahhan, B.A. Wrenn, R. Domíguez-Espinosa, Trends Biotechnol., 22 (2004) 477-485. 4. W.S. Lee, A.S.M. Chua, H.K. Yeoh, G.C. Ngoh, Chem. Eng. J., 235 (2014) 83-99. 5. C. Le Berre, P. Serp, P. Kalck, G.P. Torrence, Acetic Acid, in: "Ullmann's Encyclopedia of Industrial Chemistry", Wiley-VCH Verlag GmbH & Co. KGaA, 2000. 6. V.H. Agreda, Acetic Acid and its Derivatives, Taylor & Francis, 1992. 7. N. Alghezawi, O. Şanlı, L. Aras, G. Asman, Chem. Eng. Process., 44 (2005) 51-58. 8. S.K. Ray, S.B. Sawant, J.B. Joshi, V.G. Pangarkar, J. Membrane Sci., 138 (1998) 1-17. 9. W.S. Choi, K.-J. Kim, Sep. Sci. Technol., 48 (2012) 1056-1061. 10. J.W. Jung, H.S. Lee, K.-J. Kim, Sep. Sci. Technol., 43 (2008) 1021-1033. 11. H.M. Ijmker, M. Gramblička, S.R.A. Kersten, A.G.J. van der Ham, B. Schuur, Sep. Purif. Technol., 125 (2014) 256-263. 12. C.S. López-Garzón, A.J.J. Straathof, Biotechnol. Adv., 32 (2014) 873-904.

63

SEPARATION OF PRIMARY AND SECONDARY FATTY ALCOHOLS AND THEIR DERIVATIVES AND SUBSEQUENT

DETERMINATION OF THE POSITION OF HYDROXYL GROUP IN SECONDARY ALCOHOLS

L. Pazdur1, S. Tavernier1, K. Abbaspour Tehrani2

1University of Antwerp, Faculty of Applied Engineering, Salesianenlaan 90,

2660 Hoboken, Belgium 2University of Antwerp, Faculty of Sciences, Groenenborgerlaan 171, 2020

Antwerpen, Belgium e-mail: lukasz.pazdur@uantwerpen.be

Separation and identification process in organic synthesis are one of the most challenging parts of whole research. This part becomes more important in multistep organic synthesis where as pure as possible compounds are crucial for further steps. Moreover, the more side products are present, the more complicated purification will become. Very often one technique is not suitable to obtain a pure product. Therefore a combination of several methods will be necessary. The global research context is the study of isomerization of double bonds in unsaturated fatty alcohols and their derivatives in order to obtain α,ω-bifunctional compounds – mostly terminal diols (Fig. 1). The isomerization reaction is however an equilibrium reaction. As a consequence also internal diols (Fig. 2) can result. The most challenging part is (I) separation of terminal diols from internal diols and (II) determination of the position of hydroxyl group in the internal diols.

Fig. 6. Example of external diol Fig. 7. Example of internal diol Several chromatographic techniques were used for separation. Two gave promising results: preparative thin layer chromatography (PLC) and column chromatography. The affinity of terminal diol seems to be higher to the silica gel then the affinity of internal diols with the same carbon chain length. The determination of the position of the hydroxyl group includes the combination of different chemical reactions (dehydration (1), ozonolysis (2)) and analytical methods (column chromatography, GC-MS). Selective dehydration of secondary alcohols allows introducing a double bond and subsequently to obtain by fission technique (ozonolysis) short chain alcohols and diols, the length of them correspond to the position of the hydroxyl group. The mixture of the short chain alcohols and diols were successful analysed by means of GC-MS. The approach is presented in the figure below.

OH

OH

64

Acknowledgements: We thank the Faculty of Applied Engineering at University of Antwerp for founding the research.

References 1. J. Clayden, N. Greeves, S. Warren, Organic Chemistry 2nd edition, Oxford University Press, USA 2012, 389. 2. J.A. Sousa, A.L. Bluhm, J. Org. Chem., 25 (1960) 108-111.

65

KINETIC EXTRACTIVE RESOLUTION

Sandra Corderi1, Erik Heeres2, Boelo Schuur1 1University of Twente, Faculty of Science and technology, Sustainable Process

Technology Group, PO Box 217, 7500AE, Enschede, The Netherlands 2University of Groningen, Faculty of Mathematics & Natural Sciences,

Department of Chemical Technology, Nijenborgh 4, 9747 AG, Groningen, The Netherlands

e-mail: b.schuur@utwente.nl Extractive resolution is a technique to separate enantiomers through liquid-liquid extraction, and is also known as enantioselective liquid-liquid extraction (ELLE) (1). The technique is robust and scalable, however, the drawback is a required enantioselectivity of approximately 1.5 (2), which for many systems is not achievable at equilibrium. When operated off-equilibrium, i.e. in the kinetic regime, it may be possible to achieve higher enantiomeric excess, and with this aim, we have directed our research towards kinetic extractive resolution. In this poster, we present a study on the homogeneous organic phase complexation kinetics of azophenolic crown ether and phenyl glycinol enantiomers using a stopped-flow device. First, complexation equilibrium was studied in batch using UV-vis spectrophotometry, and then, using the same spectrophotometer, a stopped-flow setup was used to measure in time the development of the complex formation. The time resolution was 0.033 s, and it was found that already in the very first datapoints, the complexation had largely been completed. However, when using 1-octanol as diluent, reaching the final equilibrium took longer than 20 min. From this, it was concluded that a) the complexation between phenylglycinol and the azophenolic crown ether appears to be very fast, and b) hydrogen bonding interactions between the 1-octanol and the azophenolic crown ether are likely disturbing the complexation with phenylglycinol and thus responsible for the slow final equilibration. For operation in a true kinetic mode, extraction conditions should promote extremely fast mass transfer in order not to be mass transfer limited in the initial fast complexation regime. Acknowledgements: This project was funded by technology foundation STW (project 11404) and co-funded by the Institute for Sustainable Process Technology (ISPT). References 1. B. Schuur et al., Org. Biomol. Chem., 9 (2011) 36-51. 2. M. Steensma et al., Chirality, 18 (2006) 314-328.

66

IONIC LIQUIDS AS ALTERNATIVE EXTACTIVE SYSTEMS FOR QUANTITATIVE DETERMINATION OF NATURAL PRODUCTS IN

PLANTS

Ivan Svinyarov1, Rozalina Keremedchieva1, Anely Nedelcheva2, Milen G. Bogdanov1

1Faculty of Chemistry and Pharmacy, Sofia Univerity St. Kl. Ohridski,

1, James Bourchier Blvd., 1164 Sofia, Bulgaria 2Faculty of Biology, Sofia University St. Kl. Ohridski,

8, Dragan Tzankov Blvd., 1164 Sofia, Bulgaria e-mail: mbogdanov@chem.uni-sofia.bg

The majority of methods for quantification of natural products (NPs) are based on High Performance Liquid Chromatography (HPLC), which employ organic solvents, such as methanol, diethyl ether, chloroform, etc, to perform the sample preparation step. All these solvents, however, are highly volatile, flammable and toxic, which is in a contradiction with the widely accepted nowadays twelve principles of the Green chemistry. In particular, according to the 5th principle, the use of safer auxiliary substances (e.g. solvents, separation agents, etc.) is rather preferable to the harmful ones in the laboratory practice. Ionic liquids (ILs) consist of charge-stabilized organic cation and inorganic or organic anion. They are liquids at temperatures below 100°C and display a wide range of unique properties, such as negligible vapor pressure, non-flammability, high thermal stability, low chemical reactivity, etc. The above mentioned features, together with their fine tunable physicochemical properties, favor ILs application as extractants of NPs from their native sources. Following the above mentioned general trends we studied the performance of a wide variety of ILs in the sample preparation step for determination of NPs of industrial interest, e.g. glaucine (1,2), galantamine (2) and valerenic acids (3,4). All possible influential factors were comprehensively investigated, optimal conditions for quantitative extraction of the target NPs were found and safer HPLC methods for determination were developed and validated. The methods proposed avoid the use of organic solvents, while ensure quantitative yields, the latter suggesting their high potential for industrial application.

Acknowledgements: The financial support of the National Science Fund of Bulgaria at the Ministry of Education and Science (project DFNI T 02/23) is greatly acknowledged by the authors.

References 1. M.G. Bogdanov et al., Sep. Purif. Technol., 97 (2012) 221-227. 2. M.G. Bogdanov, I. Svinyarov, Sep. Purif. Technol., 103 (2013) 279-288. 3. I. Svinyarov, R. Keremedchieva, M.G. Bogdanov, Sep. Sci. Technol., (2016) DOI: 10.1080/01496395.2016.1171783. 4. I. Svinyarov, A. Nedelcheva, M.G. Bogdanov, Planta Medica, 81 (2015) PW_227.

67

MODIFIED METHACRYLATE POLYMER PARTICLES AND THEIR APPLICATION AS COLUMN PACKINGS IN HPLC

Marta Grochowicz, Przemysław Pączkowski, Barbara Gawdzik

Maria Curie Skłodowska University, Department of Polymer Chemistry,

Gliniana 33, 20-614 Lublin, Poland e-mail: mgrochowicz@umcs.pl

Permanently porous copolymers in the shape of microspheres are important materials used as column packings in different chromatographic methods. Methacrylate copolymers synthesized from monomers possessing polar functional groups are less hydrophobic than the traditional ST-DVB stationary phases. However, the radical polymerization of highly polar monomer is awkward and usually leads to the product with an insufficient amount of polar groups. Surface modification of microspheres aimed at achieving their shell-functionalization is an interesting tool for modifying their properties.

The aim of this study was to obtain uniform polymeric microspheres of glycidyl methacrylate (GMA) and 1,4-dimethacryloyloxybenzene (1,4DMB) using seed polymerization. Poly(GMA-co-1,4DMB) microspheres which were subjected to the further chemical modification possessed diameters about 8.61 µm, the surface area (SBET) equal 236 m2/g, the pore volume Vp = 0.25 cm3/g, and the pore diameters were in the range of mesopores. They were modified in two ways. In the first method, microspheres were reacted with sodium cyclopentadienide which is a derivative of the most reactive dienes in the Diels–Alder (DA) reactions (1). The chemical modification of such prepared microspheres was carried out with DA reaction. As a dienophile, the maleic anhydride was used. In the next step microspheres were reacted with water and finally the carboxylic groups were created on the surface of the microspheres. In the second method primary poly(GMA-co-1,4DMB) microspheres were reacted with methacrylic acid. As a result of the opening reaction of epoxide ring with acid, ester group and carbon-carbon double bond were created on the surface of microspheres. Polymeric beads were synthesized with the intention to use them as polymeric stationary phases in high performance liquid chromatography (HPLC). To evaluate the chromatographic properties of porous packing the Smith method was applied (2). The retention indices of five sets of homologous compounds and the selectivity test compounds (toluene, nitrobenzene, p-cresol, 2-phenylethanol, N-methylaniline) were measured. Chromatographic properties of primary poly(GMA-co-1,4DMB) microspheres and modified in two ways ones were compared. Acknowledgements: This research was supported by special purpose subsidy to conduct research aimed at developing young scientists and doctoral students at Faculty of Chemistry UMCS in 2016 year

References 1. M. Grochowicz et al., Adsorpt. Sci. Technol., 33 (2015) 677-684. 2. M. Grochowicz et al., Adsorpt. Sci. Technol., 33 (2015) 609-616.

68

HYDROPHOBIC AGGREGATION OF TALC IN AQUEOUS SOLUTION IN RELATION TO THE OIL AGGLOMERATION

PROCESS

Izabela Polowczyk, Anna Bastrzyk, Tomasz Koźlecki

Wrocław University of Technology, Faculty of Chemistry, Department of Chemical Engineering , Norwida 4/6, 50-373 Wrocław, Poland

e-mail: izabela.polowczyk@pwr.edu.pl

In this study, the stability of tri-phase systems comprising of pharmaceutical talc and kerosene dispersed in aqueous phase was investigated with regard to the oil agglomeration process. The aim of this work was also to investigate the effect of cationic surfactant presence and adsorption on the behaviour of talc particles in suspension and its agglomerates with kerosene. Hydrophobic agglomeration is a method to aggregate fine particles in aqueous solutions, which rises from the strong hydrophobic attractive force between the particles (1). In oil agglomeration process an immiscible liquid is used to bind the particles dispersed in aqueous solution. Mixing provides attachment of oil droplets to the surface of particles and, as a consequence, agglomeration of particles via so-called oil bridges. The structure of agglomerates depends on the surface properties of particles, as well as operating conditions of the process (2). It was proven that the oil agglomeration of talc proceeds irregularly without surfactant addition because of the properties of talc surface. Much used cationic surfactant dodecylammonium hydrochloride (DDA) was applied as a wetting agent and emulsifier, and kerosene was used as bridging oil. First, the talc suspensions in the presence of cationic surfactant were examined using the Turbiscan Lab Expert. After the addition of oil, the resulting mixtures’ stability was also studied using the backscattering technique. For each sample, the destabilization kinetics profile was determined and the instability index (TSI) was calculated. The amount of applied cationic surfactant, as well as volume of oil, were established with a central composite design (CCD) which was used to estimate the importance and interrelation of the talc agglomeration process parameters. In order to explain instability phenomena, the zeta potential measurements of talc and oil droplets were performed. In addition, the adsorption isotherm of DDA onto the talc surface was determined. The changes of a particle size distribution (PSD) as a result of surfactant addition were monitored using a laser diffractometer and the fractal dimensions of agglomerates were calculated. Microscopic photos of talc agglomerates formed after addition of DDA and kerosene were taken in transmission mode with an optical microscope.

Acknowledgements: This work was financially supported by the National Science Centre, Poland, grant No. 2011/01/B/ST8/02928.

References 1. Y.-Q. Ji et al., Colloid Surface A, 298 (2007) 235-244. 2. J. Drzymała, Mineral Processing. Foundations of Theory and Practice of Minerallurgy, Oficyna Wydawnicza Politechniki Wrocławskiej, Wrocław 2007, 465-497.

III. POSTERS

71

PRECONCENTRATION OF SCANDIUM FROM BAUXITE RESIDUE LEACHATES BY SUPPORTED IONIC LIQUID PHASE

Dženita Avdibegović, Mercedes Regadìo and Koen Binnemans

KU Leuven, Department of Chemistry, Celestijnenlaan 200F, 3001 Leuven,

Belgium e-mail: dzenita.kasapovic@kuleuven.be

Bauxite residue (BR) or red mud is a by-product in the production of alumina by the Bayer process. About 1–1.5 tonnes is generated for each tonne of alumina produced (1). Still, BR contains relatively large concentrations of not only elements like aluminium, iron and titanium but also of scandium, yttrium and other rare-earth elements (REEs), which are being used in high-tech applications. Therefore, BR can be considered as a secondary resource of REEs and reduce their supply risk, as their current global production is dominated by China which continues to grow the REEs export quota (2). Besides, because of a storage problem there are attempts all over the world to valorise BR. The concentration of REEs in BR is rather low comparing to other major elements. In this work the recovery of Sc(III) with supported ionic liquid phases (SILPs) was investigated as a potential adsorbent for Sc(III) from leach solutions. Ionic liquids (ILs) exhibit tuneable properties for metal recovery, but still they have a high viscosity which may involve drawbacks in a process design. On the other hand, the IL in SILPs maintain large specific surface area and mechanical properties of the support, thus circumventing mass transport limitations and being suitable for metal preconcentration. A new SILP was developed with poly(styrene-co-divinylbenzene) support and covalently bonded IL with carboxylic functional group. The SILP was tested for Sc(III) recovery from diluted chloride solutions. The effect of pH, contact time, stripping efficiency and reusability of adsorbent were investigated. Adsorption experiments were performed in the pH range of 0.5-3.0 at room temperature. The experimental data were fitted into a pseudo-second order kinetic model (R2=0.999). The theoretical maximum adsorption capacity was 0.18 mmol g-1 with adsorbent dose of 5 g L-1. Quantitative stripping of Sc(III) loaded SILP was achieved with 1 mol L-1 sulfuric acid. Even after seven batch experiment adsorption/desorption cycles there was no significant difference in adsorption efficiency of the SILP. With tuneable properties of ILs and advantages when combining with a solid supports, SILPs are promising adsorbents for recovery of valuable metals. Acknowledgments: Dženita Avdibegović was financially supported within European Training Network for Zero Waste Valorisation of Bauxite Residue (Red Mud) under grant agreement number: 636876 (REDMUD – H2020-MSCA-ITN-2014). References 1. S. Kumar, R. Kumar, A. Bandopadhyay, Resour. Conserv. Recycl., 48 (4) (2006) 301-314. 2. K. Binnemans et al., J. Clean. Prod., 99 (2015) 17-38.

72

A STUDY ON THE ELECTRODIALYTIC NICKEL SALTS CONCENTRATION

Piotr Dydo1, Dorota Babilas1, Agata Jakóbik-Kolon1, Andrzej Milewski1,

Danuta Bentkowska2, Aneta Franczak2, Ryszard Nycz2

1Department of Inorganic, Analytical Chemistry and Electrochemistry, Faculty of Chemistry, Silesian University of Technology, B. Krzywoustego 6,

44-100 Gliwice, Poland 2Nycz Intertrade CO. LTD, Płk. Dąbka 8C, 30-732 Cracow, Poland

e-mail: dorota.babilas@polsl.pl

The metal finishing industry generate a wide range of rinse waters containing precious metal ions, however, at low concentrations. Nowadays, various treatment techniques such as ion exchange, precipitation, membrane processing and electrochemical deposition can be used for heavy metal recovery from the above-mentioned wastewaters. In this work, the possibility of nickel salt concentration in the wastes with low nickel content by electrodialysis (ED) has been investigated. The experiments were carried out using an EDR-Z/10-0.8 module (MemBrain, Czech Republic) with an unit effective membrane area of 64 cm2. The ion-exchange membranes used in these investigations were AMC - AMA (IONSEP, China). A series of ED experiments of nickel electroplating wastewaters were carried out periodically. The investigations were performed at a constant voltage, which corresponded to the initial electric current density of 300 A∙m-2. Nickel ions concentration was determined using Ionic Chromatograph (ThermoDionex, USA). The objective of the experiments was to examine the applicability of an ED process to nickel salt concentration from rinse water. In addition, the nickel recovery ( +2

NiR , %) was calculated. Nickel concentrations in the feed and in the

concentrate, as well as, nickel recovery levels measured were presented in Table 1. The results indicate that, ED allows for concentration of nickel in the wastewaters in question. It was observed that nickel content in solutions after ED was approx. two times higher than in the feed, while its recovery exceeded 80%.

Table 1. The nickel concentration in processing solutions, and recovery coefficient Exp. no. Ni2+, g/dm3 (before ED) Ni2+, g/dm3 (after ED) +2

NiR , %

1. 11.6 25.0 84.3 2. 15.9 39.7 94.8 3. 22.1 33.3 98.4 4. 17.2 28.6 99.7

Acknowledgements: This work was financially supported by Polish National Center for Research and Development, Project no. GEKON2/05/267906/10/2015/NCBR.

73

THE INFLUENCE OF CHELATING AGENTS ON THE ELECTRODIALYTIC ZINC RECOVERY FROM SPENT

ELECTROPLATING BATH

Dorota Babilas, Piotr Dydo

Department of Inorganic, Analytical Chemistry and Electrochemistry, Faculty of Chemistry, Silesian University of Technology, B. Krzywoustego 6,

44-100 Gliwice, Poland e-mail: dorota.babilas@polsl.pl

Nowadays, transition-metal ions can be removed from wastewater by various methods, such as chemical precipitation, ion exchange, electrolysis, adsorption and flotation. Unfortunately, despite numerous advantages, the commonly applied methods have many drawbacks. In the case of solutions contaminated with transition-metals, conventional treatment techniques are inefficient, especially when selective recovery of metals is considered. In the recent years, the application of membrane processes for transition-metals ions recovery has been investigated. Electrodialysis (ED), one of these methods, has been effectively applied for the removal of above mentioned metal ions. Moreover, the selectivity of the ED can be substantially increased by the introduction into the diluate solution additives (ligands, chelating agents), which are known to create highly stable complexes with the metal ions. Therefore, in this work, the possibility of selective zinc salt recovery from model spent electroplating bath by ED enhanced with complex formation has been investigated. The experiments were carried in a plate-frame electrodialytic cell with an unit effective membrane area of 16 cm2. The heterogeneous membranes used in this work were AM(H)-CM(H) (Ralex, Czech Republic). Experiments included a series of EDs of two-component transition-metal salt solutions with an addition of chelating agent such as lactic acid, malic acid, as well as citric acid. The examined solutions contained iron and zinc compounds (1 g/dm3 Fe3+; 215 g/dm3 ZnSO4·7H2O). The iron was added to the test solution as Fe2(SO4)3·24H2O and zinc as ZnSO4·7H2O. All chemicals were of analytical purity. The objective of the experiments was to examine the applicability of the ED enhanced with complex formation for separation of iron species from zinc salt. The effect of the chelating agent (lactic acid, malic acid and citric acid) addition on the selectivity coefficient was examined. It was found that selectivity of the ED in Fe3+ separation from Zn2+ can be improved by the addition of citric acid to solution of the transition-metal salts. Results confirm that citric acid create more stable complexes with Fe3+ ions than lactic and malic acids.

Acknowledgements: This work was supported by the Polish National Science Centre upon decision no. DEC-2015/17/N/ST8/02313.

74

SOLVOMETALLURGICAL SEPARATION OF RARE-EARTH IONS BY EXTRACTION WITH TWO MUTUALLY IMMISCIBLE

ORGANIC PHASES

Nagaphani Kumar Batchu, Koen Binnemans

KU Leuven, Department of Chemistry, Celestijnenlaan 200F, P.O. Box 2404, B-3001 Heverlee, Belgium

e-mail: nagaphanikumar.batchu@chem.kuleuven.be Solvent extraction with two mutually immiscible organic phases is an alternative to conventional solvent extraction with an aqueous feed phase. We developed a solvent extraction process for separation of rare earths, where the more polar organic phase comprises ethylene glycol with dissolved rare-earth nitrate salts and lithium nitrate, while the less polar phase is a solution of the neutral extractant Cyanex® 923 dissolved in n-dodecane. The commercial extractant Cyanex 923® is a mixture of four trialkylphosphine oxides: R3P=O, R2R’P=O, RR’2P=O and R’3P=O, where R = n-octyl and R’ = n-hexyl. The extraction of Nd(III) from ethylene glycol has been studied as a model system. Different parameters have been investigated: concentration of extractant, concentration of Nd(NO3)3 and LiNO3 in the ethylene glycol phase, phase volume ratio, temperature and equilibration time. The extraction mechanism was investigated by slope analysis. Extraction of rare earths from ethylene glycol was compared with extraction from aqueous solution. The heavy rare earths are more efficiently extracted from ethylene glycol where-as extraction of the light rare earths is less efficient compared to aqueous solutions (Fig. 1). The separation

factor of Dy(III) over Nd(III) is 24.6 from ethylene glycol for [Cyanex® 923] = 0.01 mol.L-1, whereas it is only 1.2 from the corresponding aqueous solutions. This leads to a better separation of heavy rare earths from light rare earths. The separation of Nd(III) and Dy(III) has been studied because of its relevance for the recycling of rare earths from NdFeB permanent magnets. After extraction, the rare earths could be stripped from the n-dodecane phase by oxalic acid or simply by addition of water.

La(57) Ce(58) Pr(59) Nd(60) Gd(64) Dy(66) Yb(70)0

20

40

60

80

100

Ethylene glycolAqueous solutions

% E

xtra

ctio

n

REE

Fig. 1. Comparison of extraction behavior of rare earths from aqueous solutions and non-aqueous ethylene glycol solutions by 0.03 M Cyanex® 923

in n-dodecane

75

HYDROMETALLURGICAL SEPARATION OF NICKEL FROM SPENT RANEY Ni CATALYST USING DIFFUSION DIALYSIS

FOR RECYCLING OF SULPHURIC ACID

Helena Bendova, Hana Dvorakova, Tomas Weidlich

Institute of Environmental and Chemical Engineering, Faculty of Chemical Technology, University of Pardubice, Studentská 573, 532 10 Pardubice, CZ

e-mail: Helena.Bendova@upce.cz The application of Raney Al-Ni alloy in alkaline aqueous solution enables efficient reductive degradation (hydrodehalogenation) of halogenated anilines and phenols even at room temperature and ambient pressure. This method produces nickel slurry (spent Raney Ni) as solid product separated by sedimentation of dehalogenated reaction mixture. The proposed hydrometallurgical protocol enables simple recycling of spent Raney Ni catalyst used for hydrodehalogenation of aromatic halogenoderivatives and production of Ni(OH)2 (1). The mentioned hydrometallurgical process is based on dissolution of separated nickel slurry in hot diluted sulfuric acid aerated by air. Consecutive diffusion dialysis, which was done in a two-compartment counter-current dialyzer with an anion-exchange membrane Neosepta-AFN at steady state, enables removal of excess of sulfuric acid from model solution of aluminium and nickel sulphate in 16 wt.% of H2SO4 and simple recycling of the isolated sulfuric acid. Next, the obtained dialysate was alkalized using excess of NaOH solution to pH ~ 12-13 and precipitated Ni(OH)2 was filtered and washed with hot water. Crude Ni(OH)2 was re-precipitated by dissolution in 16 wt.% of H2SO4 and alkalization with excess of aqueous NaOH at pH ~ 12-13. Using this procedure, the Ni(OH)2 contaminated with only 4.7 wt.% Al was obtained. This material was successfully tested as precursor for preparation of dehydrodehalogenation catalyst. Acknowledgements: This work was supported by Technology Agency of the Czech Republic, project No. TG02010058-GAMA01/007. References 1. J.Y. Lee et al., J. Hazard. Mater., 176 (2010) 1122-1125.

76

PREPARATION AND CHARACTERIZATION OF SORBENT BASED ON PECTIN AND CARBON NANOTUBES

Joanna Bok-Badura, Agata Jakóbik-Kolon, Krzysztof Karoń,

Dorota Babilas, Artur P. Herman, Sławomir Boncel

Silesian University of Technology, Faculty of Chemistry, Marcina Strzody 9, 44-100 Gliwice, Poland

e-mail: joanna.bok-badura@polsl.pl

The increase of environmental contamination by heavy metals, the consequence of industrial development, is a serious problem. Various methods have been proposed for heavy metal ions removal from waste water. Adsorption is proven to be an economical, green and efficient technology. A number of natural and synthetic adsorbents, e.g. fly ash, activated carbon, zeolites, nut shells and various microorganisms have been used (1-5). Carbon nanotubes, due to their large surface area, hollow structure, light mass density, mechanical strength are considered also as a sorbent materials (6). However, their usage is limited mainly due to the problems with their separation and application in column, flow processes. Therefore, in these studies, new sorbent of carbon nanotubes immobilized in pectin matrix, in the beads form, has been investigated. Obtained sorbent combines the properties of carbon nanotubes and the pectin. Hybrid sorbent was prepared by the solution mixing method (7,8). Multi wall carbon nanotubes (MWCNTs - Nanocyl NC700) were previously modified using the Fenton`s reagent. Homogeneous dispersion of carbon nanotubes was prepared by sonication of appropriate amount of modified MWCNTs in 1% Triton X-100 solution. MWCNTs were next separated from surfactant and mixed with pectin solution (final concentration of pectin in solution – 3%, MWCNTs – 0.2%). Obtained slurry of MWCNTs in pectin was next sonicated for 15 minutes and shaken for at least 4 hours. Next, slurry was slowly instilled by peristaltic pump into 1M CaCl2 solution. As the result, black beads (c.a. 3 mm diameter) of hybrid sorbent were obtained. Beads were kept in the mother solution at 4°C for 24 hours, and next filtered and washed for complete removal of chloride ions. Finally, beads were dried in 35°C. The obtained hybrid sorbent (6% MWCNTs in relation to pectin) was characterized by scanning electron microscopy and analysed by IR spectroscopy. The affinity of some metal ions (Pb2+, Cd2+, Cu2+, Zn2+) to prepared material, in various pH, was investigated. The sorption capacity as well as the swelling index of sole pectin beads and pectin-MWCNTs were investigated and compared. References 1. I.J. Alinnor, Fuel, 86 (2007) 853-857. 2. C. Gabaldón et al., Water Res., 30 (1996) 3050-3060. 3. E. Erdem et al., J. Colloid Interface Sci., 280 (2004) 309-314. 4. E. Pehlivan et al., J. Hazard. Mater., 167 (2009) 1203-1208. 5. X. Xiao et al., Bioresour. Technol., 101 (2010) 1668-1674. 6. G.P. Rao et al., Sep. Purif. Technol., 58 (2007) 224-231. 7. P.C. Ma et al., Compos. Part A: Appl. Sci. Manuf., 41 (2010),1345-1367. 8. K. Kurzydłowski, M. Lewandowska (Eds): „Nanomateriały inżynierskie konstrukcyjne

i funkcjonalne”, Wydawnictwo Naukowe PWN, Warszawa 2010.

77

SORPTION STUDIES OF CADMIUM AND LEAD IONS ON HYBRID POLYSACCHARIDE BIOSORBENTS

J. Bok-Badura, A. Jakóbik-Kolon, A. K. Milewski, K. Mitko

Silesian University of Technology, Faculty of Chemistry, Department of

Inorganic, Analytical Chemistry and Electrochemistry, ul. B. Krzywoustego 6, 44-100 Gliwice, Poland

e-mail: agata.jakobik@polsl.pl Pollution of the environment by heavy metals is still a serious worldwide problem. Therefore, the easily accessible, efficient and cheap methods of their removal are demanded. Various sorbents of natural origin are widely used for such purpose. Pectin-based biosorbents are extensively studied due to their important advantage of easy beads formation (1-3). Our previous studies (4,5) showed that pectin beads may also immobilize other, not so readily gellable polysaccharides. Such additives influence the structure and swelling index of the obtained hybrid biosorbents (4,5) and thereby alter the sorption properties e.g. sorption kinetics (4). The aim of this work was to study the cadmium and lead sorption properties of three new hybrid pectin-based biosorbents containing gellan, xanthan and carob gum of gum to pectin ratio 1:1, 1:1 and 1:3, respectively. The biosorbents were prepared and characterized in our previous studies (5). Based on the batch studies of the cadmium and lead sorption on the obtained biosorbents, the parameters of the selected kinetic models (pseudo-first and pseudo-second) and isotherms (Freundlich, mono- and bi-site Langmuir) were estimated. Acknowledgements: This work was financed by Polish Ministry of Science and Higher Education under „Iuventus Plus” grant No IP2014 016173 (2015-2017). References 1. Y.N. Mata et al., J. Hazard. Mater., 178 (2010) 243-248. 2. Y.N. Mata et al., Chem. Eng. J., 150 (2009) 289-301. 3. P. Harel et al., Ind. Crops Prod., 7 (1998) 239-247. 4. A. Jakóbik-Kolon et al., Sep. Sci. Technol., 49 (2014) 1679-1688. 5. A. Jakóbik-Kolon et al., Sep. Sci. Technol., (2016), DOI:10.1080/01496395.2016.1162809.

78

CASCADES WITH ADDITIONAL OUTGOING FLOWS FOR SIMULTANEOUS CONCENTRATION OF INTERMEDIATE

COMPONENTS FROM MULTICOMPONENT ISOTOPE MIXTURES

Anton K. Bonarev1, Andrei Yu. Smirnov1, Georgy A. Sulaberidze1,

Shi Zeng2, Valentin D. Borisevich1, Dongjun Jiang2

1National Research Nuclear University MEPhI, 115409 Russia, Moscow, Kashirskoe shosse, 31

2Tsinghua University, 100084, Beijing, China e-mail: antonbonarev@gmail.com

A method of concentration of the intermediate (by a mass number) isotopes from multicomponent mixtures in a single separation cascade with additional outgoing flows is developed. The efficiency of such a cascade is compared with that of other known methods of intermediate components extraction with relatively high concentrations on the example of tungsten isotopes separation of the natural abundance. It is demonstrated the existing advantages of the proposed method in contrast to the other ones also used for concentration of the isotopes with intermediate mass numbers. The most impressive of them is ability to obtain a few several target products in the outgoing from a cascade flows. Acknowledgements: This research was carried in the framework of the joint Sino-Russian project supported by the Russian Fund for Basic Research (RFBR) under the contract No 16-58-53058 GFEN_a and the National Natural Science Foundation of China (NSFC) under the contract No 1151101155. This work is also supported by the grant of the President of Russian Federation for the young PhDs with the No 14.Y30.16.6284-MK.

79

ADSORPTION OF MOLYBDATE ANION (MoO42-) by Zn/Al

LAYERED DOUBLE HYDROXIDE OBTAINED FROM ZINC ASH

Laura Cocheci, Lavinia Lupa

Politehnica University of Timisoara, Faculty of Industrial Chemistry and Environmental Engineering, Blv. Vasile Parvan nr.6, 300223, Timisoara,

Romania e-mail: laura.cocheci@upt.ro

Layered double hydroxides (LDHs) have relatively large surface areas and high anion exchange capacities so they have been studied extensively to evaluate their potential as adsorbents of anionic contaminants (1,2). In this paper the studies regarding the molybdate anions adsorption by Zn/Al layered double hydroxide are presented. The studied adsorbent was obtained through co-precipitation of aluminium salts with zinc chloride in alkaline media. It can be called a low-cost adsorbent because as zinc source was used zinc ash resulted from hot-dip galvanizing process. The zinc ash was treated with hydrochloric acid in order to obtain zinc chloride solution, which was followed by a purification process. The obtained adsorbent was used as-synthesized (LDH) and also calcinated at 450°C (CLDH). Both of adsorbents were subject to XRD, FTIR, SEM and EDX analysis. The adsorption of molybdate anion was carried out in batch mode. The influence of contact time, solid:liquid ratio and initial concentration of Mo(VI) was investigated. Besides determination of kinetic parameters and adsorption isotherm, a possible adsorption mechanism of molybdate anion by the studied material was assumed. This study present an eco-compatible solution for the reuse of an industrial waste in an efficient process of water treatment. Keywords: zinc ash, acid digestion, layered double hydroxide, molybdate, adsorption Acknowledgment: This work was supported by a grant of the Romanian National Authority for Scientific Research and Innovation, CNCS - UEFISCDI, project number PN-II-RU-TE-2014-4-0771. References 1. R. Galindo et al., Appl. Clay Sci., 95 (2014) 41-49. 2. S. Britto et al., Solid State Sci., 9 (2007) 279-286.

80

THE USE OF NATURAL POLYMER IN THE REMOVAL OF RARE EARTH ELEMENTS

Corneliu Mircea Davidescu, Andreea Gabor, Adina Negrea, Mihaela

Ciopec, Petru Negrea

Politehnica University Timişoara, Faculty of Industrial Chemistry and Environmental Engineering, Victoriei Square Nr. 2, 300006 Timişoara, România

e-mail: emeline_gabor@yahoo.com

Pollution with heavy metals is a serious problem and it is increasing with the rapid development of industry. The industrial use of heavy metals introduces a large amount of toxic metals into the atmosphere and into the aquatic and terrestrial environment (1). The economic growth of a country is given by the industrial development, which increases the problem of waste disposal. The electrical and electronic compounds which have reached they lifetime, can be properly treated and become an alternative resource for many metals including rare earth elements (REEs) (2). Rare earth elements have a wide application in many fields as alloys, magnets, catalysts and are also used in equipment’s such as batteries, sensors, electric vehicles, energy efficient lighting, etc. (2). Many methods like chemical precipitation, ion-exchange, coagulation, flocculation and adsorption have been used to remove metals from waste water. Due to environmental considerations researches are trying to develop new adsorbents that are also economically advantageous. Therefore cellulose is the most abundant and renewable biopolymer in nature, being considered one of the promising materials (3). Beside using a proper solid support, it is also important that the extractant should give additional advantages for using the new material in the adsorption of metal ions. Thiourea beside being an environmental friendly extractant, it increases the adsorption proprieties of the solid support used on. In this study cellulose is functionalized with thiourea in order to obtain an environmental friendly adsorbent material and it is used for the adsorption of Nd(III) and Eu(III) ions from aqueous solutions. Kinetic, equilibrium and thermodynamic studies were carried. The adsorption capacities of the new obtained material in the removal process of the two metal ions are 30 mg/g for Eu(III) and 70 mg/g for Nd(III).

References 1. R. Saravanan et al., J. Wat. Res. Prot., 7 (2010) 530-545. 2. H-S. Yoon et al., Hydrometallurgy (2016), http://dx.doi.org/10.1016/j.hydromet.2016.01.028. 3. L.V.A. Gurgel et al., Bioresource Technol., 100 (2009) 3214-3220.

CA

NC

EL

LE

D

81

EFFICIENT BORON ABSTRACTION USING HONEYCOMB-LIKE POROUS MAGNETIC HYBRIDS: ASSESSMENT OF TECHNO-

ECONOMIC RECOVERY OF BORIC ACID

Mustafa Gazi, Akeem A. Oladipo

Department of Chemistry, Eastern Mediterranean University, Gazimagusa, TRNC via Mersin 10, Turkey

e-mail: mustafa.gazi@emu.edu.tr Boron is an essential micronutrient for animals, plants and human beings. The maximum boron tolerable limit for extremely sensitive to very tolerant plants ranges 0.5 to 10 mg/L (1). Boron deficiency causes yield loss; stunted growth and even death of the plant, while exposure to high boron levels has a toxic effect (2). According to Oladipo and Gazi (3) chronic exposure to large amounts of boron can cause kidney damage and negatively affect the reproductive system in humans. Particularly, the high boron concentration in the aquatic environment is dreadful because boron compounds can easily interact with heavy metals producing more harmful complexes. Porous magnetic hybrids were synthesized and functionalized with glycidol to produce boron-selective adsorbent. The magnetic hybrid (MH) comparatively out-performed the existing expensive adsorbents. MH had a saturation magnetization of 63.48 emu/g and average pore diameter ranging from meso to macropores. The magnetic hybrids showed excellent selectivity towards boron and resulted in 79−93% boron removal even in the presence of competing metal ions (Na+ and Cr3+). Experiments were performed in a column system, and breakthrough time was observed to increase with bed depths and decreased with flow rates. The batch experiments revealed that 60 min was enough to achieve equilibrium, and the level of boron sorption was 108.5 mg/g from a synthetic solution. Several adsorption-desorption cycles were performed using a simple acid–water treatment and evaluated using various kinetic models. The spent adsorbents could be separated easily from the mixture by an external magnetic field. The cost-benefit analysis was performed for the treatment of 72 m3/year boron effluent, including five years straight line depreciation charges of equipment. The net profit and standard percentage confirmed that the recovery process is economically feasible. Keywords: Techno-economic analysis; boron-selective adsorbents; hybrid materials; porous magnetic adsorbents; boric acid recovery; fixed-bed studies Acknowledgements: This work was supported by the Scientific and Technical Research Council of Turkey (TUBITAK 1001 Project no: 114Z461).

References 1. C.H. Demey et al., J. Chem. Technol. Biot., 89 (2014) 934-940. 2. R. Zelmanov, R. Semiat, Desalination, 333 (2014) 107-117. 3. A.A. Oladipo, M. Gazi, Environ. Chem. Lett., (2016) doi: 10.1007/s10311-016-0554-6.

82

REMOVAL OF NICKEL(II) IONS FROM AQUEOUS SOLUTION BY MAGNETIC BIOCHAR PALM SEEDS

Mustafa Gazi, Kola A. Azalok, Akeem A. Oladipo

Department of Chemistry, Eastern Mediterranean University, Gazimagusa, TRNC via Mersin 10, Turkey.

e-mail: mustafa.gazi@emu.edu.tr

The contamination of heavy metals has received considerable attention in the worldwide, this can be attributed to their difficult degradation, toxicity, and aggregation in the living organisms (1). Among these metals, nickel is one of the most used in the manufacturing process of batteries, coins, super alloys, stainless steel, etc (2). Hence, the removal of heavy metal from aqueous medium is an extremely important issue. Several efforts and methods have been attempted for nickel ion removal from aqueous solutions. Adsorption process is the most famous method for the uptake heavy metals from wastewater. Due to its inexpensive cost, easy operation and availability, biodegradability, simplicity of design and a high removal efficiencies (3). In this research, the magnetic biochar (MBC) was examined for the treatment of wastewater from Ni2+ ions, three types of MBC were prepared from agricultural waste, especially from palm seeds by reacting with Fe3O4 in three various ratios by weight for removal Ni2+ ions. Furthermore, chemical characterization of the resultant magnetic biochar was examined by using UV spectroscopy analysis, and point of zero charge. The influence of pH, initial concentration, contact time, interferes ions, adsorbent dosage, temperature, and the effect of salinity on the removal efficiency of MBC were investigated. The optimum conditions for highest uptake efficiency included adjusting the pH of nickel solution to 3 and shaking for 4 hours. The adsorption capacity of nickel ions on the adsorbent MBC was 5.134 mg/g at pH 3.2, 0.5g of adsorbent, 0.025L and 100mg/L of volume and initial concentration of nickel solution, respectively. Based on the kinetic studies and adsorption isotherm, nickel adsorption followed of the second order. All experimental results indicated that magnetic biochar can be used as potential low cost, efficient adsorbent for removal of Ni2+ ion from wastewater. Keywords: MBC; Biochar, removal; nickel(II) ions, adsorption References 1. B. Qin et al., Bioresour. Technol., 121 (2012) 458-461. 2. R.M. Shrestha et al., Journal of the Institute of Engineering (India), 9 (2014) 166-174. 3. M. El-Sadaawy, O. Abdelwahab, Alexandria Engineering Journal, 53 (2014) 399-408.

83

PARAMETERS OPTIMIZATION FOR ADSORPTION OF HEAVY METAL IONS AND DYES FROM WASTEWATERS

Paulina Gęca, Agata Góźdź, Marzena Gęca,

Dorota Kołodyńska, Zbigniew Hubicki

Department of Inorganic Chemistry, Faculty of Chemistry, Maria Curie Skłodowska University, Maria Curie Skłodowska Sq. 2, 20-031 Lublin, Poland

e-mail: paulina.geca@poczta.umcs.lublin.pl Advanced wastewater treatment requires highly efficient sorbents able to remove all impurities according to the requirements. Dyes are widely used in such industries as textiles, pulp mills, leather, dye synthesis, printing, food, and plastics. In different wastewaters they are accompanied with heavy metals such as Cu(II), Cd(II) and Cr(III). For their removal activated carbons, plant or lignocellulosic wastes, clays, fly ashes, zeolites and biopolymers are commonly used (1-3). The paper presents the results obtained in the simultaneous removal of heavy metals and dyes using a composite powder of fly ash and chitosan as well as synthetic zeolites obtained by the hydrothermal method (4). Chitosan is known as an ideal natural support for enzyme immobilization because of its special characteristics such as hydrophilicity, biocompatibility, biodegradability, non-toxicity, adsorption properties. Chitosan can be used as an adsorbent to remove heavy metals and dyes due to the presence of amino and hydroxyl groups, which can serve as the active sites (5,6). Amino groups of chitosan can be protonated, after which they adsorb anionic dyes strongly by electrostatic attractions in the acidic media. The effects of various experimental parameters, such as contact time, initial methylene blue and Cu(II), Cd(II) and Cr(III) concentrations as well as temperature and pH on the adsorption capacity were investigated. The results showed that the adsorption behaviour of the sorbents was greatly affected by pH and temperature. The results show that modification of fly ash is highly effective in removing copper, cadmium and chromium from wastewaters. Analogous results were made for the one-component as well as for multi-ion and dye solutions. Acknowledgments: We acknowledge the financial support from NCBiR within the Project GEKON 2/O2/266818/1/2015. References 1. Ch. Li et al., J. Ind. Eng. Chem., 23 (2015) 344-352. 2. W.S. Wan Ngaha et al., Carbohydr. Polym., 83 (2011) 1446-1456. 3. M.N.V.R. Kumar., React. Funct. Polym., 46 (2000) 1-27. 4. Ch. Li et al., J. Ind. Eng. Chem., 23 (2015) 344-352. 5. K.C. Gupta et al., Carbohydr. Polym., 66 (2006) 43-54. 6. P.O. Boamah et al., Ecotoxicol. Environ. Safety, 116 (2015) 113-120.

84

REMOVAL OF HEAVY METAL IONS AND PHENOL FROM AQUEOUS SOLUTIONS

Paulina Gęca, Agata Góźdź, Marzena Gęca,

Dorota Kołodyńska, Zbigniew Hubicki

Department of Inorganic Chemistry, Faculty of Chemistry, Maria Curie Skłodowska University, Maria Curie Skłodowska Sq. 2, 20-031 Lublin, Poland

e-mail: paulina.geca@poczta.umcs.lublin.pl

Removal of heavy metal ions and organic compounds present in wastewaters is very important due to their toxic effects. Phenol and substituted phenols are considered as main pollutants among various contaminants generally present in wastewaters. The discharge of effluents containing phenolic compounds is an ongoing and serious threat to human health and water quality. Various methods are known for removal of phenols from wastewaters, including adsorption–flocculation, degradation, solvent extraction, liquid membrane and adsorption (1-3). Adsorption in particular is an effective separation process for a wide variety of applications. Adsorption of phenol was studied using different materials such as activated carbon, organoclays and zeolites. In most cases phenol sorption behaviour using surfactant-modified natural zeolites depends on the type of surfactants which were used to modify the zeolite surface, source of the zeolite material, pH of phenol solutions as well as concentration of phenol (4,5). In this study fly ash and modified zeolites were selected and used as simple and renewable adsorbents for water purification from heavy metal ions and phenol. As a modifier of zeolites chitosan possessing such functional groups as −NH2, −OH was proposed. The Langmuir, Freundlich, Redlich-Peterson, Dubinin-Radushkevich isotherm models were used to explain the adsorption processes. The adsorption of phenol and heavy metal ions on zeolite based on fly ash depends on the initial pH of solutions. The experimental data were best fitted to the Langmuir isotherm. The adsorbents can be regenerated at acidic pH and reused in a few cycles. The obtained composites were characterized using spectroscopic and electron microscopic techniques. Acknowledgments: We acknowledge the financial support from NCBiR within the Project GEKON 2/O2/266818/1/2015. References 1. K. Kuśmierek et al., Przem. Chem., 92 (2013) 1257-1260. 2. A.W. Trochimczuk et al., Eur. Polym. J., 38 (2002) 1175-1181. 3. J. Pan et al., J. Hazard. Mater., 190 (2011) 276-284. 4. B.H. Hameed, Colloids Surf. A., 307 (2007) 45-52. 5. S.H. Lin et al., Waste Manage., 22 (2002) 595-603.

85

INVERSE SUSPENSION POLYMERIZATION AS A NEW TOOL FOR OBTAINING OF MOLECULARLY IMPRINTED POLYMERS

FOR BIOLOGICALLY ACTIVE COMPOUNDS UPTAKE

Anna Jakubiak-Marcinkowska, Agnieszka Głowińska

Faculty of Chemistry, Wrocław University of Science and Technology, Wybrzeże Wyspiańskiego 27, 50-370 Wrocław, Poland

e-mail: anna.jakubiak@pwr.edu.pl Molecularly imprinted polymers (MIPs) are artificially synthesized materials with specific cavities in the polymer matrix, complementary in size, shape and functionality to the template molecule. These polymers possess molecular recognition ability and selectivity towards the target compounds, which makes them useful in separation techniques as extraction, chromatography, sorption

and membrane processes, but also sensors and drug carriers (1,2). For most of applications, spherical beads with regular shape and size attainable by suspension polymerization are preferred (3). Inverse suspension polymerization is a promising method for synthesis of carriers of water-soluble biologically active compounds. As it was described previously, in order to

achieve optimum rebinding properties, the same or very similar solvent is required during polymerization and sorption processes (4). The aim of the investigations was to obtain MIPs acting as carriers of chosen compound – ibuprofen by inverse suspension polymerization of methacrylic acid (MAA) and N,N’-methylenebisacrylamide (MBA) (Fig. 1). Polar groups in polymer matrix increase hydrophilicity of its surface, which is crucial in polymer-template interactions. Two types of organic phase were tested: silicone oil and paraffin oil. The best synthesis conditions (initial temperature, amount of surfactant, stirring speed etc.) were determined experimentally. The properties of obtained materials, such as rebinding capacity, selectivity and beads morphology (Fig. 2), were found to be related to the type of continuous phase.

References 1. J. Haginaka, J. Chrom. B, 866 (1,2) (2008) 3-13. 2. J. Czulak, A. Trochimczuk, A. Jakubiak-Marcinkowska, Wiadomości Chemiczne, 68 (2014) 783-809. 3. W. Meouche et al., Macromol. Rapid Commun., 33 (2012) 928-932. 4. G. Vasapollo et al., Int. J. Mol. Sci., 12 (2011) 5908-5945.

Fig. 2. SEM image of MIPs synthesized with a) paraffin oil,

b) silicone oil

Fig. 1. Schematic representation of MIP-MAA/MBA

a

b

86

APPLICATION OF HYBRID CHITOSAN MEMBRANES

CONTAINING METAL OXIDES IN PERVAPORATIVE

DEHYDRATION OF ETHANOL/WATER MIXTURE

Małgorzata Gnus1, Gabriela Dudek1, Roman Turczyn1, Krystyna Konieczny2

1Silesian University of Technology, Faculty of Chemistry, Dapartment of

Physical Chemistry and Technology of Polymers, Strzody 9, 44-100 Gliwice, Poland

2 Silesian University of Technology, Faculty of Energy and Environmental Engineering, Institute of Water and Wastewater Engineering, Konarskiego 18,

44-100 Gliwice, Poland e-mail: malgorzata.gnus@polsl.pl

Mixed-matrix membranes are a well-known route to enhance the properties of polymeric membranes. Their microstructure consists of an inorganic material in the form of micro- or nanoparticles incorporated into a polymeric matrix. The use of two materials with different flux and selectivity provides the possibility to better design a membrane, allowing the synergistic combination of polymers’ easy processability and the superior pervaporation separation performance of inorganic materials. In principle, the incorporation of the inorganic component can be seen as a relatively easy modification of existing methods for fabricating large-surface area polymeric membranes. Therefore, mixed-matrix membranes possess an economic advantage over inorganic membranes. In addition, they may offer enhanced physical, thermal and mechanical properties for aggressive environments and could be a way to stabilize the polymer membrane against change in permselectivity with temperature.

The aim of this work was the comparison of separation properties of composed chitosan membranes filled with different metal oxides in the pervaporative dehydration of ethanol. For this purpose, series of membranes with different amount of inorganic filler such as Fe3O4, Cr2O3, TiO2 and crosslinked in the same manner were prepared. Pervaporation experiments were caried out at room temperature and as feed mixture was used 96% ethanol solution. Then based on the determined total flux and GC estimated concentration the transport characteristic of investigated membranes was evaluated. The influence of kind of inorganic filler and their amount on the separation properties, physicochemical properties and dehydration process efficiency was discussed. Comparing permeation coefficients of discussed membranes the better separation properties for the iron oxide hybrid membranes were observed. The best ideal selectivity was received for membranes with iron oxide content of 10 w/w %.

Acknowledgements: The autors would like to thank the Silesia University of Technology for providing financial support under the project BKM-526/RCH4/2016. References 1. G. Dudek et al., Sep. Purif. Technol., 133 (2014) 8-15. 2. G. Dudek et al., Sep. Purif. Technol., 109 (2013) 55-63. 3. G. Dudek et al., Sep. Purif. Technol., 47 (2012) 1390-1394.

87

REMOVAL OF BORON FROM AQUEOUS SOLUTION BY

COMPOSITE CHITOSAN BEADS

Joanna Kluczka, Małgorzata Gnus, Gabriela Dudek, Roman Turczyn

Silesian University of Technology, Faculty of Chemistry, Ks. M. Strzody 9, 44-100 Gliwice, Poland

e-mail: malgorzata.gnus@polsl.pl Boron dissolved in surface and ground waters is present at concentration levels of 0.3–100 mg/L and higher, anthropogenic and geothermal activity dependent (1). Boron is a significant micronutrient for plants, however, it is need only in small amounts. Its high levels are injurious and even lethal to plants. In humans, an excess of boron may lead to damage of the nervous system (2). The recommended level of boron in drinking and irrigating water and wastewaters discarded to the environment is 1.0 mg/L in Poland and EU. The adsorption process is the most studied and applied method for removing boron from aqueous solution. Chitosan, being cheap, environment-friendly and possessing good ability to adsorb pollutants, has attracted great interests in water and wastewater treatment. However, adsorption of boron species onto the chitosan beads occurred with physical forces and characterised with not high enough capacity (3). An Al, Fe, Ce and Zr oxide/hydroxide adsorbent demonstrates high efficiency for boron removal (4-6). However, post-treatment requires the elimination of particles as colloidal precipitates using additional processes such as coagulation, sedimentation and filtration. In order to avoid this step, metal-oxide nanoparticles may be immobilized on inert surfaces, such as activated carbon, foams or nanofibers. The objective of this research was to investigate boron sorption properties of various metal-oxide/hydroxide nanoparticles (titanium dioxide, chromium oxide, iron oxide and iron hydroxide) doped chitosan gel and to determine the optimal conditions of boron removal from aqueous solutions. The effects of temperature, pH, time, and composite chitosan beads dosage on boron removal were examined in the batch system. The experimental data were evaluated by the equilibrium isotherm and kinetic models. By combining the advantageous properties of chitosan and metal nanooxides, an effective adsorbents for boron were developed.

Acknowledgements: The autors would like to thank the Silesia University of Technology for providing financial support under the project BKM-526/RCH4/2016.

References 1. N. Hilal et al., Desalination, 273 (2011) 23-35. 2. E. Bobrowska-Grzesik et al., Chemical elements. Compendium, Cesky Tesin, 2 Theta, 2013. 3. E.A. Bursali et al., J. Appl. Polym. Sci., 122 (2011) 657-665. 4. A. Demetriou, J. Pashalidis, Desal. Wat. Treat., 37 (2012) 315-320. 5. N. Öztürk, D. Kavak, Desalination, 223 (2008) 106-112. 6. J. Kluczka, Int. J. Environ. Res., 9 (2015) 711-720.

88

SURFACE ACTIVATED HYDROTHERMAL FLY ASH AND ITS COMPOSITES FOR SIMULATANEOUS HEAVY METALS AND

DYE REMOVAL

Agata Góźdź, Paulina Gęca, Marzena Gęca, Dorota Kołodyńska, Zbigniew Hubicki

Department of Inorganic Chemistry, Faculty of Chemistry, Maria Curie Skłodowska University, Maria Curie Skłodowska Sq. 2, 20-031 Lublin, Poland

e-mail: agata.gozdz@poczta.umcs.lublin.pl

Biopolymers such as chitosan can be used for removing of low-concentration heavy metal ions and dyes from wastewaters and aqueous solutions. Toxic and allergic metals including cadmium, copper, nickel, zinc and organic compounds like formaldehyde, pentachlorophenol and chlorinated hydrocarbons can exist in natural structures of textiles or are introduced in their production, dying process or storage. On the other hand zeolites are porous crystalline aluminosilicates which in their structure have plurality of channels and pores. Crystalline zeolites skeleton is made up of tetrahedra SiO4 and AlO4. Because conventional adsorbents based on zeolites are characterized by low adsorption capacities toward dyes their modification is needed. A well-known example of a polymer which improves their capacities is chitosan (CS), the deacetylated product of chitin, which exhibits a high adsorption capacity toward many classes of dyes due to its multiple functional groups. It is also an excellent adsorbent for heavy metal ions (1-4). In the paper the obtained zeolite from fly ash by the hydrothermal method was used for simultaneous removal of heavy metal ions Cu(II), Cd(II) and Pb(II) and Acid Red 18 (also known as New Coccine). The investigations were conducted for individual metal ion adsorption along with co-adsorption of both metal ion and dye. It was found that, for single component system, zeolite can achieve adsorption of metal ion depending on the various parameters such as initial concentration, phase contact time, pH and temperature. For co-adsorption, complexation of heavy metals and dye can plays an important role. Zeolite NaP1 modified by chitosan was characterized by the FT-IR, XRD, AFM and SEM methods. The obtained results suggest that the prepared sorbents are suitable for heavy metal ions and Acid Red 18 removal at different pH values and can have great potential applications in the environmental protection. Acknowledgments: We acknowledge the financial support from NCBiR within the Project GEKON 2/O2/266818/1/2015.

References 1. R.S. Blissett et al., Fuel, 97 (2012) 1-23. 2. W.S. Wan Ngah et al., Bioresource Technol., 96 (2005) 443-450. 3. J.Y. Je et al., Bioorg. Med. Chem. Lett., 16 (2006) 2122-2126. 4. G.Z. Kyzas et al., J. Colloid Interface Sci., 331 (2009) 32-39.

89

CHITOSAN-ZEOLITES COMPOSITES FOR MICROELEMENTS ADSORPTION

Agata Góźdź, Paulina Gęca, Marzena Gęca,

Dorota Kołodyńska, Zbigniew Hubicki

Department of Inorganic Chemistry, Faculty of Chemistry, Maria Curie Skłodowska University, Maria Curie Skłodowska Sq. 2, 20-031 Lublin, Poland

e-mail: agata.gozdz@poczta.umcs.lublin.pl

Chitosan, a cationic polysaccharide obtained by alkaline N-deacetylation of chitin, is one of the most widely employed biopolymer composed of N-acetyl-d-glucosamine and D-glucosamine. The D-glucosamine content is dependent on the degree of deacetylation (DDA). However, contrary to chitin, the presence of a large number of amine groups on the chitosan chain increases the adsorption capacity of chitosan (1).

Several unique properties such as nontoxicity, biocompatibility, and biodegradability offer chitosan good potentials for different branches of industry (2). In order to enhance the sorption capacity of chitosan for metal ions chemical modifications are often made and used for obtaining novel zeolite based fertilizers. One of the main advantages of using zeolites as a base or additive to fertilizers is their beneficial effect of retention of nutrients in the soil gradually released (3,4). Therefore the influence of experimental conditions such as pH, phase contact time, shaking speed and concentration of Fe(III), Mn(II), Zn(II) and Cu(II) ions on effectiveness of sorption on chitosan modified zeolite was studied. For metal complexation biodegradable complexing agents were used. The Langmuir and Freundlich equations were used to fit the equilibrium isotherm. The adsorption rates were determined quantitatively and compared by the pseudo first-order, pseudo-second-order and the intraparticle diffusion models. The information is useful for further applications of the system to design slow release fertilizers. Acknowledgments: We acknowledge the financial support from NCBiR within the Project GEKON 2/O2/266818/1/2015. References 1. E. Guibal et al., Ind. Eng. Chem. Res., 37 (1998) 1454-1463. 2. R.S. Blissett et al., Fuel, 97 (2012) 1-23. 3. E. Polat et al., Plant Res., 12 (2004) 183-189. 4. K. Ramesh et al., Adv. Agronomy, 113 (2011) 215-230.

90

SORPTION OF SELECTED PESTICIDES ON POLY(MAA-CO-EGDMA) POLYMERIC SORBENT

Marta Grochowicz, Łukasz Szajnecki

Department of Polymer Chemistry, Faculty of Chemistry, Maria Curie-

Skłodowska University, Pl. M. Curie-Skłodowskiej 5, 20-031 Lublin, Poland e-mail: mgrochowicz@umcs.pl

Sorption of selected pesticides on porous copolymers of methacrylic acid (MAA) and ethylene glycol dimethacrylate (EGDMA) was studied. Poly(MAA-co-EGDMA) matrices are widely used in molecular imprinting technology based on highly selective polymeric sorbents called molecularly imprinted polymers (MIPs). During MIPs synthesis diazinon (popular insecticide) was used. Several MAA-EGDMA copolymeric systems (imprinted and non-imprinted) were obtained in bulk polymerization in the presence of selected porogenic solvent. Product of each copolymerization was crushed, grounded and used as the sorbent. The influence of imprinting process on selectivity of the sorbent was investigated. Elution profiles of diazinon (DIA) and o,p'-DDT (DDT) were determinated. An empty glass SPE column was filled with suitable amount of imprinted sorbent. After conditioning and equilibrating the polymeric bed, standard solution (mixture of DIA and DDT in isooctane) was introduced into the column. Eluate was collected into the glass vials (1 ml to each vial) with the flow of 1 ml/min. Concentration of DIA and DDT in each vial was determined (GC). In a similar way breakthrough volumes of DIA and DDT were studied for non-imprinted sorbent.

Eluate volume [ml]

0 5 10 15 20

Pe

stic

ide

con

ce

ntr

atio

n in

elu

ate

[ µg

/ml]

0

20

40

60

80

100

120

140

160DIA on NIPDIA on MIP

DDT on MIPDDT on NIP

The higher breakthrough volume of DIA on MIPs was noticed – such effect wasn’t observed in the case of DDT. The obtained results indicate an increase in the selectivity of the imprinted sorbent only to the DIA which was used as a template to produce molecular imprints on the surface of the imprinted sorbent.

91

REMOVAL OF PPCPS BY MOLECULAR STACKING

Yusuke Imamura1, Tadashi Okobira2

1Advanced Chemical Science and Engineering Course, National Institute of Technology, Ariake College,

150 Higashihagino-Machi, Omuta, Fukuoka 836-8585, Japan 2Department of Creative Engineering,

National Institute of Technology, Ariake College, 150 Higashihagino-Machi, Omuta, Fukuoka 836-8585, Japan

e-mail: c48404@ga.ariake-nct.ac.jp

Recently, the residues of Pharmaceuticals and Personal Care Products (PPCPs) are increasing in rivers and seas all over the world. There is a wide variety of PPCPs such as antimicrobial agents, antibiotics and nervous system agents. They are discharged from home or hospital into natural world, although some are subjected to the action of decomposition at the sewage treatment plant. PPCPs are originally designed to be physiologically active in human. Therefore, they might have harmful effects even at low concentrations. There are growing concerns about biological effects on aquatic organisms and human beings via tap water. Today, it is very common to purchase medicines and drugs at pharmacy and convenience stores. It means that the dose of them might increase and lead to increase in environment day by day. Moreover, they are persistent due to aromatic rings in their structure and have long life span. Thus, more knowledge about PPCPs like actual situation and development of removal technology are needed urgently. As a method for removing PPCPs at the moment, removal by ultraviolet light and/or ozone are established. However, the energy of their processes for decomposition is considered high. The efficient solutions should be found before PPCPs cause some damage for human. In this study, we suggested to use porous hollow fiber membrane chemically-modified by electron beam induced graft polymerization to achieve efficient removal of PPCPs and focused on the structure of PPCPs. They have some aromatic rings which can form structure like stacking of coins called π-stacking. We adopt 2-phenylphenol as model of PPCPs and flow it through membranes which have functional group assumed to be able to remove PPCPs such as Aniline (Ani), 1-amino-4-methylbenzene (AMB), 3,4-dimethylaniline (DMA), benzyl amine (BA), 4-isopropylaniline (IPA), stearylamine (SA). As a result of adsorption experiment, trend of adsorption capacities in consideration of molar conversion of functional groups were IPA > BA> DMA > others.

Fig. 1. Adsorbed amount of 2-phenylphenol solution through grafted membranes

92

RECOVERY OF PRECIOUS METALS FROM ELECTRONIC WASTE

Mateusz Sambor, Krzysztof Mitko, Agata Jakóbik-Kolon

Silesian University of Technology, Faculty of Chemistry, ul. B. Krzywoustego 6, 44-100 Gliwice, Poland

e-mail: agata.jakobik-kolon@polsl.pl

Over the last years, the sales of the consumer electronics have grown significantly; on the other hand, the lifespan of the product has decreased. This generated a serious environmental issue: the utilization of so-called „electronic waste”. Components of electronic products contain toxic substances, which can generate a threat to the environment, as well as to human health. On the other hand, consumer electronics contain highly priced metals, such as silver, gold, and palladium. The precious metal can be recovered by pyro-, hydro-, and biometallurgical processes. In this work, we examine the possibility of precious metal recovery from a leachate generated by hydrometallurgical treatment of waste consumer electronics. Wastewater was obtained by leaching the old CPUs and cell phone motherboards with potassium cyanide and hydrogen peroxide solution. Next, a liquid-liquid extraction using solutions of three different carriers (18-crown-6 ether, dibenzo-18-crown-6 ether, dicylohexyl-18-crown-6, concentration range 0.04 – 0.2 g/cm3) in chloroform was performed. Based on the results of the extraction experiments – see Fig. 1 – we can conclude that silver and gold can be selectively recovered from the consumer electronics leachate.

Fig. 1. An example of the carrier influence on partition coefficient, K, during

conventional extraction of metals from dissolved electronic waste (receiving phase: 0.1, 0.1, 0.05 g/cm3 of 18-crown-6, dicyclohexyl-18-crown-6, dibenzo-18-crown-6 ether,

respectively, in chloroform, feed phase: 84 ppm of Ag, 57 ppm of Au, 1032 ppm of Cu in KCN aqueous solution)

93

KINETICS OF ZINC IONS REMOVAL ON HYDROLYSED PMMA SORBENTS

Agata Jakóbik-Kolon, Dominik Zdybał, Andrzej K. Milewski, Krzysztof

Mitko, Ewa Laskowska, Joanna Bok-Badura

Silesian University of Technology, Faculty of Chemistry, M. Strzody 9, 44 – 100 Gliwice, Poland,

e-mail: agata.jakobik@polsl.pl

Heavy metals, present in waste waters from various branches of industry and agriculture, are a serious environmental hazard. Zinc, in small amounts, is an essential element, but its excess may be dangerous for the environment. According to the regulations by Polish Ministry of Environment (1), the zinc content in the wastes discharged to groundwater and soil must not be higher than 2 mg/dm3. In this work, kinetics of zinc ions removal on hydrolysed PMMA (Poly(methyl methacrylate)) sorbents has been studied. The application of PMMA for zinc removal will be beneficial from the ecological point of view, because the use of waste PMMA – Plexiglas is present in abundance and widely applied throughout all industries. Our sorbents were obtained by hydrolysis of commercially available (Sigma Aldrich, MW 996 000 Da (A) and MW 350 000 Da (B)) as well as waste (MW 117 000 Da (C)) PMMA. The “one pot” synthesis was used (2,3). The materials were then ionic cross-linked by magnesium and calcium ions. The kinetics studies (Fig. 1) show that sorption in investigated system is fast - equilibrium capacity was achieved after ca. 1 hour. Starting materials (original (A, B) or waste (C) PMMA) as well as kind of ion (Mg, Ca) used for cross-linking did not influence significantly on sorption kinetics of zinc ions on prepared ion-exchangers.

Fig. 1. Comparison of zinc ions sorption kinetics on hydrolysed PMMA prepared from

original (A ,B) and waste (C) materials (CZn = 30 mg/l, pH=6, T=22°C) Acknowledgements: This work was financed by the National Centre for Research and Development (NCBiR) under Grant No. LIDER/032/651/L-5/13/NCBR/2014.

References 1. Dz. U. [Journal of Laws] No 137 item 984 of 31 July 2006. 2. D. Zdybał et al., patent application P.412896 (2015). 3. D. Zdybał et al., patent application P.415344 (2015).

94

UPTAKE OF METAL IONS IN THE PRESENCE OF BIODEGRADABLE EDDS ON SUPERABSORBENTS

Dorota Kołodyńska1, Alicja Skiba2, Bożena Górecka2, Zbigniew Hubicki1

1Department of Inorganic Chemistry, Faculty of Chemistry, Maria Curie

Skłodowska University, Maria Curie Skłodowska Sq. 2, 20-031 Lublin, Poland 2New Chemical Synthesis Institute, Al. Tysiąclecia Państwa Polskiego 13a, 24-

110 Puławy, Poland e-mail: d.kolodynska@poczta.umcs.lublin.pl

Polymer superabsorbents commonly known as hydrogels are cross-linked highly molecular compounds able to absorb water from physicochemical fluids in the amounts from tenfold to one hundredfold larger than their dry mass. Numerous investigations have shown that they can help reduce irrigation water consumption, lower the death rate of plants, improve fertilizer retention in soil and increase plant growth rate. Besides water absorption and retention, the superabsorbent polymers have many advantages over conventional ones, such as a sustained supply of nutrition to plants for a longer time, thus increasing the phosphate fertilizer use efficiency and decreasing application frequency (1-6). The aim of this study was to investigate the influence of chemical conditions on hydrogels, kinetic and adsorption behaviour towards metal ions in the presence of the chelating agent of a new generation such as ethylenediaminedisuccinic acid EDDS. The complexes with the structure presented below are formed:

Kinetic and adsorption parameters of the sorption process at different doses of TerraHydrogel®Aqua, THA (Terra, Poland), Agro® hydrogel, AH (EverChem, Poland) and Zeba® hydrogel, ZH (Agrecol, Poland) were investigated. Moreover changing pH, initial concentration of metal complexes Cu(II), Zn(II), Mn(II) and Fe(III) with EDDS as well as phase contact time were also studied by the static method.

References 1. S.M. Ahmed, J. Adv. Res., 6 (2015) 105-121. 2. J.R. Witono et al., Carbohydr. Polym., 103 (2014) 325-332. 3. Y. Samchenko et al., Adv. Coll. Interf. Sci., 168 (2011) 247-262. 4. D. Buenger et al. J. Groll, Prog. Polym. Sci., 37 (2012) 1678-1719. 5. R. Liang et al. React. Funct. Polym., 67 (2007) 769-779. 6. W.E. Rudzinski et al., J. App. Polym. Sci., 87 (2003) 394-403.

95

CHARACTERISTICS OF SYNTHETIC ZEOLITE FOR REMOVAL OF Cr(VI) IONS

Dorota Kołodyńska, Agata Góźdź, Paulina Gęca,

Marzena Gęca, Zbigniew Hubicki

Department of Inorganic Chemistry, Faculty of Chemistry, Maria Curie Skłodowska University, Maria Curie Skłodowska Sq. 2, 20-031 Lublin, Poland

e-mail: d.kolodynska@poczta.umcs.lublin.pl

Chromium is one of the most important agents polluting surface and ground waters. In the environment chromium occurs in its trivalent and hexavalent forms. Cr(VI) is highly toxic and carcinogenic while Cr(III) presents less toxicity and can be considered an essential micronutrient. However, in significant concentrations, Cr(III) can cause further adverse effects because of its increased ability to coordinate various organic compounds (1-3). The aim of this research is to investigate sorption characteristic of fly ash, fly ash modified by chitosan, zeolite as well as zeolite modified by chitosan for the removal of Cr(VI) ions from aqueous solutions. The sorption of Cr(VI) ions was carried out by the batch method. Optimal conditions of sorption were determined. The sorbent was characterized by the XRD, SEM and BET surface area methods.

The BET surface areas of the obtained sorbents were several times as large as those of the original fly ash. Furthermore, its mean particle size increased compared to the raw fly ash. The Langmuir and Freundlich models were used to estimate sorption capacities. Concentrations of chromium in solution were determined by the flame atomic absorption spectrometry and colorimetric method with diphenylcarbazide. The optimal pH of adsorption was 4.0 while that of chromium(VI) partially reduced in the range pH ≤ 3.0. It was found that the developed sorbent is effective for hexavalent chromium wastewater treatment. Acknowledgments: We acknowledge the financial support from NCBiR within the Project GEKON 2/O2/266818/1/2015. References 1. K.D. Trimukhe et al., Carbohydr. Polym., 71 (2008) 66-73. 2. G. Rojas, et al., Sep. Purif. Technol., 44 (2005) 31-36. 3. W.S. Wan Ngah, et al., Adsorption, 12 (2006) 294-257.

96

FACILE DETERMINATION OF FROTHER FOAMABILITY INDEX

Przemyslaw B. Kowalczuk

Wroclaw University of Science and Technology, Faculty of Geoengineering, Mining and Geology, Wybrzeże Wyspiańskiego 27, 50-370 Wrocław, Poland

e-mail: przemyslaw.kowalczuk@pwr.edu.pl

Separation by flotation of particulate matters is a process of interdisciplinary significance and importance in many areas of research and technology. Flotation efficiency depends on many parameters. Parameters of special importance in flotation are frother type and dose. The role of frother is to prevent bubble coalescence, stabilize froth and shorten the time of three-phase contact formation. The foaming properties of frothers can be characterized by different parameters including dynamic foamability index (DFI) and critical coalescence concentration (CCC). The relationship between those parameters allows to classify frothers into selective and powerful. Determination of DFI and CCC requires advanced techniques and methods. Therefore, in this work a versatile method for characterizing foamability of selected polyglycols frothers is reported. The method is based on measuring the foam height in a conventional laboratory flotation machine. Basing on the relationship between the foam height h and frother concentration c (Fig. 1a), the foamability index FIh can be determined by utilizing the empirical equation:

( )( )

⋅−⋅−+=

3minmaxmin/2

1exp

hFIchhhh .

By normalizing the foam height (h-hmin)/(hmax-hmin) and frother concentration in relation to the FIh values for investigated frothers it can be seen that all the experimental data points converge to a single universal curve (Fig. 1b). It indicates that all the frothers used act similarly but at different concentrations expressed as FIh. It also proves that the foamability index FIh can be a useful parameter for characterizing flotation frothers.

0

2

4

6

8

10

12

14

0.0 0.2 0.4 0.6 0.8

foam

he

igh

t, m

m

concentration, mmol/dm3

C4P3C3P3C1P3C4P1C2.1P2C4E2C6E2C4E3

(a)

0.0

0.2

0.4

0.6

0.8

1.0

0 2 4 6 8 10

no

rmal

ized

fo

am h

eig

ht

c/FIh

C4P3

C3P3

C1P3

C4P1

C2.1P2

C4E2

C6E2

C4E3

(b) Fig. 1. Influence of (a) frother concentration and (b) normalized frother concentration

(c/FIh) on foam height Acknowledgements: This work was financed by the National Science Centre Research Grant 2012/07/D/ST8/0262.2.

97

HIGHLY SELECTIVE AND EFFICIENT TRANSPORT OF Au(III), Pt(IV), Pd(II) FROM HYDROCHLORIC ACID ACROSS POLYMER INCLUSION MEMBRANES CONTAINING IONIC LIQUID AS ION

CARRIER

Marta Kołodziejska2, Jolanta Kozłowska1, Iwona Zawierucha1, Cezary Kozłowski1

1Institute of Chemistry, Environmental Protection and Biotechnology,

2Department of Metal Extraction and Recirculation, Częstochowa University of Technology, 42-200, Częstochowa, Armii Krajowej 19, Poland

e-mail: c.kozlowski@ajd.czest The solvent extraction and membrane methods are applied for separation of gold(III) from spent liquors. The removal of gold(III) from aqueous chloride media is often conducted by using high molecular weight amines or tertiary amines diluted in nonpolar organic solvents, where gold(III) is extracted in the form of anionic tetrachloroaurate with protonated amines. Recently, several researchers have studied the extraction of gold(III) by ionic liquids (1-3). This work presents the selective transport of Au(III), Pt(IV), Pd(II) using ionic liquid, i.e. N-Methyl-N’-1-(4-t-butylphenylphosphinyl)butylimidazolium bis(trifluoromethylsulphonyl)imide as ion carrier in membrane system. This ionic liquid patented by Professor Drabowicz team (patent pending P-411260) is a tertiary phosphine oxide with the terminal N-methylated imidazole ring.

N+

N

P

O

N+

N

P

O

Cl

F3CS

NS

CF3

O

O

O

OLi

+F3C

S

N S

CF3

O

O

O

O

The transport of some precious metals: Au(III), Pd(II), Pt(IV) from HCl solutions was carried out using polymer inclusion membrane (PIM) containing cellulose triacetate as support and ionic liquid as ion carrier. A good selectivity for Au(III) with 20% ion carrier in membrane was obtained at lower HCl concentration of 0.01 M. The extractability of Au(III) across PIM was greater than other metal ions; the selectivity of metal ions transported was found to be: Au(III) >> Pt(IV), Pd(II). The maximal values of the recovery factors for gold, platinum, and palladium ions after 4 hours of transport were 98%, 3% and 1%, respectively. The Au(III) was more effectively extracted from the membrane phase by using 0.01M KJ + 0.01M HCl solution than by KJ solution. The long term integrity of transport across PIM with this ionic liquid was also studied. Acknowledgments: The authors acknowledge the National Science Centre for financial support of this projects: Grants no. UMO-2011/01/D/ST5/05781 and no. UMO-2011/01/B/ST5/06304. References 1. J. Yang et al., Solvent Extr. Res. Dev., Jpn., 21 (2014), 89-94. 2. S. Boudesocque, A. Mohamadou, L. Dupont, New J. Chem., 38 (2014) 5573-5581. 3. V.T. Nguyen et al., Ind. Eng. Chem. Res., 54 (2015) 1350-1358.

98

APPLICATION OF CALIXPYRROLES FOR Ag(I) AND Cu(II) SEPARATION FROM ELECTRONIC WASTE SOLUTIONS

Anna Nowik-Zając, Cezary Kozłowski

Institute of Chemistry, Environmental Protection and Biotechnology, Jan Dlugosz University of Częstochowa, 42-201 Częstochowa, Armii Krajowej

13/15, Poland e-mail: c.kozlowski@ajd.czest

Calixpyrroles, belonging to the heterocalixarene compounds, were applied in separation of primarily noble metals, but they are beginning to interest researchers for their application as ligands for heavy metal cations (1-4). A hybrid calixpyrroles chelating resin has been used for sorption studies of some noble metals like Au(III), Ag(I), Pt(IV), Pd(II) and other metal cations including Cu(II), Pb(II) and Cd(II) (2). Amiri et al. demonstrated that calix[4]pyrrole immobilized to the SLM-type membrane based on the polypropylene matrix are efficient and selective carriers of Ag(I) ions, but they do not transport Cu(II), Ni(II), Zn(II), Pb(II), Co(II), Cd(II), Cr(III), Fe(II) and Fe(III) (3). The polymer inclusion membranes (PIMs) were prepared by physical immobilization of the ion carriers (calixpyrrole 1 and 2, Fig. 1) into cellulose triacetate containing plasticizer (o-nitrophenyl pentyl ether). Transport experiments were carried out in permeation cell in which the membrane was tightly clamped between two compartments. The aqueous source phase was a printed circuit material; the aqueous receiving phase was a 0.1 mol/dm3 Na2S2O3. The application of PIMs for selective transport of Ag(I) and Cu(II) is increasingly drawing attention especially by use of macrocyclic carriers. The competitive transport of Ag(I) and Cu(II) from aqueous phases across PIM is an effective separation method for silver(I) ions.

R=

1 2

Fig. 1. Structures of calixpyrroles

Acknowledgments: Project financed by National Science Center funds allocated on the basis of the decision number DEC-2013/09/N/ST5/02984.

References 1. K. Vinod et al., Talanta, 79 (2009) 1331-1340. 2. A. Kałędkowski, A.W. Trochimczuk, React. Funct. Polym., 66 (2006) 957-966. 3. A.A. Amiri et al., J. Membr. Sci., 325 (2008) 295-300. 4. A. Nowik-Zając, C. Kozłowski, A. Trochimczuk, Desalination, 294 (2012) 25-29.

99

INVESTIGATIONS OF COPPER(II) AND CADMIUM(II) IONS SORPTION USING MAGNETIC BIOCHAR

Justyna Krukowska, Dorota Kołodyńska

Department of Inorganic Chemistry, Faculty of Chemistry, Maria Curie

Skłodowska University, Maria Curie Skłodowska Sq. 2, 20-031 Lublin, Poland e-mail: justyna.krukowska@poczta.umcs.lublin.pl

Biochar is a carbonaceous material obtained by heating biomass in nitrogen atmosphere. The thermochemical processes of biomass are pyrolysis, carbonization, gasification or torrefaction of sludge, peels, barks, leaves and wood (1). The suitable properties of biochar such as: porous and aromatic structure, large surface area, cation exchange capacity, content of carbon decide about its applications. Recently research on the application of synthetic nano-composites, has been extensively developing. Such materials are very important because they combine the advantages of biochar and nano-materials. Magnetic biochar was obtained using a reducing agent like iron. Such sorbent can be used for removal of heavy metal ions, nitroaromatics, perchlorates from aqueous solutions (2-4). The zero-valent iron magnetic biochar composites were synthesized from biochar, heptahydrate iron sulfate and sodium borohydride. Sodium borohydride was used as an agent to reduce Fe(II) to Fe(0). The investigations of sorption of Cu(II) and Cd(II) were carried out by the static method at various contact times from 1 to 360 minutes and different initial concentrations from 50 to 200 mg/L. It was found that the adsorption process is dependent on the initial concentration of heavy metal ions and the phase contact time. Additionally, the Fourier transform infrared spectroscopy (FT-IR) of magnetic biochar before and after the Cu(II) adsorption was applied. The kinetic data of sorption show better fit of the pseudo second order model. References 1. S.Y. Wang et al., Bioresource Technol., 174 (2014) 67-73. 2. P. Devi, Bioresource Technol., 169 (2014) 525-531. 3. P. Devi et al., Chem. Eng. J., 271 (2015) 195-203. 4. X. Hu et al., Water Res., 68 (2015) 206-216.

100

REMOVAL OF ARSENIC(V) AND CHROMIUM(VI) FROM AQUEOUS SOLUTIONS WITH BIOCHAR APPLICATION

Justyna Krukowska, Dorota Kołodyńska

Department of Inorganic Chemistry, Faculty of Chemistry, Maria Curie

Skłodowska University, Maria Curie Skłodowska Sq. 2, 20-031 Lublin, Poland e-mail: justyna.krukowska@poczta.umcs.lublin.pl

Chromium and arsenic are heavy metals whose presence in the environment is a global problem due to the negative impact on human and animal health and life. Arsenic occurs in the +3 and +5 oxidation states and chromium in the +3 and +6 oxidation ones. These metals are microelements necessary for life, since chromium in the +3 oxidation state reduces blood glucose level and metabolic control. But even small amounts of chromium in the +6 oxidation and arsenic compounds are carcinogenic. Permissible concentration of arsenic in drinking water is 10 µg/L and the concentration of chromium should not exceed 100 µg/L. Arsenic and chromium are widely used in various industries, such as: semiconductor production, industrial leather tanning, electroplating, photography and pigmentation (1-4). The presence of heavy metals in the wastewaters creates the need for their removal and search for new disposal methods. These include a lot of physical and chemical methods such as: chemical precipitation, ion exchange, membrane filtration, coagulation and adsorption (5). Research confirms that biochar is an effective adsorbent for heavy metal ions removal. Due to that biochar is produced mainly as a result of pyrolysis of wooden wastes, agricultural wastes, animal manures and many others, it can provide an alternative to expensive active carbons. Commonly it is used to fertilize soil as a source of nitrogen and phosphorus. It has a highly large specific surface area and developed porous structure (1). Sorption of Cr(VI) and As(V) on biochar was carried out by the static method at different initial concentrations from 50 to 200 mg/L and various contact times from 1 to 360 minutes. In addition, the influence of interfering ions the depends on the phase contact time. It was found that the kinetic parameters of the sorption process were also determined. The pseudo second order model describes Cr(VI) and As(V) sorption on biochar best.

References 1. E. Agrafioti et al., J. Environ. Manage., 133 (2014) 309-314. 2. S. Wang et al., Bioresource Technol., 175 (2015) 391-395. 3. Y.S. Shen et al., Bioresource Technol., 104 (2012) 165-172. 4. S.A. Baig et al., Biomass Bioenergy, 71 (2014) 299-310. 5. D. Mohan et al., Chem. Eng. J., 236 (2014) 513-528.

101

INFLUENCE OF VARIOUS SILICA MODIFICATIONS ON THE SELECTIVITY OF HARD-TEMPLATED MOLECULARLY

IMPRINTED POLYMERIC ADSORBENTS

Małgorzata Kujawska, Andrzej W. Trochimczuk

Wrocław University of Science and Technology, Department of Chemistry Wybrzeże Wyspiańskiego 27, 50-370 Wrocław, Poland

e-mail: malgorzata.kujawska@pwr.edu.pl Selectivity resulting from tailored functionality caused that molecularly imprinted polymers (MIPs) are widely applied in sensors, membranes and as a selective adsorbents in solid-phase extraction (1). MIPs can be synthesized using various techniques, such as bulk, emulsion or multi-step swelling polymerization. Previously, we reported preparation of polymeric adsorbent using novel method combining synthesis of molecularly imprinted polymers and hard template technique with structured functionalized silica (2). Obtained material revealed selectivity towards β-blockers due to the implementation of epoxy ring, subsequently modified with isopropylamine at the surface of silica sacrificial template. Moreover, application of structured silica let to design the porous structure of resulting polymer. To get better insight into the imprinting process using hard template synthesis, further studies were performed. In this work we present the influence of various modifications of silica template on the selectivity of resulting MIPs. First, structured silica was modified with 3-glicydoxypropyltrimetoxysilane. Later, reactions with isopropylamine, ammonia and metoprolol were performed. Prepared materials were characterized for the content of nitrogen, surface area, pore size and volume. Modified silicas were used as a sacrificial templates during bulk polymerization of methacrylic acid and ethylene glycol dimethacrylate. After silica removal polymers were studied for the selective sorption of metoprolol and propranolol in the presence of other commonly used pharmaceuticals, such as: ibuprofen, naproxen and caffeine. Materials were characterized for the content of carboxylic groups and swelling properties. Porous structure of materials was studied using nitrogen adsorption at liquid nitrogen temperature and scanning electron microscopy. Due to the presence of active sides and designed porous structure, polymeric materials prepared using modified silica template, after further studies, could be applied as useful sorbent for selective extraction of pharmaceuticals. Acknowledgements: This work was financially supported by National Science Center, Poland, grant No. 2014/15/N/ST5/02025. References 1. V. Pichon et al., Anal. Chim. Acta, 622 (2008) 48-61. 2. M. Kujawska, A.W. Trochimczuk, Sep. Sci. Tech., DOI: 10.1080/01496395.2016.1200090 (2016).

102

IMPACT OF ORGANIC COMPONENT ON SEPARATION EFFICIENCY OF HYDROPHILIC PERVAPORATION

WITH POLYMERIC MEMBRANES

Wojciech Kujawski1, Andrzej Kraslawski2, Karolina Jarzynka3, Katarzyna Knozowska1, Edyta Rynkowska1, Marek Bryjak4, Jan Kujawski4,

Joanna Kujawa1

1Nicolaus Copernicus University in Toruń, Faculty of Chemistry, 7 Gagarina str., 87-100 Toruń, Poland

2Lappeenranta University of Technology, Lappeenranta, Finland 3Nicolaus Copernicus University in Toruń, 11 Gagarina str., 87-100 Toruń,

Poland 4Wrocław University of Technology, Faculty of Chemistry, Department of

Polymeric and Carbon Materials, Wybrzeże Wyspiańskiego 27, 50-370 Wrocław, Poland

e-mail: kujawski@chem.umk.pl

Hydrophilic pervaporation is a membrane separation operation used for the dehydration of organic liquid mixtures. In this technique the feed is placed in contact with one side of a hydrophilic polymeric membrane, whereas permeate is removed in a vapor state from the opposite side, kept either under the vacuum (vacuum pervaporation) or under a stream of an inert gas (sweeping gas pervaporation). Pervaporation can be operated also at the "thermo" mode (i.e. thermopervaporation), using a difference of temperatures between feed and permeate as the driving force. The aim of this research was to discuss an impact of organic solvents possessing various polarity on the efficiency of pervaporation dehydration. The results of pervaporation dehydration experiments are presented using different binary and multicomponent aqueous-organic mixtures as feed. During experiments various types of hydrophilic polymeric based membranes were used (ion-exchange and PVA based polymeric). The organic solvents (methanol, ethanol, n-propanol, propan-2-ol, n-butanol, methyl acetate, ethyl acetate) were characterized by their polarity/hydrophobicity properties, expressed in terms of dielectric constant (ε), Hansen's solubility parameter (δ) and/or the partition coefficient between octanol and water (Kow). It was found that the efficiency of dehydration by pervaporation depends both on the morphology of the membrane and the physicochemical properties of organic component of the aqueous mixture. The results obtained in vacuum pervaporation mode were compared with the results obtained in the sweeping gas pervaporation experiments. These results will be further used for a case-based reasoning approach allowing to design the best pervaporation separation system for a given mixture.

Acknowledgements; This research was supported by statutory funds of Nicolaus Copernicus University in Toruń, Poland (Faculty of Chemistry NCU, T-109).

103

THE INFLUENCE OF pH ON THE SORPTION OF ORGANIC ACIDS ON NOVEL POLYMERIC ION EXCHANGE RESIN

Magdalena Legan, Andrzej Trochimczuk

Department of Chemistry, Wrocław University of Science and Technology, 50-370 Wrocław, Poland

e-mail: magdalena.legan@pwr.edu.pl

Separation of organic anions such as malate, citrate, malonate, tartate, lactate and oxalate from wastewater and various post-fermentation solutions is very important. Accurate separation of organic acids have been considered difficult, since most of the dicarboxylic acids present similar structure and properties and similar pKa values (1). The aim of this work was to study the influence of pH on the sorption of organic anions: (malate, citrate, malonate, tartate, lactate and oxalate) using new type of ion-exchanger: porous, highly basic monolith with HIPE (High Internal Phase Emulsion) structure. Poly(HIPE)Vim monolith of 1H-imidazolium-1,1'-[1,4 phenylenebis(methylene)]-bis [3-ethenyl] dichloride was prepared in the water in oil in water emulsion (W1/O/W2). The ion-exchange capacity of the poly(HIPE)Vim is 4.20 mmol/g. Ion-exchange ability and selectivity of monolithic anion-exchanger was tested towards anions mentioned above at the pH range of 5.0–10.0. The analyte solution was prepared using buffers (HEPES, CAPSO, MES). Sorption of anions was done from single and from multicomponent solutions. The concentration of anions before and after the sorption was measured using ion-chromatography. As observed in this study the pH effect on sorption depends on the degree of dissociation of acid. The adsorption of organic anions on poly(HIPE)Vim decreases with decreasing pH. Sorption of organic anions depends on the degree of dissociation, thus the net ion charge and electrostatic interactions plays crucial role. The maximum sorption obtained for oxalate (3.73 mmol/g) was higher than the values found for other anions, showing the following capacity order: oxalate > malate > lactate > tartate > malonate > citrate. In this work we propose the use of poly(HIPE)VimM resin to separation of organic anions from aqueous solutions. The present method allows the sorption of organic anions: malate, citrate, malonate, tartate, lactate and oxalate with high efficiency. This method can be easily applied for separation of organic anions from water solution in analytical chemistry. References 1. D.L. Jones, D.S. Brassington, Eur. J. Soil Sci., 49 (1998) 447-455.

104

MEMBRANE FOULING INVESTIGATION - A COMPARISION OF DIFFERENT TECHNIQUES

Agnieszka Miśkiewicz1, Grażyna Zakrzewska-Kołtuniewicz1, Anna

Abramowska1, Sylwia Pasieczna-Patkowska2

1Institute of Nuclear Chemistry and Technology, Dorodna 16, 03-195 Warsaw, Poland

2University of Maria Curie-Skłodowska, Faculty of Chemistry, Pl. M. Curie-Skłodowskiej 3, 20-031 Lublin, Poland

e-mail: a.miskiewicz@ichtj.waw.pl

There are many methods which are widely used for membrane fouling investigation. Some of them are used for the study of the kinetics of membrane fouling, other are used for the determination of deposit thickness and the degree of membrane blocking (1,2). Unfortunately, not many of those above mentioned, methods can be used on-line. This is mostly connected with specific requirements of membrane construction or others restrictions. Optical methods such as DOTM (Direct Observation Through the Membrane) or DVAM (Direct Visualization Above the Membrane) need modules made of glass, while the Electrical Impedance Spectroscopy (EIS) need a special metallic thick layer deposited on the membrane surface, etc. Each method has some limitations and is associated with the making certain assumptions, therefore the key issue is to find for a given application an appropriate method, which can be comparable with at least one other method. In the paper a new approach of application of two different techniques for the membrane fouling investigation is presented. One of those techniques is the radiometric method using radiotracers. Radioactive compounds can be added to the feed solution in a very small amount and due to the specifics of gamma radiation, which simply penetrate most materials used for membrane module preparation, the radioactivity can be easily detected by scintillation probe placed near the module. In the literature there are a few papers considering this method as useful in membrane fouling studies (3). The second technique, proposed in this work as a reference technique is a photoacoustic spectroscopy (PAS). This method is finding increasing use as a powerful tool also for surface investigation, however it has not been intensively explored in the membrane processes investigation. There are only few papers describing results from the utilisation of the PAS in membrane fouling studies (4). However, the overall advantages of this method such as: non-destructive measurement, depth profiling capability as well as high signal saturation limit make the PAS a very promising technique for membrane surface characterisation.

The study was supported by Polish National Centre for Science, Grant agreement No DEC-2013/11/D/ST8/03328.

References 1. J.C. Chen, Q. Li, M. Elimelech, Adv. Col. Interf. Sci., 107 (2004) 83-108. 2. S. Shirazi, Ch.-J. Lin, D. Chen, Desalination, 250 (2010) 236-248. 3. R.M. McDonogh, et al., J. Membr. Sci., 104 (1995) 51-63. 4. Y. Segal, R. Linker, C.G. Dosoretz, Desalination, 271 (2011) 231-235.

105

PURIFICATION OF FLOWBACK FLUIDS AFTER HYDRAULIC FRACTURING OF POLISH GAS SHALES BY HYBRID METHODS

A. Abramowska1, D. K. Gajda1, K. Kiegiel1, A. Miśkiewicz1, P. Drzewicz2,

G. Zakrzewska-Kołtuniewicz1

1Institute of Nuclear Chemistry and Technology, Dorodna 16,

03-195 Warsaw, Poland 2Polish Geological Institute - National Research Institute, Rakowiecka 4,

00-975 Warsaw, Poland e-mail: a.abramowska@ichtj.waw.pl

Hydraulic fracturing is a process which is used for stimulation of the impermeable rock to release the trapped natural gas from there. When the reservoir rock is a shale, the fracturing process causes opening of microreservoirs of natural gas in the shale formation which increases the efficiency of gas extraction. The fracking action is carried out at a depth of 2,000 to 4,500 meters underground and it consists of initiation and further propagation of cracks in the wellbore by a pumped fluid under high pressure, which can reach up to 1000 bar (1). Fracking fluids comprise water (more than 90 %wt.), proppants (silica is usually used) and other additives (> 1%) like biocides, buffers, corrosion inhibitors, crosslinkers, gelling agents, surface tension reducers, etc. Every hydraulic fluid has specific composition and can be an efficient lixiviant for many shale minerals. Various compounds found in the rocks can be leached during the fracking process. The production of a large amount of toxic fluids causes necessity of purification for recycling to reduce environmental impact and to make technology more acceptable by the environment. The purification process proposed by the INCT begins from mechanical separation of suspensions. In the second step the soluble organic compounds are removed by sorption on activated carbons or by oxidation processes e.g. Fenton reaction (2) or ozonation (3). Nanofiltration process and then, reverse osmosis are used for final treatment and water recovery In addition heavy metals flushed from welbore, which are concentrated in retentate after nanofiltration are separated by commercial ion-exchangers. The proposed separation scheme is intended to recover water, which can be reused in hydraulic fracturing process. The removal of organic compounds and heavy metals from flowback fluid decreases environmental impact. Acknowledgements: The research were supported by Research Project „Conspan – BlueGas – technology of purification of flowback with recovery of water and valuable metals” References 1. The Polish Exploration and Production Industry Organization, www.opppw.pl. 2. A. Babuponnusami and K. Muthukumar, J. Env. Chem. Eng., 2 (2014) 557-572. 3. S.H. Lin and C.M. Lin, Water Res., 27 (1993) 1743-1748.

106

THE FUNCTIONALIZATION OF POROUS MATERIAL BY IMMOBILIZED ENZYME

Tomoya Nishioka1, Tadashi Okobira2

1Advanced Chemical Science and Engineering Course, National Institute of Technology, Ariake collage, 150 Higashihagio-Machi,

Omuta, Fukuoka 836-8585, Japan 2Department of Creative Engineering,National Institute of Technology,

Ariake collage, 150 Higashihagio-Machi, Omuta, Fukuoka 836-8585, Japan e-mail: c48429@ga.ariake-nct.ac.jp

Recently, the enzymatic reactions which make the various reactions possible under the mild condition are expected for application to industry process from the view of green chemistry. On the other hand, in the case of using at industry processes, there are some problems such as denaturation by heat and/or an organic solvent, the preservation stability and the decreased efficiency of enzymatic reaction. Enzyme immobilization method is the superior technology to solve those problems. This technology has many advantages such as the easily recover/recycle of enzyme after the reaction and a realization of continuous operation. However, it encounters some problems such as deactivation caused by conformational changing of active site at the progress of immobilization, inhibition for the transport of the substrate to vicinity of enzyme by diffusion mass transfer resistance. Moreover, it is necessary to be able to retain a high activity in organic media for industry application. In this study, we carried out the immobilization of enzyme to porous hollow fiber membrane which was chemically-modified by electron beam-induced graft polymerization (EIGP). The EIGP is the one of the methods which produces polymer brushes onto the polymeric substrate. This method enables high-density multi-layering of enzymes by introducing suitable functional groups (e.g. amino ethanol, amine, hydroxyl group). In this work, Laccase is adopted as the immobilized enzyme to use in the environmental purification. Laccase is copper-containing oxidase enzyme that is found in many plants, fungi, and microorganisms. It is able to act on various chemical materials by using only oxygen. The activity evaluations of immobilized Laccase were carried out using ABTS substrate (Fig. 1). As the results, an activity of immobilized Laccase was found to be affected by Space velocity of substrate, amount of the immobilized enzyme and the kind of introduced functional groups.

Fig. 1. Effects of SV for immobilized laccase activity in aqueous solution

(g-Lac./kg-fiber) (g-Lac./kg-fiber) (g-Lac./kg-fiber) (g-Lac./kg-fiber)

107

3D STRUCTURAL ANALYSIS OF SUPERMOLECULES IN AQUEOUS SOLUTION BY X-RAY SCATTERING AND

COMPUTATIONAL CHEMISTRY METHODS

Tadashi Okobira1, Tomoya Ueda1, Koudai Ikesue1, Yusuke Sanada2, Shota Fujii3, Kazuo Sakurai3

1Department of Creative Engineering, Ariake National College of Technology,

150 Higashihagio-Machi, Omuta, Fukuoka 836-8585, Japan 2Department of Chemistry, Faculty of Science, Fukuoka University

8-19-1 Nanakuma, Jonan-ku, Fukuoka 814-0180, Japan 3Department of Chemistry and Biochemistry, University of Kitakyushu, 1-1 Hibikino, Wakamatsu-ku, Kitakyushu, Fukuoka 808-0135, Japan

e-mail: okobira@ariake-nct.ac.jp

Supermolecules such as micelles, nucleic acids, polysaccharides and lipids are used as various functional materials. Their functionality is dependent on the amount and/or type of interactions involved in supermolecules and it is mainly expressed in the aqueous solution. Therefore, we have to understand the 3D structure of supermolecules in aqueous solution, and this information plays important role in creation of novel functional materials. Small-angle X-ray scattering (SAXS) provides nanoscale information about size and shape of dispersed particles. Recently, SAXS has been used to determine structure of the proteins. However, it is difficult to understand details of the 3D configuration of the aggregate of the molecules forming the supermolecules with SAXS only. We considered that the 3D configuration of the aggregate of the molecules can be understand by combination of the computational chemistry method and SAXS. Molecular mechanics and molecular orbital method make a significant contribution to the evaluation of the static model. By molecular dynamics simulation, it is possible to obtain the information of temporal change about the behaviour closer to reality. On the other hand, a program called “Crysol” for evaluating the solution scattering from created model by computational chemistry and fitting it to experimental scattering curves from SAXS was reported (1). We tried to determine the 3D structure of nucleic acid and calixarene micelle by SAXS and Crysol. Fig. 1 shows the fitting results about case of nucleic acid between an experimental and theoretical curves from SAXS and Crysol. We suggest a new method to determine the 3D structure of supermolecules.

Acknowledgements: This work was financially supported by the JST CREST program.

References 1. D.I. Svergun, C. Barberato, M.H.J. Koch, J. Appl. Cryst., 28 (1995) 768-773.

0

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1.5

2

2.5

3

3.5

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Inte

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ty [

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SAXS

Crysol

Fig. 1. Fitting curves about case of nucleic acid from SAXS and Crysol. Both curves are completely overlap

108

SELECTIVE RECOVERY OF SILVER FROM CHLORIDE SOLUTIONS ON FUNCTIONALIZED RESINS

Magdalena Pilśniak-Rabiega, Katarzyna Wejman-Gibas

Faculty of Chemistry, Wrocław University of Science and Technology

Wybrzeże Wyspiańskiego 27, 50-370 Wrocław, Poland e-mail: magdalena.pilsniak@pwr.edu.pl

The recovery of precious metals, including silver, attracted the attention of many researches over last several years. This noble metal, although sometimes present in its native state, is often extracted from complex ores such as sulphide refractory ores, waste recycle materials, e.g. electronic and jewelry scraps. The majority of silver is obtained from ores using alkaline cyanide leaching but this process is not an ideal one on account of its toxicity, low leaching rate and its inefficiency in treatment of certain classes of refractory ores. Other leaching processes utilizing thiosulphate, acidified thiourea, hydrochloric acid and ammonia solution have been also studied and some of these processes have found applications in the industry. The chloride leaching has several advantages due to the higher dissolution rate of silver, low price of leaching reagents and non-polluting character. For the silver recovery from leaching solutions, sorption on activated carbon (CIP method, called “carbon in pulp”) and sorption on polymeric resins (RIP method, called "resin in pulp”) is applied. Silver-selective resins have some distinct advantages over activated carbon for the recovery of silver. Resins have potentially higher loading capacities, higher loading rates, are less likely to be poisoned by organics, and do not require thermal regeneration (1). Polymeric materials, ion-exchange resins, containing selective functional groups, and chelating resins are widely used in hydrometallurgy, especially for the separation of noble metal ions from various solutions (2). Chelating polymers are characterized by the presence of reactive functional groups containing O, N, S and P donor atoms that are capable of forming complexes with metal ions. The aim of this work is to present the possibility of the silver(I) sorption from the chloride solutions on the vinylbenzyl chloride-divinylbenzyl copolymer functionalized with 1-methylimidazole, 1,2-dimethylimidazole, 2-diethylaminoethanol, diethylenetriamine and tetraethylenepentamine. The obtained resins were characterized using FTIR and elemental analysis for nitrogen and chlorine. These polymeric materials were used for the removal of silver from chloride solution (0.10 M HCl, 4.0 M NaCl), containing 50.0 mg/L of Ag(I). The highest sorption of Ag(I), 19.9 mg/g, is reached in the case of 1-methylimidazole resin, log Kd (distribution coefficient) value is 3.28. Additionally, the sorption of silver(I) ions was tested from chloride pregnant leach solutions (PLS), coming from an atmosphere leaching of the copper flotation concentrate from Lubin Concentrator (KGHM Polska Miedź S.A.).

References 1. B.R. Green, M.H. Kotze, J.P. Wyethe, JOM, 54 (10) (2002) 37-43. 2. A. Parodi et al., Hydrometallurgy, 92 (2008) 1-10.

109

THE USE OF ACTIVATED CARBON OBTAINED FROM WASTE BLEACHING EARTH TO REMOVAL OF CHROMIUM(VI)

I. Polowczyk1, R. Sawicki1, A. Bastrzyk1, E. Lorenc-Grabowska2

1Department of Chemical Engineering, Faculty of Chemistry, Wrocław University of Technology, Norwida 4/6, 50-373 Wrocław, Poland

2Department of Polymer and Carbonaceous Materials, Faculty of Chemistry, Wrocław University of Technology, Gdańska 7/9, 50-344 Wrocław, Poland

e-mail: izabela.polowczyk@pwr.edu.pl The aim of this study was to investigate the possible use of activated carbon obtained from spent bleaching earth as an adsorbent for the removal of chromium(VI) ions from aqueous solution. Equilibrium and kinetic studies of Cr(VI) removal by prepared adsorbents were carried out and the experimental data were fitted to adsorption isotherm and kinetics models. Bleaching earth is a montmorillonite mineral and is used extensively in the refining of edible oils and fats (1). Spent bleaching earth derived from the purification process of vegetable oil was subjected to thermal and chemical activation (2). A horizontal tube furnace was used for thermal activation. The waste material was placed in the central part of furnace, then it was heated at different temperatures, i.e. 400, 600, 800°C for 1 h in the nitrogen stream. Also, waste-bleaching earth was mixed with 10% aqueous solution of sulfuric acid and sodium sulfate in the ratio of 1:3 by weight and soaked for 24 h. Afterwards samples were washed several times with deionized water. The adsorbents were dried and ground in a mortar (2). The prepared carbon-mineral adsorbents were characterized for the uptake of chromium(VI) from aqueous solution. The effect of adsorbent dosage, initial concentrations and contact time were investigated. The highest adsorption capacity of chromium(VI) ions (16 mg∙g-1) was obtained for the waste material carbonized at 400°C. The isotherm experimental data were tested by the Langmuir and Freundlich models. The results confirmed that the Freundlich isotherm model best fit to the equilibrium data. Adsorption kinetics of Cr(VI) ions were investigated by Elovich, parabolic diffusion, pseudo first-order and pseudo second-order models. The kinetics data were described well using the pseudo second-order chemisorption model. This study showed that the prepared carbon-mineral adsorbents may be used as an effective material for the removal of chromium(VI) and other metal ions from wastewater.

Acknowledgements:The work was financed by a statutory subsidy from the Polish Ministry of Science and Higher Education for the Faculty of Chemistry of Wroclaw University of Technology.

References 1. R. Leboda et al., J. Colloid Interface Sci., 259 (2003) 1-12. 2. K.S. Low et al., Environ. Technol., 24 (2) (2003) 197-204.

110

APPLICATION OF THIOSALICYLATE-BASED IONIC LIQUID FOR HEAVY METAL REMOVAL FROM MODEL WASTEWATER

USING POLYMER INCLUSION MEMBRANES

B. Pośpiech1, J. Gęga1, W. Kujawski2, P. Czuprynski3, T. Janda3

1Department of Chemistry, Częstochowa University of Technology, Armii Krajowej 19, 42-200 Częstochowa, Poland

2Nicolaus Copernicus University in Toruń, Faculty of Chemistry, 7 Gagarina St., 87-100 Toruń, Poland

3EDF Poland, 1 Ciepłownicza St., 31-587 Kraków, Poland e-mail: b.pospiech@wip.pcz.pl

Recycling of industrial wastewater is necessary and very important from ecological and economical points of view. Heavy metals are one of the most hazardous substances among the water pollutants. This work describes the removal of Zn(II), Cd(II), Cu(II) and Fe(III) from model wastewaters using transport process across polymer inclusion membrane (PIM). In this type of membrane, an ion carrier is confined within cellulose triacetate polymeric matrix (CTA). Plasticizer can be used as an additional substance in order to improve mechanical properties of membrane. Moreover, plasticizer plays a role of a solvent for carrier. Therefore, the choice of a suitable carrier and plasticizer is very important. Thiosalicylate-based ionic liquid, trioctylmethylammonium thiosalicylate [A336][TS] was applied as the carrier for the separation of various metal ions from aqueous solutions. Factors affecting transport kinetics were studied experimentally. Optimum parameters as well as optimum membrane composition for the selective removal of metal ions have been determined. Moreover, the influence of the receiving phase on the efficiency, transport rate and the selectivity of the facilitated transport were discussed.

111

RECOVERY OF PLATINUM(IV) FROM AQUEOUS SOLUTIONS BY TRANSPORT ACROSS POLYMER INCLUSION MEMBRANES

WITH THIOSALICYLATE-BASED IONIC LIQUID AS CARRIER

B. Pośpiech

Department of Chemistry, Częstochowa University of Technology, Armii Krajowej 19, 42-200 Częstochowa, Poland

e-mail: b.pospiech@wip.pcz.pl

This work evaluates the transport through a novel polymer inclusion membranes (PIM) with thiosalicylate-based ionic liquid – trioctylmethylammonium thiosalicylate (TOMATS) as a specific carrier. The study was focused on the recovery of platinum(IV) from acidic chloride solutions. Up to know, liquid membranes with the typical extractants as the ion carriers to the separation and recovery of platinum and platinum group metals (PGMs) from aqueous solutions were intensively investigated. Recently, ionic liquids (ILs) are subject of many studies and are very often used as solvents, extractants as well as carriers. This huge interest in these compounds is connected with their very interesting physicochemical properties. ILs are liquid salts composed of an organic cation and either an organic or inorganic anion. In this work, thiosalicylate-based ionic liquid was used as effective carrier for the transport of Pt(IV). The membrane was obtained by casting a solution containing TOMATS as carrier and base polymer, cellulose triacetate (CTA) to form a thin, transparent, stable, and flexible film. The membranes were prepared with and without addition of a plasticizer. The experimental conditions such as hydrochloric acid concentration in the source phase, type and concentration of the receiving phase and membrane composition were optimized for the quantitative recovery of this metal ions. The obtained results suggested that transport across PIM with TOMATS has a potential to be used as the effective method for recovery of Pt(IV) ions from hydrochloric acid solutions.

112

DEVELOPMENT OF HYBRID CHITOSAN/Fe3O4 NANOCOMPOSITES FOR Gd3+ AND Gd-DTPA ADSORPTION

Ie. V. Pylypchuk1, D. Kołodyńska2, P. P. Gorbyk1

1Chuiko Institute of Surface Chemistry of National Academy of Sciences of Ukraine, Nanomaterials Department, 17 General Naumov Str., 03164 Kyiv,

Ukraine 2Faculty of Chemistry, Maria Curie-Skłodowska University, pl. Maria Curie-

Skłodowskiej 3, 2-031 Lublin, Poland e-mail: ievgenpylypchuk@gmail.com

Nanocomposites based on magnetite (Fe3O4) are widely used for magnetic resonance imaging (MRI) and targeted drug delivery. Promising trends of using magnetic materials with the well-developed surface are preparation of magnetosensitive nanocomposites with natural biopolymers (e.g. chitosan). Combination of chitosan and magnetite properties opens the way to creation of new effective pH-controllable drug delivery and release systems with high biocompatibility. The previous studies exhibited a great potential of chitosan-inorganic mineral composites. Chitosan/Fe3O4 nanocomposites with 4%wt. or 8% of chitosan were obtained. The DTPA and EDTA chemical groups were grafted to the nanocomposites surface. Adsorption of Gd3+ and Gd-DTPA on different kinds of chitosan-magnetite nanocomposites was investigated. The Langmuir and Freundlich adsorption models were applied to describe adsorption processes. Nanocomposites were characterized by the scanning electron microscopy (SEM, Fig. 1), differential thermal analysis (DTA), Fourier-transform infrared spectroscopy (FTIR), X-ray diffraction (XRD) and specific surface area determination (ASAP) methods.

Fig. 1. SEM images of magnetite (right), and Chitosan/Fe3O4 composite (left) Acknowledgement: This research was funded by the International Visegrad Fund (Visegrad/V4EaP Scholarship No 51500518).

113

MOLECULAR MODELLING STUDIES OF POLY(VINYL ALCOHOL) HYDROGEL SWELLING PROCESS AS A TEMPLATE

FOR A QSPR ANALYSIS

Łukasz Radosiński, Karolina Labus

Group of Bioprocess and Biomedical Engineering, Chemistry Department, Wrocław University of Science and Technology, Wybrzeże Wyspiańskiego 27,

51-370 Wrocław, Poland e-mail: lukasz.radosinski@pwr.edu.pl

Poly(vinyl alcohol) hydrogel is an important material having variety of applications in separation processes, enzyme immobilisation and biomedical industry (1-3). Its mechanical, transport and adsorption properties depend on many factors such as water swelling degree, crosslinking degree or temperature. The understanding of the functional dependence between aforementioned parameters-properties has crucial impact on the design and application of given hydrogel matrix. So far, the investigations were concentrating on experimental approaches with only few of theoretical research (4,5). In our work we use state-of-the art multiscale modelling (4) technique that allows to study the properties of the given hydrogel matrix (PVA) as a function of its atomic composition and contribution of specific atomic coupling the overall free energy. Using a combination of NPT Molecular Dynamics (4) and Monte Carlo (5) technique we perform initial calculations of the dependence of density and sorption properties as a function of a temperature and swelling degree. The analysis is performed using various force field including COMPASS, COMPASS II, Dreiding, cvff and Universal. The results agree well with experimental results available in the literature and we provide a detailed comparison of the accuracy of the given force fields. Furthermore we present a concept for finding a statistical correlation (QSPR – Quantitive Structure-Property Relationship) between given macroscopic properties of the hydrogel system and its atomistic composition. References 1. T.S. Gaaz et al., Molecules, 20 (2015) 22833-22847. 2. J.F. Zhan et al., Braz. J. Chem. Eng., 30 (2013) 721-728. 3. M.I. Baker at al., J. Biomed. Mater. Res. B Appl. Biomater., 100 (2012) 1451-1457. 4. J.S. Bermejo at al., Macromol. Theor. Simul., 18 (2009) 317-327. 5. J.S. Bermejo at al., Macromol. Theor. Simul., 18 (2009) 259-267.

114

STUDIES ON PERMEATION OF SOME TRANSITION METALS USING 1,2,4-TRIMETHYLIMIDAZOLE AS SELECTIVE ION

CARRIER

Elżbieta Radzymińska-Lenarcik, Agnieszka Michalak

Faculty of Chemical Technology and Engineering, Department of Inorganic Chemistry, UTP University of Science and Technology,

Seminaryjna 3, 85-326 Bydgoszcz, Poland, e-mail: elaradz@utp.edu.pl

Recently shown, that 1-alkylimidazoles (1), 1-alkyl-2-methylimidazoles (2,4), and 1-alkyl-4-methylimidazole (3,4) can be used for separation of the Cu(II) ions from an equimolar mixture of the Cu2+, Zn2+, Co2+, Ni2+ and Cd2+ ions in the transportation process across polymer inclusion membrane (PIM). With elongation of the chain length of substituent -R in the imidazole ring, the initial flux of the ions increases, but the separation coefficients decrease. It was also proved that an increase in chloride-ion concentration in the source phase resulted in the increase in the permeability coefficients which attained their top values at 1.0 M concentration of the chloride ions (1). In this work, the authors present results of their investigation of the competitive transportation of Cu2+ from different equimolar mixture of transition metal ions as Cu2+, Zn2+, and Cd2+ ions from dilute chloride solutions across polymer inclusion membranes (PIMs), which consist of cellulose triacetate (CTA) as polymeric support, o-nitrophenyl octyl ether (ONPOE) as plasticizer and 1,2,4-trimethylimidazole as ion carrier. Also, the influence of the carrier concentration on the separation process was investigated. It has been shown that the optimum concentration of the carrier in the membrane is 1M. The membrane is characterized by atomic force microscopy (AFM) and thermal analysis (DTA and TG) techniques. The results show that Cu2+ and Cd2+ can be separated very effectively from other transition metal cations. The separation coefficients were found order of SCu/Zn < SCu/Cd. The recovery factor of Cu2+ and Cd2+ ions during transport across PIM from different mixture is equal to 96% and 82%, respectively. More details will be presented on poster. Acknowledgements: The new developments presented above were carried out within the 2007-2013 Innovative Economy Operational Programme, Sub-action 1.3.2., Support of the protection of industrial property generated by scientific entities as result of R&D works within project no. UDA-POIG.01.03.02-04-077/12-01, financed by the European Regional Development Fund (ERDF) (85% of co-financing) and from a designated subsidy (15% of co-financing). References 1. M. Ulewicz, E. Radzymińska-Lenarcik, Physicochem. Probl. Miner. Process., 46 (2011) 119-130. 2. E. Radzymińska-Lenarcik, M. Ulewicz, Sep. Sci. Technol., 47 (2012) 1113-1118. 3. M. Ulewicz, E. Radzymińska-Lenarcik, Sep. Sci. Technol., 49 (2014) 1713-1721. 4. E. Radzymińska-Lenarcik, M. Ulewicz, Pol. J. Chem. Technol., 17 (2015) 51-56.

115

EXTRACTION OF RARE EARTHS FROM CHLORIDE SOLUTIONS TO A NITRATE IONIC LIQUID BY THE NEUTRAL

EXTRACTANT CYANEX 923

Mercedes Regadío, Koen Binnemans

KU Leuven, Dept of Chemistry, Celestijnenlaan 200F, 3001 Heverlee. Belgium e-mail: Mercedes.Regadio@kuleuven.be

The rare-earth elements (REEs) are listed as critical metals in Europe due to their high economic value (increasing demand in motors, electronics, renewal energy and catalysts) and supply risks (>95% sourced from China) (1). Solvent extraction (SX) is currently the most important process for separating and obtaining REEs. First, a leaching solution with the dissolved elements (aqueous feed phase) is intensively mixed with a solvent (organic phase), which selectively extracts only the desired element/s. Then, the process is reversed by contacting the loaded organic phase with an acidic aqueous strip solution that recovers the desired element/s back out of the solvent. For this purpose, large amount of organic solvent and acids are required. In the present work, a more environmentally friendly approach is tested using “split-anion extraction” (2). The organic phase consisted of Cyanex® 923 (extractant) added to the quaternary phosphonium ionic liquid (IL) Cyphos® IL-101 in its nitrate form (diluent). The aqueous phase consisted of a synthetic feed solution that simulates the composition of a HCl releachate originated from Kringlerne REE deposit in Greenland (77 g/L of REE chlorides) in a 2.5 M CaCl2 matrix. Addition of Cyanex® 923 to the nitrate IL has two major advantages. Firstly, the loading capacity of the organic phase substantially increased due to the strong interactions of the phosphine oxides in Cyanex® 923, with the Lewis acidic REE. Secondly, the extraction sequence across the lanthanide series was changed from a negative one (La more extracted than Lu) to a positive one (La less extracted than Lu), with Y behaving similarly to Pr-Nd. This is convenient since La, Ce, Pr, Nd and Y make up the 77 w% of the total REE, and they will remain in the aqueous phase after SX, what reduces the organic phase consumed and the extraction stages needed for their full separation from the rest of heavier REE. For completing such a separation at a volume ratio aqueous:organic 1:1 and room temperature, the extraction isotherm/McCabe–Thiele diagram predicted five theoretical stages and 35-40 g/L of loading capacity. Finally, stripping the loaded organic phase with water (1:1 v:v) is possible, with almost 100% recovery of the previously extracted REE (Sm to Lu) , after one stage. Using ILs instead of molecular organic diluents (volatile, flammable and non-electrically conductive) and stripping with water instead of acids leads to safer and environmentally friendlier solvent extraction processes.

Acknowledgements: These results has received funding from the European Community’s Seventh Framework Programme ([FP7/ 2007-2013]) under grant agreement n°309373. This work reflects only the author’s view, exempting the Community from any liability.

References 1. European Commission (2010). Report of the Ad hoc Working Group on defining critical raw materials. Critical raw materials for the EU. 2. K. Larsson, K. Binnemans, Hydrometallurgy, 156 (2015) 206-214.

116

Co(II) REMOVAL FROM CHLORIDE AND SULFATE SOLUTIONS WITH ACIDIC AND BASIC EXTRACTANTS

Francisco J. Alguacil1, Magdalena Regel-Rosocka2

1Centro Nacional de Investigaciones Metalúrgicas (CSIC), Avda. Gregorio del

Amo, 8, 28040 Madrid, Spain 2Poznań University of Technology, Faculty of Chemical Technology, Institute of

Chemical Technology and Engineering, Berdychowo St. 4, 60-965 Poznań, Poland

e-mail: magdalena.regel-rosocka@put.poznan.pl

Cobalt is a valuable metal which is applied in a wide spectrum of products. Except from the natural ores cobalt can be produced also from secondary sources, e.g. sulfate or chloride solutions after leaching cobalt-bearing materials such as for example superalloys. In such solutions Co(II) can be accompanied by Ni(II), Cr(III), Zn(II), Cu(II), Al(III) and iron ions (1). Liquid-liquid extraction is widely used in the recovery and separation of metals from aqueous solutions (2). Though there are many research papers on application of various extractants for Co(II) recovery from aqueous solutions, mainly sulfates (1-5) still new challenges appear to separate Co(II) from various metallic contaminants. Typical acidic extractants such as Cyanex 272, Cyanex 301, Cyanex 302 or DEHPA can be successfully replaced by their sodium salts for extraction of metal ions from aqueous solutions (3). Good extraction efficiency of Na-Cyanex 272 towards Cu(II) is proven by Staszak et al. (4) and towards Co(II) and Zn(II) by Regel-Rosocka et al. (5). Also, quaternary phosphonium and ammonium salts or their mixtures with other types of extractants are able to enhance Co(II) extraction, and show synergy giving higher distribution ratios than organic phases including individual extractants (6,7). However, there is still problem of selective recovery of Co(II) from mixtures of metal ions. Thus, the aim of the work is to investigate extraction-stripping of Co(II) from solutions containing mixture of metal ions (Ni(II), Cu(II), Zn(II), Al(III)) to obtain selective separation of cobalt ions with binary mixtures of Cyanex 272 and phosphonium or ammonium quaternary salts. The following issues are investigated: i) the effect of initial pH of feeds on the selectivity of Co(II) extraction, ii) composition and molar ratio of organic components of binary mixtures on Co(II) extraction, iii) flowsheet for selective extraction of Co(II).

Acknowledgements: F.J. Alguacil thanks CSIC (Spain) for support. Polish research was supported by the 03/32/DS-PB/0601 grant.

References 1. D. Darvishi et al., Hydrometallurgy, 77 (2005) 227-238. 2. M. Regel-Rosocka and F.J. Alguacil, Rev. Metal. Madrid, 49 (2013) 292-315. 3. P.K. Parhi and K. Sarangi, Sep. Purif. Technol., 59 (2008) 169-174. 4. K. Staszak et al., Sep. Sci. Technol., 85 (2012) 183-192. 5. M. Regel-Rosocka et al., Clean Technol. Environ. Policy (2016) DOI 10.1007/s10098-016-

1123-1. 6. P. Rybka and M. Regel-Rosocka, Sep. Sci. Technol., 47 (9) (2012) 1296-1302. 7. I. García-Díaz et al., Proceedings of International Solvent Extraction Conference, ISEC 2014,

Germany, 2014, 1083-1087.

117

REMOVAL OF PRECIOUS METALS FROM AQUEOUS SOLUTIONS BY POLYMERIC MATERIAL

CONTAINING SULFUR ATOMS

Sylwia Ronka, Sara Targońska

Wrocław University of Science and Technology, Faculty of Chemistry, Wybrzeże Wyspiańskiego 27, 50-370 Wrocław, Poland

e-mail: sylwia.ronka@pwr.edu.pl Polymers containing sulfur atoms are very efficient in gold and other precious metal removal and usually are more selective (1-3). Introduction of sulfur atoms to macromolecular chains gives them specific properties due to the presence of two free electron pairs. Divalent sulfur can form specific short-range interactions with other atoms by transferring the electron density. In order to obtain specific polymer sorbent for precious metals removal, the sulfur containing material was synthesized in radical polymerization using bead polymerization. This work presents the sorption experiments using newly obtained copolymer 2,2`-thiobisethanol dimethacrylate/ethylene glycol dimethacrylate (TEDM/EGDMA). Sorption studies were performed from single component solutions for precious metal ions and for comparison for copper, cobalt, nickiel and cadmium. Sorption processes were carried out with 10 – 20 ppm metal solutions containing 0.001 M HCl at room temperature. Also, the influence of pH on the metal ions sorption was studied. The concentrations of metal ions were analyzed using ASA and ICP techniques. The presence of sulfur atoms in the resulting polymer allows sorption of precious metal ions, such as Au(III), Pt(II), Pd(II) or Hg(II). The affinity of the synthesized material to trivalent gold ions is very high - up to 330 mg/g depending on the hydrochloric acid concentration. Increase of the concentration of hydrochloric acid significantly affect the process efficiency, but even in 2 M hydrochloric acid the uptake of gold ions is still significant (140 mg/g). The sorption efficiencies from 0.001 M HCl solutions for platinum, palladium and mercury ions are 250 mg/g, 80 mg/g and 100 mg/g, respectively. The studies also show that ions of precious metals such as gold, platinum and palladium can be selectively separated from the mercury ions from solutions of pH = 2 and pH = 1, where sorption of mercury ions does not occur. Acknowledgements: The work was financed by a statutory activity subsidy from the Polish Ministry of Science and Higher Education for the Faculty of Chemistry of Wrocław University of Science and Technology. References 1. H. Li, et al., Chem. Eng. J., 280 (2015) 399-408. 2. R. Awual, et al., Sensor Actuat. B. Chem., 209 (2015) 790-797. 3. Y. Niu, et al., Int. J. Quantum Chem., 111 (2011) 991-1001.

118

PREPARATION OF POLY(ACRYLAMIDE) GRAFTED ONTO CROSSLINKED POLY(HEMA-co-MMA) BEADS FOR REMOVAL

OF PHENOLS

Handan Usta, Fatih Bildik, Gülçin Torunoglu Turan, Bahire Filiz Senkal

Istanbul Technical University, Chemistry Department, 34469 Maslak-Istanbul,

Turkey e-mail: bsenkal@itu.edu.tr

Phenol and its substituted compounds are important organic intermediates for the products of industry and agriculture (1). The largest use of phenol is as an intermediate in the production of phenolic resins. Phenols are generally considered to be one of the most important organic pollutants discharged into the environment causing unpleasant taste and odor of drinking water (2).

Various methods are used for removal of phenol from wastewater such as, photodecomposition, adsorption, volatilization and other various biological and non-biological methods. Various adsorbents such as zeolites (3), polymeric sorbents (4), carbon nanotubes (5) and clay (6) have been investigated for the removal of phenol and phenolic pollutants from wastewater. In this study, hydroxyethyl methacrylate (HEMA), methyl methacrylate (MMA) and ethylene glycol dimethacrylate (EGDMA) as crosslinking agent were copolymerized by suspension polymerization method. Grafting of poly(acrylamide) onto poly(HEMA-co-MMA) beads was carried out by using redox polymerization method in the presence of cerium (IV) ammonium nitrate as oxidant.

P C

O

O CH2 CH2 OH Ce(IV)P C

O

O CH2 CH2( CH2 CH )

C=O

O

NH2

Acrylamide n

Scheme 1. Preparation of the sorbents for removal of phenol

This sorbent has been used to remove phenol and bisphenol A from water solutions. References 1. B.K. Korbahti, K. Tanyolac, Water Res., 37 (2003) 1505-1514. 2. G. Busca et al., J. Hazard. Mater., 160 (2008) 265-288. 3. M. Ghiaci et al., Sep. Purif. Technol., 40 (2004) 217-229. 4. B. Pan et al., J. Hazard. Mater., 157 (2008) 293-299. 5. K. Yang et al., Environ. Sci. Technol., 42 (2008) 7931-7936. 6. M. Ahmaruzzaman, Adv. Colloid Interface Sci., 143 (2008) 48-67.

119

OPTIMIZATION OF CASCADES FOR BINARY ISOTOPE SEPARATION USING VARIOUS EFFICIENCY CRITERIA

Andrei Yu. Smirnov1, Anton K. Bonarev1, Shi Zeng2, Georgy A.

Sulaberidze1, Valentin D. Borisevich1, Dongjun Jiang2

1National Research Nuclear University MEPhI, 115409 Russia, Moscow, Kashirskoe shosse, 31

2Tsinghua University, 100084, Beijing, China e-mail: a.y.smirnoff@rambler.ru

In the past decade nuclear power passes through a renaissance. It leads to the need for large-scale production of low-enriched uranium to produce fuel for nuclear power plants. As is known, on the industrial scale uranium for this purpose is enriched by multi-stage separation facilities, i.e. cascades. Design and construction of these facilities require significant investments, so the problem to search for the efficiency criterion for optimizing the separation cascade parameters is extremely relevant today. As the optimum cascade we usually understand the installation that allows to obtain the required number of commercial low-enriched uranium meeting all requirements of the standard fuel specifications with the minimum unit cost. At the same time, in many situations, the minimum unit cost is responded to the cascade having the smallest possible number of separating elements (e.g. gas centrifuges). In theoretical studies it is generally accepted to apply as an efficiency criterion the minimum flow to supply the cascade stages instead of the mentioned above the minimum unit cost or the number of separation elements. However strictly speaking, this criterion is justified only in the case when separation elements at all cascade stages run in an identical mode. In general case, parameters of separation elements (overall separation factor, cut, and others) do not coincide, and hence the parameters of the optimum cascades found by these two efficiency criterion should not coincide either. In this paper, the optimum cascade with parameters of a single gas centrifuge changing from stage to stage and that of with equal to the averaged over cascade stages overall separation factor is compared. The minimum of separation elements in cascade is chosen as an efficiency criterion. The results obtained allow us to estimate the difference in the optimum parameters for two performance criteria.

Acknowledgement: This research was carried in the framework of the joint Sino-Russian project supported by the Russian Fund for Basic Research (RFBR) under the contract No 16-58-53058 GFEN_a and the National Natural Science Foundation of China (NSFC) under the contract No 1151101155. This work is also supported by the grant of the President of Russian Federation for the young PhDs with the No 14.Y30.16.6284-MK.

120

APPLICATION OF ION EXCHANGERS DOWEX M 4195 AND LEWATIT® MONOPLUS TP 220 FOR REMOVAL OF Zn(II) AND

Cu(II) IONS FROM GALVANIC WASTEWATERS

W. Sofińska-Chmiel1, D. Kołodyńska2, Z. Hubicki2 and E. Mendyk1

1Analytical Laboratory, Faculty of Chemistry, Maria Curie Skłodowska

University, 20-031 Lublin, Poland 2Department of Inorganic Chemistry, Faculty of Chemistry, Maria Curie

Skłodowska University, Lublin, 20-031, Poland e-mail: wschmiel@umcs.pl

The aim of the presented study was to investigate the sorption and physicochemical properties of the chelating ion exchangers with bis-(2-pyridylmethyl)amine, functional groups before and after the sorption of galvanic wastewaters. The study was carried out on the Dowex M 4195 and Lewatit® MonoPlus TP 220 ion exchangers. For the practical use of the studied ion exchangers in the process of wastewater purification, sorption capacity of the above mentioned ions was determined depending on the phase contact time. The study of Zn(II) and Cu(II) sorption was carried out by the static method. The contents of Zn(II) and Cu(II) ions were determined by the atomic absorption spectrometry method (AAS). Optical microscopy and scanning electron microscopy were used in order to determine physicochemical properties of the ion exchangers. The presented paper showed the results of XPS and FTIR-ATR spectroscopy. It also presented linear maps of the elemental composition of the cut ion exchangers beads after the sorption of galvanic wastewaters. The microscopic examination showed the distribution of Zn(II) and Cu(II) after the sorption process in the whole volume of the beads of the studied ion exchangers. In the case of Dowex M 4195 the concentration of Cu(II) ions was higher than that of Zn(II). The opposite situation was observed in the case of the Lewatit® MonoPlus TP 220 resin. Based on the studies it can be stated that the sorption processes proceed mainly on the surface of ion exchanges. Moreover, the effectiveness of the sorption of Zn(II) and Cu(II) is greater using the Lewatit® MonoPlus TP 220 resin. References 1. C.V. Diniz et al., Hydrometallurgy, 78 (2004) 147-155.

121

APPLICATION OF ION EXCHANGERS FOR PURIFICATION OF GALVANIC WASTEWATER FROM HEAVY METALS

W. Sofińska-Chmiel1, D. Kołodyńska2, Z. Hubicki2 and E. Mendyk1

1Analytical Laboratory, Faculty of Chemistry, Maria Curie-Skłodowska

University, 20-031 Lublin, Poland 2Department of Inorganic Chemistry, Faculty of Chemistry, Maria Curie-

Skłodowska University, Lublin, 20-031, Poland e-mail: wschmiel@umcs.pl

The society with greater awareness of the own health and the surrounding environment pays more attention to the issues of industrial wastes purification. Effective and economical methods for removal of heavy metals from wastewaters coming from production processes are searched for. The main sources of contamination are, among others, chemical, mining, energetic metallurgical and electrotechnical industries. Due to various galvanic processes large amounts of noxious chemical substances get into the environment. From the ecological point of view heavy metals are an essential problem as their effect on the environment is disadvantageous. The metals applied in the surface treatment which negatively affect the environmental and human health are: cadmium, chromium, nickel, lead, copper, cobalt, iron and zinc (1). Therefore there were carried out the studies whose aim was to find the ion exchanger of the best physicochemical parameters for purification of galvanic wastewaters. In the studies there were applied the chelating ion exchangers with the functional aminophosphonic groups: Purolite S 940 and Purolite S 950. For practical application of the ion exchangers for purification of wastewaters, sorption of galvanic wastewaters on chosen ion exchangers was conducted. Sorption of galvanic wastewaters on Purolite S 940 and Purolite S 950 was conducted using the static method. There were also carried out microscopic studies of the above mentioned ion exchangers using the high resolution scanning electron microscope Quanta 3D FEG with the detector EDX (Fei). The linear profile of elemental composition of cut through ion exchanger grains was made to study qualitative and quantitative distribution of sorbed metal ions. The grain of the ion exchangers were cut through using the ultramicrotome EM UC7 (Leica). A special attention was paid to sorption of Zn(II) and Cu(II) ions present in galvanic wastewaters coming from the process of zinc coating formation. The paper presents the results of spectroscopic studies XPS (X-ray photoelectron spectroscopy) using the Ultra High Vacum multi-chamber analytical system (Prevac). The studies allowed to estimate the surface conditions of the above mentioned ion exchangers after the galvanic wastewaters process. The XPS analyses of Purolite S 940 and Purolite S 950 as the whole and the ground ion exchanger beads were made. These studies were compared with the profile of sorbed ions distribution made using the scanning electron microscope Quanta 3D FEG with the detector EDX. References 1. P. Kakkar, F. Jaffery, Environ. Toxicol. Pharmacol., 19 (2005) 335-349.

122

COMPARISON OF VARIOUS SEPARATION POTENTIALS FOR MULTI-ISOTOPE MIXTURE SEPARATION

Georgy A. Sulaberidze1, Andrei Yu. Smirnov1, Shi Zeng2, Valentin D.

Borisevich1, Dongjun Jiang2

1National Research Nuclear University MEPhI, 115409 Russia, Moscow,

Kashirskoe shosse, 31 2Tsinghua University, 100084, Beijing, China

e-mail: sula39@mail.ru

Different approaches applied for introduction of various separation potentials used in theory of multicomponent isotope separation are analyzed. It is demonstrated that all known for the date potentials are not satisfied to the Dirac-Peierls axiomatic introduced for the binary mixture of uranium isotope that makes impossible their practical application. The main reason for that consists in inability to design the model separation cascade which would play a role of the ideal one in the theory of binary mixture separation. Consequently the only universal way to search the optimum parameters of the multicomponent separation cascade is its numerical optimization by the criterion of the minimum of separation elements. Acknowledgement: This research was carried in the framework of the joint Sino-Russian project supported by the Russian Fund for Basic Research (RFBR) under the contract No 16-58-53058 GFEN_a and the National Natural Science Foundation of China (NSFC) under the contract No 1151101155. This work is also supported by the grant of the President of Russian Federation for the young PhDs with the No 14.Y30.16.6284-MK.

123

EXTRACTION OF PLATINUM GROUP METALS WITH NITROGENOUS EXTRACTANTS AND ITS EXTRACTION

MECHANISM ANALYSIS

Yuki Ueda, Shintaro Morisada, Hidetaka Kawakita, Keisuke Ohto

Department of Chemistry and Applied Chemistry, Saga University, 840-8502, 1-Honjo-machi, Saga, Japan

e-mail: yu19891109yu@gmail.com Platinum group metals (PGMs) are absolutely necessary metals for technological society, however, the amount of PGMs primary ores are generally scarce in the surface of the earth and the ores exist in limited locations, e.g. South Africa and Russia (1). For these reasons, the recycling from the secondary resources as the spent automobile exhaust gas catalysts and electronic devices is most important issue for the securement of the PGMs resources. Solvent extraction is one of the most general and useful metal separation method in hydrometallurgical process. The development of the novel extractants for the PGMs have been actively carried out by Narita and Costa et al. (2,3). In our group also the development of the novel extractants as shown in Fig.1 have been carried out. In particular, the tripodal extractants exhibited the extremely high extractability of the PGMs than the corresponding monopodal analogue. The extraction behaviour of the PGM and base metals from HCl aqueous solutions with the nitrogenous extractants and the spectroscopic analysis of the extraction mechanism were investigated in this work.

Acknowledgements : This research was partly financed Research Fellowships of Japan Society for the Promotion of Science for Young Scientists.

References 1. F.L. Bernardis et al., React. Funct. Polym., 65 (2005) 205-217. 2. H. Narita et al., Solvent Extr. Ion Exch., 33 (2015) 426-471. 3. M.C. Costa et al., Solvent Extr. Ion Exch., 31 (2013) 12-23.

Fig. 1. Chemical structures of the nitrogenous extractants in present work

Amide type R1~3: alkyl chain

Urea type R1~2: alkyl chain

Tripodal type R: CH3, C(CH3)3,

Ph, NHC4H9

124

EQUILIBRIUM AND KINETIC STUDIES OF CHROMIUM IONS ADSORPTION ON Co(II) BASED PHOSPHONATE METAL

ORGANIC FRAMEWORKS

Lavinia Lupa1,2, Bianca Maranescu1, Aurelia Visa1

1Institute of Chemistry Timisoara of Romanian Academy, 24 Mihai Viteazul Blv.,

300223 Timisoara, Romania 2University Politehnica Timisoara, Faculty of Industrial Chemistry and

Environmental Engineering, 6 V. Parvan Blv, RO-300223, Timisoara, Romania

e-mail: apascariu@yahoo.com Chromium is present in wastewaters resulted from a lot of industrial processes such as: electroplating, dye, cement, leather tanning, paint. Its presence at values higher than maximum admitted value of 0.05 mg/L can affect the human health and the environment. Therefore is essential to remove chromium from wastewaters before discharge (1,2). Phosphonate metal organic frameworks were obtained in our labs by the reaction of CoSO4

.7H2O with phosphonoacetic acid (CP), N,N-bis(phosphonomethyl)glycine (Gly) or vinyl phosphonic acid (VP) in hydrothermal conditions. The synthesized compounds were characterized by FTIR, X-Ray crystallography and thermogravimetric analysis (3,4). In this study the adsorption potential of three type of Co(II) based phosphonate metal organic frameworks (Co-CP, Co-Gly, Co-VP) for removal of Cr(VI) ions from wastewaters has been investigated. The study involves batch types experiments investigating the effects of the solution pH, solid:liquid ratio, initial concentration of Cr(VI) and contact time upon the adsorption efficiency of the studied materials. Langmuir, Freundlich and Temkin were applied to adsorption equilibrium data to find the best amongst these models. The kinetics of adsorption was found to follow the pseudo-second order model. It was found that the adsorption efficiency of the studied materials in the removal process of Cr(VI) ions from aqueous solutions is in the following order: Co-CP < Co-Gly < Co-VP.

Acknowledgments: This work was supported partially by Program no 2 from the Institute of Chemistry Timisoara of Romanian Academy and by a grant of the Romanian National Authority for Scientific Research, CNCS – UEFISCDI, project number PN-II-RU-TE-2014-4-1398. Dedicated to the 150th anniversary of the Romanian Academy.

References 1. P.K. Pandey et al., Int. J. Environ. Sci. Tech., 7 (2) (2010) 395-404. 2. A.A. Attia et al., Braz. J. Chem. Eng., 27 (1) (2010) 183-193. 3. B. Maranescu et al., Phosphorus, Sulfur Silicon Relat. Elem., 190 (2015) 902-904. 4. B. Maranescu et. al., J. Coord. Chem., 67 (2014) 1562-1572.

125

USE OF CHITOSAN COMPLEX WITH AMINOPHOSPHONIC GROUPS AND COBALT FOR Sr(II) IONS REMOVAL

Bianca Maranescu1, Adriana Popa1, Lavinia Lupa2, Aurelia Visa1

1Institute of Chemistry Timisoara of Romanian Academy, 24 Mihai Viteazul Blv.,

300223 Timisoara, Romania 2University Politehnica Timisoara, Faculty of Industrial Chemistry and

Environmental Engineering, 6 V. Parvan Blv, RO-300223, Timisoara, Romania e-mail: apascariu@yahoo.com; apopa_ro@yahoo.com

Chitosan was discovered in 1859 by Professor C. Rouget. It is one of the most abundant natural polymer, highly studied due to its applications in various areas as food, cosmetics, biomedical and pharmaceutical (1,2). Chitosan has drawn particular consideration as efficient biosorbent due to its low cost compared to activated carbon and its high contents of amino and hydroxyl functional groups showing high adsorption potential for various aquatic pollutants (2-4). We briefly described the chemical modifications of chitosan with aminophosphonic group – cobalt complex and their characterization by FT-IR, energy dispersive X-ray analysis (EDX) and scanning electron microscope image (SEM). The EDAX image provided information about the elements: cobalt, phosphorus, oxygen, nitrogen and carbon which were clearly identified. In order to determine the adsorbent performance of the chitosan complex with aminophosphonic groups and cobalt it was used in the removal process of Sr(II) ions from aqueous solutions. The strontium adsorption was studied as a function of initial strontium concentration, contact time and temperature. Adsorption isotherms like Langmuir, Freundlich, Dubinin-Radushkevich (D-R) and Temkin were used to analyze the equilibrium data at the different concentrations. The kinetics of the Sr(II) sorption was analyzed using the pseudo-first order and pseudo-second order kinetic models. The thermodynamic parameters were determined using the equilibrium constant values obtained at different temperatures. The results clearly indicates that the chitosan complex with aminophosphonic groups and cobalt is an efficient adsorbent with respect to its capacity to absorb Sr(II) ions from aqueous solutions. Acknowledgments: This work was supported partially by Program no 2 from the Institute of Chemistry Timisoara of Romanian Academy and by a grant of the Romanian National Authority for Scientific Research, CNCS – UEFISCDI, project number PN-II-RU-TE-2014-4-1398. Dedicated to the 150th anniversary of the Romanian Academy. References 1. A. Bhatnagar, M. Sillanpää, Adv. Colloid Interfac. Sci., 152 (2009) 26-38. 2. E. Guibal, Sep. Purif. Technol., 38 (2004) 43-73. 3. C. Gerent et al., Crit. Rev. Environ. Sci. Technol. 37 (2007) 41-121. 4. G. Crini, P.M. Badot, Prog. Polym. Sci., 33 (2008) 399-447.

126

ADSORPTION BEHAVIOR OF CESIUM AND STRONTIUM ONTO CHITOSAN IMPREGNATED WITH IONIC LIQUID

Lavinia Lupa1, Raluca Voda1, Adriana Popa2

1Politehnica University of Timisoara, Faculty for Industrial Chemistry and

Environmental Engineering, Piata Victoriei No. 2, Timisoara, RO-300006, Romania

2Institute of Chemistry Timisoara of Romanian Academy, 24 Mihai Viteazul Blv., 300223 Timisoara, Romania e-mail: raluca.voda@upt.ro

Adsorption behaviour of Cs+ and Sr2+ ions onto ionic liquid-impregnated chitosan has been studied. It was showed that the use of ionic liquids onto suitable solid supports improve the adsorption performance of the solid supports in the removal process of radionuclides from aqueous solutions. In this paper as ionic liquid – n-butyl triphenyl phosphonium bromide was used. The impregnation of chitosan with the studied ionic liquid (IL) was realized through ultrasonication, an efficient and economical process. The obtained adsorbent was subjected to FTIR, SEM and EDX analysis in order to put in evidence that the chitosan was impregnated with the studied IL. The adsorptive properties of ionic liquid-impregnated chitosan for the removal of Cs+ and Sr2+ ions from aqueous solutions were studied in a batch adsorption system. The adsorption was studied as a function of initial concentration, contact time and temperature. The experimental data were analyzed by both Langmuir and Freundlich isotherms. The kinetic adsorption experimental results were studied using pseudo-first order and pseudo-second order kinetic models. The adsorption kinetic was found to follow a pseudo-second order kinetic model. The adsorption process was conducted also in the presence of other cations Na+ and Ca2+. The adsorption properties of the chitosan impregnated with the studied ionic liquid was determined in binary, tertiary and quaternary systems. The adsorption capacity of the ionic liquid-impregnated chitosan is not significantly influenced in the binary systems when the present cations have different oxidation number (ex. Cs+ in the presence of Ca2+). In the binary systems where the cations have the same oxidation number (e.x. Cs+ and Na+), the adsorption capacity of the studied materials presents a slow decrease. The adsorption capacity of the ionic liquid-impregnated chitosan decreases with the increasing number of the cations present in solutions. It was observed that the studied adsorbent has a higher affinity for the Cs+ ions than for Sr2+ ions. Keywords: ionic liquid, chitosan, impregnation, strontium, cesium, adsorption

Acknowledgements: This work was supported by a grant of the Romanian National Authority for Scientific Research, CNCS – UEFISCDI, project number PN-II-RU-TE-2012-3-0198.

127

COMPARATIVE ADSORPTION OF PHENOL AND LEAD FROM AQUEOUS SOLUTIONS ONTO Co3O4

Raluca Voda, Lavinia Lupa, Laura Cocheci

Politehnica University of Timisoara, Faculty for Industrial Chemistry and

Environmental Engineering, Piata Victoriei No. 2, Timisoara, RO-300006, Romania

e-mail: raluca.voda@upt.ro

In this study, cobalt oxide (Co3O4) was prepared by thermolysis of homopolynuclear coordination compound, namely [CoC2O4·2.5H2O] at 500°C. This oxide was characterized by IR spectroscopy, XRD (X-ray diffraction) and SEM (scanning electron microscopy). The adsorption of phenol and lead(II) ions, both singly and in combination, on obtained and characterized Co3O4 was studied in batch system. Kinetic and equilibrium experiments were conducted to study the effects of contact time, initial pH, adsorbent dose and initial concentration of the pollutants. The studied adsorbent exhibited better efficiency in the adsorption process toward Pb(II) compared to phenol. In case of lead ions adsorption the equilibrium is achieved in a shorter time than in case of the phenol adsorption. In case of the coexistence of the both pollutants in the aqueous solutions at low concentrations, the adsorption efficiency of the studied adsorbent is not significantly influenced. At higher concentrations the adsorption efficiency of the studied material decrease for the phenol removal but is not significantly influenced for the Pb(II) ions. The results demonstrate that Co3O4 could be efficiently applied in treatment of water contaminated with both inorganic and organic pollutants.

128

STRONGLY BASIC ANION EXCHANGER LEWATIT MONOPLUS SR-7 FOR ACID, REACTIVE AND DIRECT DYES REMOVAL

FROM WASTEWATERS

Monika Wawrzkiewicz, Zbigniew Hubicki

Maria Curie-Skłodowska University, Faculty of Chemistry, Department of Inorganic Chemistry, M. Curie Skłodowska Sq. 2, 20-031 Lublin, Poland

e-mail: m.wawrzkiewicz@op.pl The polystyrene anion exchange resin of the quaternary ammonium functionalities (Lewatit MonoPlus SR-7) was tested as the effective sorbent for the removal of anionic dyes of increasing molecular size (Fig. 1).

Fig. 1. Dyes structure The sorption of C.I. Acid Orange 7 (AO7), C.I. Reactive Black 5 (RB5) and C.I. Direct Blue 71 (DB71) was investigated by the batch and column methods. Modelling of kinetic results showed that the sorption of dyes was best described by the pseudo second-order equation. The Langmuir monolayer capacities were found to be 713.4 mg/g, 791.6 mg/g and 956.7 mg/g for AO7, DB71 and RB5, respectively. The influence of electrolytes such as Na2SO4, Na2CO3 and NaCl on the anion exchanger loading was also investigated. Methanol addition to the 1M HCl and 1M NaOH solutions improved dyes desorption.

a) C.I. Acid Orange 7 b) C.I. Reactive Black 5

c) C.I. Direct Blue 71

129

COMPARISON OF EFFICIENCY OF SILICA-ALUMINA OXIDES IN C.I. DIRECT BLUE 71 REMOVAL FROM AQUEOUS SOLUTIONS

Monika Wawrzkiewicz1, Małgorzata Wiśniewska1, Zbigniew Hubicki1,

Stanisław Chibowski1, Vladimir M. Gun’ko2, Vladimir I. Zarko2

1Maria Curie-Skłodowska University, Faculty of Chemistry, M. Curie Skłodowska Sq. 2, 20-031 Lublin, Poland

2National Academy of Science of Ukraine, Institute of Surface Chemistry, 17 General Naumov Str., 03164 Kiev, Ukraine

e-mail: m.wawrzkiewicz@op.pl

Synthetic mixed oxides have many important industrial applications. They are widely used as components of ceramics, fine optics, lasers, semiconductors, piezoelectrics, catalysts, nuclear fuels, pigments, etc. Due to their unique properties such as specific structure, high surface area and pore size, they are currently considered as effective, efficient, economic and ecofriendly adsorbents for removal of both organic and inorganic pollutants such as chlorophenols, complexones, polyelectrolytes and polymers, surfactants, dyes, metal ions and gases (1). Adsorption of organic compounds like dyes on the mixed oxides provides a great challenge faced by scientists as these substances are dangerous for the environment because of toxicity and resistance to natural degradation. As improper treatment and disposal of dye-contaminated effluents provoked serious environmental concerns all over the world, the adsorption behaviour of textile dye of anionic type (C.I. Direct Blue 71, abbr. DB71) onto the mixed alumina-silica oxides was investigated. Two oxides of different composition were applied: SA96 including 4% of SiO2 and 96% of Al2O3, and SA3 including 97% of SiO2 and 3% of Al2O3. The kinetic studies revealed that with the increasing initial dye concentration from 10 to 30 mg/L and the contact time from 1 to 240 min, the sorption capacities (qt) increased and the equilibrium of adsorption for DB71 was observed after 240 min. Sorption of the dye on SA96 and SA3 proceeds through the pseudo second-order mechanism rather than the pseudo first one or intraparticle diffusion. The experimental data fitted better the Langmuir isotherm model than the Freundlich one. The monolayer sorption capacities (Q0) were found to be 7.7 mg/g for SA3, and 49.2 mg/g for SA96. The effects of auxiliaries such as sodium chloride and anionic surfactant (SDS) on DB71 removal from the system containing 5-20 g/L NaCl and 0.1-0.75 g/L SDS were investigated, too. The auxiliaries presence influenced not only the sorption capacities but also the solid surface charge density (σ0) and shift of pHpzc. Acknowledgement: The research leading to these results has received funding from the People Programme (Marie Curie Actions) of the European Union’s Seventh Framework Programme FP7/2007-2013/ under REA grant agreement noPIRSES-GA-2013-612484.

References 1. M. Wawrzkiewicz et al., Powder. Technol., 278 (2015) 306-315.

130

SEPARATION OF CHLORINATED BIOCIDES FROM AQUEOUS EFFLUENTS USING IONIC LIQUIDS

T. Weidlich, M. Frantíková, L. Nováková, M. Štěpánková

Institute of Environmental and Chemical Engineering, Faculty of Chemical Technology, University of Pardubice, Studentská 573, CZ-532 10 Pardubice,

Czech Republic e-mail: tomas.weidlich@upce.cz

3,6-Dichloro-2-pyridinecarboxylic acid (Clopyralid) is selective herbicide widely used for control of broadleaf weeds. 2-(4-Chlorophenoxy)-2-methylpropanoic acid (Clofibric acid) is used as plant growth regulator, moreover, it is a metabolite of the cholesterol-lowering pharmaceutical drug Clofibrate. Both these mentioned acids are quite water soluble and persistent compounds. Their concentration can be evaluated for example using AOX (adsorbable organic halides) parameter. In this work adsorption using charcoal as standard technique was tested for removal of both mentioned biocides and it was compared with the new method based on precipitation of acidic biocides caused by addition of suitable ionic liquid (1-3). The new technique based on application of ionic liquids as liquid ion exchangers was successfully tested for facile removal of Clopyralid and Clofibric acid in quite broad pH range from model wastewater streams. The attempts for recycling of used ionic liquids from isolated organic phase were performed. It was proved that hydrophobic ionic liquids (for example Aliquat 336) are the most effective precipitation agents for the facile removal of low concentrations of studied biocides from contaminated water. Acknowledgements: This work was supported by Technology Agency of the Czech Republic, project No. TG02010058-GAMA01/007. References 1. T. Weidlich et al, Sep. Sci. Technol., 47 (9) (2012) 1310-1314. 2. J. Martinková, T. Weidlich, Dye precipitation process from aqueous solutions; Patent, CZ20120359, (2013). 3. M. Šimek, T. Weidlich et al., Chem. Pap., 70 (4) (2016) 470-476.

131

THE UPTAKE OF SILVER(I) FROM CHLORIDE LEACHING SOLUTIONS BY AMINE EXTRACTANTS

Katarzyna Wejman-Gibas, Magdalena Pilśniak-Rabiega

Faculty of Chemistry, Wrocław University of Science and Technology

Wybrzeże Wyspiańskiego 27, 50-370 Wrocław, Poland e-mail: katarzyna.wejman@pwr.edu.pl

Silver has many physical properties which are very difficult to substitute using other metals. It responds greatly to light, it does not corrode, it is a very unusual electricity conductor and has antibacterial properties. It is because of these properties that many electronics and solar cell manufacturers, as well as clothing and pharmaceutical industries have taken an interest in silver (1). Its recovery becomes economically attractive, even from low-grade ore such as Polish copper deposits containing also Cu, Pb, Zn, Ni and Co. Interest in hydrometallurgical methods based on chloride solution leaching of copper sulphide concentrates is due to the obvious advantages of these solutions. The higher solubility of chlorides in comparison to e.g. sulphates allows to operation with more concentrated solutions and the simultaneous recovery of associated metals, like silver, gold and lead. In addition chloride leaching outclasses other leaching methods (thiourea, cyanide and thiosulphate) due to low toxicity, low costs and the level of technical “maturity” (2). Solvent extraction gains importance in the hydrometallurgical processing of ores and secondary resources, due to development of organic extractants which selectively extract metals from complex leach solutions. Organic solvents selectively extract the desired metals leaving other constituents in the aqueous raffinate, or sometimes minor impurities are extracted to purify the leach solution for further processing and metal recovery. Additionally removal of metal ions from diluted aqueous medium is generally considered as a great advantage of extraction. The presented work focuses on silver(I) extraction from chloride solution by amine extractants. The influence of sodium chloride, hydrochloric acid and extractant concentrations on the extraction efficiency, as well as the type of stripping agent were examined. The obtained results showed that, regardless of the initial Ag(I) concentration, the extraction was almost complete in sodium chloride and hydrochloric acid of 4.0 mol/L and 0.1 mol/L, further decrease of the solution acidity resulted in decreased extraction. The stripping of Ag(I) ions from the loaded organic phase can be proceed with 0.5 mol/L solution of sodium hydroxide and ammonia. Additionally, the extraction of silver ions was tested from chloride pregnant leach solutions (PLS), coming from an atmosphere leaching of the copper flotation concentrate from Lubin Concentrator (KGHM Polska Miedź S.A.).

References 1. J.E. Dutrizac, Hydrometallurgy, 29 (1992) 1-45. 2. Y.J. Park, D.J. Fray, J. Hazard Mater., 164 (2009) 1152-1158.

132

SEPARATION OF SOME TRANSITION METALS BY SOLVENT EXTRACTION USING 3-SUBSTITUTED DERIVATIVES

OF β-DIKETONES AS SELECTIVE EXTRACTANTS

Katarzyna Witt, Elżbieta Radzymińska-Lenarcik

Faculty of Chemical Technology and Engineering, UTP University of Sciences and Technology, Seminaryjna 3, PL-85326 Bydgoszcz, Poland

e-mail: Katarzyna.Witt@utp.edu.pl Metals such as cobalt, nickel, copper or zinc are widely applied in industry, in addition to being very important microelements in organisms. Their various uses include the production of catalysts, batteries, alloys, paints and varnishes, anti-corrosive coatings, automobile parts, copper is also used in water supply piping and electrical wiring systems. This means that the demand on the metals is immense. Their numerous uses and high consumption volume have one disadvantage: considerable amounts of the metals get through to natural environment and contaminate it. Due to the fact that this metals do not biodegrade and do not decompose to simple compounds, they are really hazardous for living organisms and are, therefore, classified as so-called “heavy metals”. Taking into consideration the above facts, scientists have started to investigate into methods to separate and recover the metals from industrial solid and liquid waste. Our research showed that 3-substituted derivatives of β-diketones may be use as extractants for separation of the Co(II) and Cu(II) ions by solvent extraction. Selectivity of this separation depend on differences in the stability, structure of the coordination sphere, and solubility of transition metal complexes. More details will be presented on poster. Acknowledgements: The new developments presented above were carried out within the 2007-2013 Innovative Economy Operational Programme, Sub-action 1.3.2., Support of the protection of industrial property generated by scientific entities as result of R&D works within project no. UDA-POIG.01.03.02-04-077/12-01, financed by the European Regional Development Fund (ERDF) (85% of co-financing) and from a designated subsidy (15% of co-financing).

133

pH-RESPONSIVE MOLECULARLY IMPRINTED POLYMER FOR SORPTION AND RAPID DESORPTION OF DIBUTYL

PHTHALATE

Joanna Wolska, Małgorzata Kujawska

Wrocław University of Science and Technology, Faculty of Chemistry, Wyb. Wyspiańskiego 27, 50-370 Wrocław, Poland

e-mail: joanna.wolska@pwr.edu.pl

Phthalates such as dibutyl phthalate (DBP) are synthetic compounds used as plasticizers in plastics, rubber, cellulose and styrene production. Due to the widespread use in industry, they are considered as ubiquitous environmental pollutants (1). They have adverse effects on human health, regarding as endocrine disrupting compounds by means of their carcinogenic action (2). Due to refractory content of phthalates and other endocrine disruptors in water bodies it is hardly to control a content of such pollutants as well as to develop the efficient methods for their removal. The presented studies are focused on preparation of pH-sensitive molecularly imprinted polymers (PS-MIPs) that can be used for removal of DBP from solutions. Methyl methacrylate (MMA), methacrylic acid (MAAc) and divinylbenzene (DVB) copolymers were used to form polymer matrices synthesized in block polymerization. The studies have focused on selection of monomers composition, kind of solvent and amount of template to obtain the best material. The molecular recognition of PS-MIPs to dibutyl phthalate has been evaluated at wide range of pH value. The obtained materials showed significant dependence on pH compared with their non-imprinted analogues. The highest efficiency for DBP removal was noted at about pH=6 for material obtained with monomers ratio MAAc:MMA as 3:7, 70% of crosslinker, 5% of footprint in n-octane as porofor. The maximum dibutyl phthalate capacity for this PS-MIP was about 130 mg DBP/g. The best desorption condition was reached at pH=8.

Acknowledgements The work was financed by a statutory activity subsidy from the Polish Ministry of Science and Higher Education for the Faculty of Chemistry of Wroclaw University of Technology No. S50099/Z0309. References 1. J. He , R. Lv, J. Zhu, K. Lu, Anal. Chim. Acta, 661 (2010) 215-221. 2. X. Li et al., Talanta, 131 (2015) 354-360.

134

REMOVAL OF DIETHYL PHTHALATE BY MEANS OF HYBRID MEMBRANE-SORPTION PROCESS

Joanna Wolska, Katarzyna Jackiewicz, Małgorzata Kujawska

Wrocław University of Science and Technology, Faculty of Chemistry Wybrzeże

Wyspiańskiego 27, 50-370 Wrocław, Poland e-mail: joanna.wolska@pwr.edu.pl

Phthalate esters are a class of compounds that can increase the flexibility of plastics. The plasticizers usually exist as a freely mobile phase in polymers, and so they can potentially leach to the environment or food and beverages from the packing materials of polymers. Some recent investigations have showed that the phthalates and their metabolites are suspected to be carcinogenic and endocrine disrupting (1). Diethyl phthalate and other endocrine disruptors are active at concentrations of order of ng/L (2) and the search for effective methods of their depletion is still the hot topic for environment engineers. Adsorption is usually considered as one of the best choices, because it is suitable for the removal of hydrophobic compounds at trace concentrations. Taking into account economic considerations it is still postulated to find more efficient and cheaper method. One of them is a hybrid system compromising sorption on fine adsorbent particles with membrane microfiltration (3,4). The objective of this paper is to evaluate the possibility for removal of diethyl phthalate from water by means of pH-responsive molecularly imprinted polymers and microfiltration membranes. The system was evaluated with two resins with and without DEP imprints and with various process parameters. The goal was to check the process efficiency and select those factors that offered the higher removal ratio. It was concluded that adsorption membrane filtration hybrid process is good alternative to the column removal of trace amounts of DEP.

Acknowledgements: The work was financed by a statutory activity subsidy from the Polish Ministry of Science and Higher Education for the Faculty of Chemistry of Wroclaw University of Technology No. S50099/Z0309.

References 1. J.-H. Hu et al., J. Chromatogr. A, 1330 (2014) 6-13. 2. M. Bodzek, M. Dudziak, Pol. J. Environ. Stud.,15 (2006) 35-40. 3. A. Kołtuniewicz, A. Witek, K. Bezak, J. Membr. Sci., 239 (2004) 129-141. 4. J. Wolska, M. Bryjak, N. Kabay, Environ. Geochem. Health, 32 (2010) 349-352.

135

COMPARISON OF STRONGLY BASIC ION EXCHANGERS APPLICABILITY FOR PALLADIUM(II) IONS REMOVAL

Anna Wołowicz, Zbigniew Hubicki

Maria Curie-Skłodowska University, Faculty of Chemistry, Department of Inorganic Chemistry, Maria Curie-Skłodowska Sq. 2, 20-031 Lublin, Poland

e-mail: annamyrta@poczta.onet.pl As natural deposits of noble metals are being depleted and their price increases, the technologies for noble metals removal and recovery from the secondary raw materials such as anodic slimes, used chemical and auto catalysts, used electric and electronic equipment, wastewaters etc. are becoming more important. Usually, the (bio-)hydrometallurgical and pyrometallurgical methods are successfully applied for these purposes. Moreover, the increasing noble metals demand results in their emission to the environment. One of the most promising methods for removal and recovery of Platinum Group Metals, PGMs (in particular, palladium) is sorption (usually from the chloride, sulphate and nitric acidic media solutions) using different types of adsorbents, characterized by selectivity and high efficiency (1-7). Of commercially available ion exchangers, the anion exchangers of different basicity of their functional groups found wide application for such purpose (1,4,7). The studies are focused on palladium(II) chlorocomplexes removal from acidic solutions by some anion exchangers with different structures and functional groups (Lewatit SR-7 – strongly basic, polystyrenic, macroporous; Purolite A400 TL – strongly basic, polystyrenic, gel; Dowex PSR-2 – strongly basic, polystyrenic, gel and Dowex PSR-3 - strongly basic, polystyrenic, macroporous). The palladium uptake was compared and the effect of hydrochloric acid concentration was evaluated. Moreover, the strongly basic anion exchange kinetic studies were carried out using the batch method. The experimental results were fitted with the calculated values using the pseudo-first (PSO) and pseudo-second order (PSO) kinetic equations. The effects of initial palladium concentration on the sorption process (equilibrium studies) and maximum sorption capacities were determined (Freundlich and Langmuir isotherms equations were applied). Additionally, possibilities of anion exchange resin regeneration (palladium desorption from the loaded resin) were examined. References 1. Z. Hubicki, M. Wawrzkiewicz, A. Wołowicz, Chem. Anal., 53 (2008) 759-784. 2. A. Wołowicz, Przem. Chem., 91 (2012) 53-68. 3. A. Wołowicz, Przem. Chem., 92 (2013) 479-485. 4. O.N. Kononova, N.G. Goryaeva, O.V. Dychko, Natura Sci., 1 (2009) 166-175. 5. A.N. Nikoloski, K-L. Ang, Miner. Process. Extr. Metall. Rev., 35 (2014) 369-389. 6. A. Wołowicz, Przem. Chem., 94 (2015) 884-893. 7. A. Kilislioglu, Ed., “Ion Exchange, studies and application”, InTech, Rijeka 2015, Chapter 1 -

Z. Hubicki, M. Wawrzkiewicz, G. Wójcik, D. Kołodyńska, A. Wołowicz, 3 -35.

136

STUDIES ON REMOVAL OF HEAVY METAL(II) IONS BY ION-EXCHANGE METHOD

Anna Wołowicz, Zbigniew Hubicki

Maria Curie-Skłodowska University, Faculty of Chemistry, Department of Inorganic Chemistry, Maria Curie-Skłodowska Sq. 2, 20-031 Lublin, Poland

e-mail: annamyrta@poczta.onet.pl Environmental pollution by heavy metal ions such as zinc(II), copper(II), nickel(II), cobalt(II), lead(II), mercury(II), cadmium(II) etc. occurs globally due to industrial expansion, agricultural production intensification and waste disposal. A need for efficient methods of removing heavy metal ions before their release into the environment is a matter of concern because of their toxicity, non-degradability, biomagnification, bioaccumulation and negative impact on human health (1,2). Among many conventional methods (precipitation, filtration, ion exchange, oxidation-reduction, reverse osmosis, solvent extraction, membrane separation) that are being used for this purpose, sorption of heavy metal ions onto various adsorbents such as ion exchange resins, activated carbon, zeolites, bioadsorbents is the most common route applied for decontamination of wastewater and industrial effluents (3,4). Ion exchange methods for heavy metal ions removal have been widely used due to their many advantages, such as high treatment capacity, high removal efficiency, selectivity, recovery of valuable metals, low operational cost, less sludge volume produced than while using the chemical precipitation and in many cases fast kinetics (3-5). Moreover, ion exchangers can be easily incorporated into automated analytical procedures for preconcentration, separation and determination of trace amount of heavy metal ions in different samples. In the present work effectiveness of adsorptive removal of heavy metal ions such as nickel(II), copper(II), cobalt(II) and zinc(II) from aqueous solutions of different concentrations of hydrochloric acid using different adsorbents was studied. An attempt was also made to relate the obtained adsorption results with the physicochemical properties of sorbents. Of the adsorbents the ion exchangers of different matrices (carbonaceous, polystyrenic and polyacrylic) were applied and the sorption capacities were determined. The effect of phases contact time and hydrochloric acid concentration using the batch method were evaluated. References 1. K. Pyrzyńska, M. Bystrzejewski, Colloids Surf. A: Physicochem. Eng. Asp., 362 (2010) 102-

109. 2. A. Kilislioglu, Ed., “Ion exchange technologies”, InTech, Rijeka 2012, Chapter 8 - Z. Hubicki,

D. Kołodyńska, 193-240. 3. A. Dąbrowski et al., Chemosphere, 56 (2004) 91-106. 4. F. Fu, Q. Wang, J. Environ. Manag., 92 (2011) 407-418. 5. B. Alyüz, S. Veli, J. Hazard. Mater., 167 (2009) 482-488.

137

INVESTIGATIONS OF CHROMIUM(VI) IONS SORPTION AND REDUCTION ON STRONG BASIC ANION EXCHANGER

Grzegorz Wójcik, Zbigniew Hubicki

University of Maria Curie-Skłodowska, Faculty of Chemistry, Department of

Inorganic Chemistry Pl. M. Curie-Skłodowskiej 2, 20-031 Lublin, Poland e-mail: grzegorzwojcikumcs@wp.pl

Chromium exists in the environment in the chromium(III) and chromium(VI) oxidation states. The chemical properties of chromium(III) and chromium(VI) are different. Chromium(III) is considered to be an essential nutrient agent and for the maintenance of normal glucose tolerance while chromium(VI) can have acute and chronic toxic, as well as carcinogenic effects. Moreover, chromium is a major water pollutant, usually as a result of some industrial pollution including tanning factories, steel works, chromium plating and wood preservation. For this reason, recovery of chromium especially chromium(VI) from wastewaters is a very important issue. There are numerous technologies of chromium removal from wastewaters. Precipitation is traditionally used for the treatment of Cr(VI) containing wastewaters. This requires that Cr(VI) should be reduced to Cr(III) prior to chemical precipitation in order to form poorly soluble chromium(III) hydroxide. After the process the residual level of Cr(VI) is still higher than the discharge limits. Moreover, the disadvantage of chemical reduction is the increasing concentration of sulfate(VI) anions or iron(III) cation in sludge after the reduction process. For this reason the removal of chromium(VI) ions from water solution was investigated.

Sorption of chromium(VI) was studied in the batch process. The anion exchanger Dowex PSR-2 was used for removal of chromium(VI and III) ions. Dowex PSR-2 is a gel-type strong basic anion exchanger. The ion exchanger has tri-n-butyl amine groups. Kinetic parameters were calculated on the basis of static results. Sorption of chromium(VI) was studied in the pH range from 1.5 to 10. It was stated that sorption of chromium(VI) ions depends on the solution acidity. The speciation of chromium was investigated in the studied pH range. The results show very fast kinetics of chromium ions removal in the range of pH from 1.5 to 10. Reduction of chromium(VI) to chromium(III) under acidic conditions was observed. Chromium was determined by using the spectrophotometric and atomic absorption spectroscopy methods. Both methods permit to observe changing of valence of chromium in (III) and (VI) oxidation states. The speciation of chromium in the solid phase of anion exchanger was investigated in the studied pH range by the Diffuse Reflectance Spectroscopy (DRS) method which is very useful to investigate chromium(VI) to (III) reduction process.

138

INVESTIGATIONS OF A NEW EXTRACTION AGENT FOR CHROMIUM(VI) IONS REMOVAL FROM WATER

Grzegorz Wójcik1, Zbigniew Hubicki1, Bogdan Tarasiuk2

University of Maria Curie-Skłodowska, Faculty of Chemistry, 1Department of Inorganic Chemistry, 2Department of Organic Chemistry, Pl. M. Curie-Skłodowskiej 2, 20-031

Lublin, Poland e-mail: grzegorzwojcikumcs@wp.pl

Chromium is an element which is extensively used in industry. Chromium(VI) and chromium(III) are the most popular forms of chromium. Chromium(VI) ions are about one hundred times toxic as toxic as those of chromium(III). Chromium(VI) ions are carcinogenic and mutagenic. Moreover, good solubility in water can cause that chromium ions can propagate the long distances from their sources in the natural environmental. For that reason chromium ions must be removed from their sources and their concentration should be controlled in the water and sludge. In the industry the reduction process is used to decrease chromium(VI) concentration. This process involves using inorganic compounds such as sulfur dioxide, sodium sulfate(IV) salt or ferrous sulfate(VI) to reduce chromium(VI) ions to chromium(III) hydroxide. One of the disadvantages of chemical reduction is increasing concentration of sulfate(VI) anions or iron(III) cation in water or sludge after the reduction process. Among numerous methods for toxic metal ions removal, the solvent extraction is widely applied in purification of solution. The best advantage of solvent extraction is very fast kinetics of toxic metal ions removal. For solvent extraction of toxic metal ions like chromium(VI) ions some extractants are reported in the literature. The extractants can be divided into three groups: basic extractants: tertiary amine or quaternary ammonium salt Aliquate 336 or Alamine 336, neutral: tri-n-butyl phosphate, tri-n-octyl phosphine oxide TBP or TOPO, acidic: DEHPA, Cyanex 272. A new extractant was prepared. This is S-(n-dodecane-1-yl) isothiuronium bromide. This extractant belongs to the basic extractant groups and has a positive charge on the nitrogen atom. The isothiuronium salt have two donor nitrogen atoms and one sulfur atom. The extractant was dissolved in toluene. Solvent extraction of chromium(VI) was studied in the batch process in the pH range from 1.5 to 10. The extraction parameters were calculated based on static results. It was stated that the extraction of chromium(VI) ions depends on acidity solution. The speciation of chromium was investigated in the studied pH range. Reduction of chromium(VI) to chromium(III) under acidic conditions was observed. Chromium was determined using the spectrophotometric and atomic absorption spectroscopy methods. Both methods make it possible to observe changing of valence of chromium in (III) and (VI) oxidation states. The extraction of chromium(VI) ions were characterized by fast kinetics. The time necessary to extract 100 ppm of chromium ions was about 10 min.

139

DETERMINATION OF EUGENOL IN CLOVES WITH VOLTAMMETRIC TECHNIQUE BY USING A RESIN MODIFIED

CARBON PASTE ELECTRODE

Gülcemal Yildiz1, Filiz Şenkal1, Zeynep Aydogmus2

1Department of Chemistry, Faculty of Science and Letters, Istanbul Technical

University, 34469 Maslak, Istanbul, Turkey 2Department of Analytical Chemistry, Faculty of Pharmacy, Istanbul University,

34116, Beyazıt, Istanbul, Turkey e-mail: gyildiz@itu.edu.tr

Eugenol is a phenolic major component of clove oil and can also be found in nutmeg, cinnamon, bay leaf, basil, tulsi and lemon balm. Consuming of eugenol in small amount gives the advantage of anti-microbial, anti-bacterial and anti-fungal properties but exceeding the limit causes various harmful effects. It is commonly used by dentist due to its anti-septic and anti-inflammatory property. In common dental surgeries such as filling, tooth extraction and root canals, it is effectively used to kill germs and relieve the pain. Eugenol sources such as clove oil, cinnamon, basil and nutmeg oil are one of the basic ingredients in mouthwashes, soaps, toothpastes, perfumes, and in various veterinary medications. Voltammetry is a technique which is used in analytical chemistry for quantitative determination of organic and inorganic substances. It is used in variety of fields, which includes studies of oxidation and reduction processes in different medium, adsorption processes on surface, kinetic of electron transfer processes and transfer mechanisms, and thermodynamic properties of solvated substances (1). A modified carbon paste electrode was prepared by using a resin (quaternary chloroacetamide containing 2-(diethylamino)ethyl methacrylate) as a modifier agent. This resin was prepared according to the reaction below:

OCH2CH2N

C2H5

C2H5

C=OP

OCH2CH2N

C2H5

C2H5

C=OP

ClCH2C-NH2

Ochloroacetamide

The electrochemical properties of eugenol were investigated by cyclic voltammetry with this modified CPE. And then the quantitative determination of eugenol in clove was carried out by using differential pulse voltammetry. References 1. A.J. Bard and L.R. Faulkner, Electrochemical Methods, Wiley, New York, 1980, Chapter 7.

140

REMOVAL OF DYES FROM WATER BY POLY(3-SULFOPROPYL ACRYLATE POTASSIUM SALT-co-2-

DIETHYLAMINOETHYL METHACRYLATE) HYDROGEL

Ebru Tekneci, Gulcin Torunoglu Turan, Gülcemal Yıldız, Bahire Filiz Senkal

Istanbul Technical University, Department of Chemistry, Maslak 34469 Istanbul/ Turkey

e-mail: gyildiz@itu.edu.tr

Dyes usually have a synthetic origin and complex aromatic molecular structure which make them more stable and more difficult to biodegrade (1). The interactions between polymer and dye leading to polymer-dye complex formation exhibit many interesting and important practical features. Hydrophilic polymer gels have found wide applications in chemical separation (2,3). For this purpose, a hydrogel was prepared by copolymerization of 3-sulfopropyl acrylate potassium salt and 2-diethylaminoethyl methacrylate with crosslinking agent ethylene glycol dimethacrylate (EGDMA) in aqueous solution with K2S2O8 as an initiator at 80 °C.

O

CH3

O

S

O

O

OK

CH2=C

CH3

C=O

CH2

CH2

C=O

CCH2=

CH3

K2S2O8

H2O, 800CHydrogel

C=O

CH3

OCH2CH2N

CH2CH3

CH2CH3

CH2=C

Scheme 1. Preparation of the hydrogel

Dye extraction experiments were carried out simply by contacting wet gel samples with aqueous dye solutions at room temperature. Capacities were determined by colorimetrical analysis of the residual dye contents. The material is able to remove the cationic dyes completely even from highly diluted aqueous dye solutions.

References 1. S. Seshadri, P.L. Bishop, A.M. Agha, Waste Manage., 15 (1994) 12-137. 2. H. Matsuyama et al., Sep. Sci. Technol., 31 (1996) 687-704. 3. B.F. Senkal, D. Erkal, E. Yavuz, Polym. Adv. Technol., 17 (2006) 924-927.

141

SEPARATION OF LITHIUM FROM SPENT LIQUORS USING THE MALIC ACID COPOLYMERS

Iwona Zawierucha1, Cezary Kozłowski1, Jolanta Kozłowska1, Michał

Michalak2

1Institute of Chemistry, Environmental Protection and Biotechnology, Jan Długosz University of Częstochowa, Armii Krajowej 13/15, 42-200

Częstochowa, Poland 2Centre of Polymer and Carbon Materials, Polish Academy of Sciences, 34, M.

Curie-Skłodowska St., 41-819 Zabrze, Poland e-mail: i.zawierucha@ajd.czest.pl

Lithium has gained increasing applications in recent years in many industries such as glass, ceramics, pharmaceuticals, and mostly, in electronic and electrical industries (1). In addition to spodumene; brine water, geothermal spring water and spent lithium ion batteries are other major lithium resources (2). Recycling of lithium from waste lithium batteries is a growing problem, and new technologies are needed to recover the lithium (3). The adsorption/solid phase extraction (SPE) processes are the most attractive methods for effective removal of metals from different aqueous solutions due to their high efficiency in a wide range of metal ion concentration, and easy handling under relatively flexible working conditions; one should also point out the selectivity and rapidity of these methods. In SPE procedure, the choice of appropriate adsorbent is a critical factor to obtain full recovery and high enrichment factor (4). Currently, there is a lack of highly selective adsorption/ion exchange materials that can be used to recover lithium. For this reason, modification and impregnation techniques of solid phase have been employed to increase the surface adsorption capacity and to enhance the removal efficiency and selectivity of the solid phase. The modification of solid phase (e.g. quartz sand) with new ligands results in the high capacity and selectivity of the sorbents (4,5). Polymer inclusion membrane systems also possess several important advantages concerning the separation aspects, i.e. easy setup, high selectivity and durability (6). In this study the efficiency of supported copolymer of 3-hydroxybutyric and malic acid (P3HBMA) as solid extractant and sorption characteristics of novel sorbent for Li(I) ions were evaluated. Results of the batch systems showed the removal of Li(I) using supported P3HBMA depends particularly on pH of solution. Moreover it was found that novel sorbent had high extraction ability towards Li(I) ions and low one for Na(I) ions. The competitive transport of Li(I) and Na(I) ions across PIM using P3HBMA as ion carrier was also examined. References 1. Y. Pranolo et al., Hydrometallurgy, 154 (2015) 33-39. 2. A. Chagnes, B. Pospiech, J. Chem. Technol. Biotechnol., 88 (2013) 1191-1199. 3. X. Luo et al., RSC Adv., 6 (2016) 12809-12818. 4. M. Ghaedi et al., J. Hazard. Mater., 172 (2009) 802-808. 5. I. Zawierucha et al., Desalin. Water Treat., 52 (2014) 314-323. 6. I. Zawierucha et al., Waste Manage., 33 (2013) 2129-2136.

142

SEPARATION OF CESIUM-137 FROM SPENT NUCLEAR FUEL AND STORAGE POOL

Liang Zhao, Andrzej G. Chmielewski

Institute of Nuclear Chemistry and Technology, Dorodna 16, Warsaw, Poland

email: l.zhao@ichtj.waw.pl

With the operation of nuclear reactor, spent nuclear fuel after the fission process and spent nuclear fuel storage pond cooling water are purified from fission products, including radioactive elements by ion exchange. The process can be performed in a column or stirred tank (suspension or fluidized bed). Magnetic field separation could be applied for the realization of the purification process if the sorbent itself is with magnetism. The main objective of the work is the synthesis of ferromagnetic type ion exchanger. Due to their magnetic properties, they allow for better separation effect from the liquid phase with the application of magnetic field than the beds of sorbents. The adsorbent for Cs-137 -- core-shell magnetic particles of Fe(hydr) Oxide@K2CoFe(CN)6 have been synthesized in the present work. An easy method to prepare core material Fe(hydr) Oxide particles is co-precipitating of Fe2+ and Fe3+ ions under ammonia solution under hydrothermal conditions. In order to synthesize the core-shell materials, a better method is co-precipitation method. Under the stirring condition the K4Fe(CN)6 solution is added into the Fe(hydr) Oxide nano colloidal. Finally the Co(NO3)2 solution is dropped into the mixture slowly. The structure of the sorbent is characterized by Scanning Electron Microscopy-Energy Dispersive Spectroscopy (SEM-EDS), X-ray Fluorescence (XRF), X-ray Diffraction (XRD). The specific surface area is characterize by Brunauer–Emmett–Teller (BET). The hydrodynamic radius is characterized by Dynamic Light Scattering (DLS). The magnetism is characterized by Vibrating Sample Magnetometer (VSM). The results of these methods illustrate that the coprecipitation method could be applied to synthesize sorbent with core-shell structure with supermagnetism. The optional sorption capacity is to be studied by batch sorption method. The thermodynamics of the sorption shows that the sorption process is a spontaneous process for the removal of Cs-137 process. Reference 1. L. Zhao et al., Radiochim. Acta, 104 (2016) 423-433. 2. Y. Yurekli, J. Hazard. Materi., 309 (2016) 53-64.

143

LABSCALE AUTOMATION OF CYCLIC ION EXCHANGE PROCESSES

Luděk Jelínek1, Helena Parschová1, Richard Seydl2, Jiří Mikeš1 and Eva Mištová1

1Department of Power Engineering, University of Chemistry and Technology, Prague, Czech Republic

2Ledvice Power Station, ČEZ a.s., Czech Republic e-mail: ludek.jelinek@vscht.cz

In the industry, majority of ion exchange resins is utilized in columns that are repeatedly exhausted and regenerated in a processes that are usually controlled by more or less sophisticated software. The lifetime of the resins is usually couple of years and in some cases couple of decades. Therefore, the ion exchangers are subjected to thousands of cycles. In the lab scale, it is difficult to estimate the mechanical properties of ion exchangers with respect to the ability to withstand osmotic shocks resulting from the regeneration of ion exchangers. The common analysis of mechanical strength such as Chatillon crush test offers only limited information (1). Device and procedure for simulation of the real conditions were developed using speeded up cyclic change of the ion exchanger form (2). Model solutions, water and regenerant were sequentially pumped through the ion exchange column using multiway valve. The integrity of the particles was evaluated using image analysis with NIS Elements software. Also, the changes of total capacities were evaluated. The results can be used for the prediction of long term stability of ion exchangers. The knowledge gained from the stress test automation is presently used in the automation of lithium isotope separation on cation exchange column. From the single purpose multiway valve controlling software that used timing as the only way of control. The procedure was moved to LabView software that allows for integration of different devices through I/O ports and A/D converter. Thus, devices such as pumps, multiway valves and fraction collectors can be controlled based on the input from sensors such as ion selective electrodes or conductivity meters. References 1. D. Mauer, VGB PowerTech, 91 (8) (2011) 82-86. 2. R. Seydl et al., CZ 28729 U1.

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153

AUTHORS INDEX

A Abramowska A. 104 105 Alguacil F.J. 116 Avdibegović Dž. 71 Aydogmus Z. 139 Azalok K.A. 82 B Babilas D. 51 72 73 76 Bastrzyk A. 68 109 Batchu N.K. 74 Bendova H. 75 Bentkowska D. 72 Bildik F. 118 Binnemans K. 71 74 115 Bogdanov M.G. 66 Bok-Badura J. 76 77 93 Bonarev A.K. 78 119 Boncel S. 76 Borisevich V.D. 78 119 122 Bryjak M. 55 102 Buczkowski R. 44 C Campos Assuncao M. 40 Chagnes A. 40 Chibowski S. 129 Chmielewski A.G. 142 Cichosz M. 44 Ciopec M. 80 Cocheci L. 79 127 Corderi S. 65

Cote G. 40 Cytarska P. 47 Czuprynski P. 110 D Davidescu C.M. 80 Drzewicz P. 105 Dudek G. 86 87 Dvorakova H. 75 Dydo P. 51 72 72 F Franczak A. 72 Frantíková M. 130 Fujii S. 107 G Gabor A. 80 Gajda D.K. 105 Gawdzik B. 67 Gazi M. 81 82 Gęca M. 83 84 88 89 95 Gęca P. 83 84 88 89 95 Gęga J. 110 Gherasim C.V. 45 Głowińska A. 85 Gnus M. 86 87 Gorbyk P.P. 112 Górecka B. 94 Góźdź A. 83 84 88 89 95

154

Grochowicz M. 67 90 Gun’ko V.M. 129 H Halleux H. 40 Harano T. 33 Heeres E. 65 Herman A.P. 76 Hubicki Z. 83 84 88 89 94 95 120 121 128 129 135 136

. 137 138 I Ikesue K. 107 Imamura Y. 91 J Jackiewicz K. 134 Janda T. 110 Jakóbik-Kolon A. 72 76 77 92 93 Jakubiak-Marcinkowska A. 85 Jarzynka K. 102 Jelínek L. 143 Jiang D. 78 119 122 K Kabay N. 26 Karoń K. 76 Kawakita H. 22 123 Keremedchieva R. 66

Kersten S.R.A. 59 Kiegiel K. 105 Kim J.-Y. 22 Kluczka J. 87 Knozowska K. 44 102 Kołodyńska D. 83 84 88 89 94 95 99 100 112 120 121 Kołodziejska M. 97 Konieczny K. 58 86 Koter S. 47 Kowalczuk P.B. 96 Kozłowska J. 97 141 Kozłowski C. 97 98 141 Koźlecki T. 68 Kraslawski A. 102 Krukowska D. 99 100 Kujawa J. 44 102 Kujawska A. 44 Kujawska M. 101 133 134 Kujawski J. 55 102 Kujawski W. 44 58 102 110 L Labus K. 113 Laskowska E. 51 93

155

Legan M. 103 Lorenc-Grabowska E. 109 Love J. 21 Luelf T. 45 Lupa L. 79 124 125 126 127 M Maciejewska M. 28 Maeki M. 22 Maranescu B. 124 125 Mendyk E. 120 121 Michalak A. 114 Michalak M. 141 Mikeš J. 37 143 Milewski A.K. 72 77 93 Mištová E. 143 Miśkiewicz A. 104 105 Mitko K. 51 77 92 93 Miyazaki M. 22 Morisada S. 22 123 N Negdelcheva A. 66 Negrea A. 80 Negrea P. 80 Nishihama S. 33 Nishioka T. 106 Nováková L. 130 Nowik-Zając A. 98 Nycz R. 72 O Ohto K. 22 123

Okobira T. 91 106 107 Oladipo A.A. 81 82 P Parschová H. 143 Pasieczna-Patkowska S. 104 Pazdur L. 63 Pączkowski P. 67 Pilśniak-Rabiega M. 108 131 Polowczyk I. 68 109 Popa A. 125 126 Pośpiech B. 110 111 Pylypchuk Ie.V. 112 Q Qian X. 27 R Radosiński Ł. 113 Radzymińska-Lenarcik E. 114 132 Regadìo M. 71 115 Regel-Rosocka M. 35 116 Reyhanitash E. 59 Ronka S. 117 Roth H. 45 Rychlewska K. 58 Rynkowska E. 102 Rzelewska M. 35 S Sakurai K. 107 Sambor M. 92 Sanada Y. 107 Sathuluri R.R. 22 Sawicki R. 109 Schuur B. 41 59 65

156

Senkal B.F. 118 139 140 Seydl R. 143 Siekierka A. 55 Skiba A. 94 Słowik M. 51 Smirnov A.Yu. 78 119 122 Sofińska-Chmiel W. 120 121 Sprakel L.M.J. 41 Štĕpánková M. 130 Stobiński L. 47 Sulaberidze G.A. 78 119 122 Svinyarov I. 66 Szajnecki Ł. 90 T Tarasiuk B. 138 Targońska S. 117 Tavernier S. 63 Tehrani K.A. 63 Tekneci E. 140 Trochimczuk A.W. 101 103 Turan G.T. 118 140 Turczyn R. 86 87 Turek M. 51 U Ueda T. 107 Ueda Y. 123 Usta H. 118 V Visa A. 124 125 Voda R. 126 127 W Wawrzkiewicz M. 128 129

Weidlich T. 75 130 Wejman-Gibas K. 108 131 Wessling M. 45 Wickramasinghe S.R. 27 Witt K. 132 Wiśniewski M. 35 Wiśniewska M. 129 Wolska J. 133 134 Wołowicz A. 135 136 Wójcik G. 137 138 Y Yildiz G. 139 140 Yoshizuka K. 33 Z Zakrzewska-Kołtuniewicz G. 104 105 Zarko V.I. 129 Zawierucha I. 97 141 Zdybał D. 93 Zeng S. 78 119 122 Zhao L. 142

S18

157

TRIPODAL POLYAMINE – AMBIVALENT RECEPTORS FOR CATION AND ANION EXTRACTION

Marco Wenzel, Karsten Gloe and Jan J. Weigand

TU Dresden, Chemistry and Food Chemistry, Inorganic Molecular Chemistry,

01062 Dresden, Germany e-mail: Marco.Wenzel@tu-dresden.de

Tripodal polyamines based on the tris(2-aminoethyl)amine (tren) platform are useful complexing agents for cations (I) or anions (II) depending on the pH of the solution (1,2). The binding properties of such compounds can be tuned by the introduction of aromatic spacers and potential donor blocks into the molecule. A series of substituted tren derivatives were synthesised and characterised. Here we present results of solvent extraction and liquid membrane studies for various transition metal cations, halides and oxoanions. The influence of selected parameters on the changing coordination behaviour of the investigated ligands will be discussed using additional results of 1H NMR and X-ray structure studies of cation and anion complexes. Further, first results of new heteroditopic ligands of a comparable tripodal structure as potential receptors for simultaneous binding and extraction of cations and anions are presented.

I II References 1. A.G. Blackman, Polyhedron, 24 (2005) 1-39. 2. K. Wichmann, et al., Coord. Chem. Rev., 250 (2006) 2987-3003.